TW202105086A - Process liquid, and method for forming pattern - Google Patents

Abstract

The present invention addresses the problem of providing a treatment liquid for patterning a resist film and a pattern forming method which are capable of suppressing both the occurrence of pattern collapse and film loss in an exposed portion. A treatment liquid for patterning a resist film according to the present invention is used for performing at least one among development and washing on a resist film obtained from an actinic ray-sensitive or radiation-sensitive composition, and includes an organic solvent, the treatment liquid comprising a first organic solvent satisfying a predetermined condition and a second organic solvent satisfying a predetermined condition.

Description

Treatment liquid, pattern forming method

The present invention relates to a treatment liquid for forming a resist film pattern and a pattern forming method. In more detail, the present invention relates to a processing liquid used in semiconductor manufacturing steps such as IC (Integrated Circuit), circuit substrates such as liquid crystals and thermal heads, and other lithography steps in induction etching processing. And pattern forming method.

In the past, in the manufacturing process of semiconductor devices such as IC (Integrated Circuit) and LSI (Large Scale Integrated circuit), microfabrication was performed by using resist composition lithography. In recent years, with the increasing integration of integrated circuits, it is required to form ultra-fine patterns in the sub-micron area and the quarter-micron area. Following this, the exposure wavelength also tends to be shorter, such as from g-rays to i-rays, and further to KrF excimer lasers. Moreover, in addition to excimer laser light, the development of lithography using electron beam, X-ray or EUV light (Extreme Ultra Violet, extreme ultraviolet) is also being promoted. In this type of lithography, after forming a film from a resist composition (also known as a sensitizing ray or radiation-sensitive composition, or a chemically amplified resist composition), the resulting film is Perform development or wash the developed film with a rinse solution. For example, Patent Document 1 discloses that an organic treatment liquid containing a mixture of a first organic solvent and a second organic solvent selected from a ketone solvent and an ester solvent is used as a developer.

[Patent Document 1] JP 2012-181523 A

In recent years, with the increasing integration of integrated circuits, it is required to use resist compositions (sensitizing rays or radiation-sensitive compositions) to form fine patterns. In the formation of such fine patterns, with the miniaturization, the distance between the patterns becomes narrower, which generates a strong capillary force and is likely to cause "pattern collapse" when forming L/S (line and space) patterns. "The problem. Moreover, with the miniaturization, the film thickness of the pattern also tends to become thinner. Therefore, it is more remarkably required than ever to solve the performance degradation of the pattern caused by the "film deterioration of the exposed part" during the development process and the rinsing process. In other words, there is a need for a developer and rinse solution that can simultaneously solve the pattern collapse and the film loss of the exposed portion.

The present invention was made in view of the above problems, and its subject is to provide a resist film patterning treatment solution and a pattern forming method that can simultaneously suppress pattern collapse and film loss in the exposed portion.

The inventors of the present invention conducted intensive studies on the above-mentioned problems and found that the above-mentioned problems can be solved by the following configuration, and completed the present invention.

[1] A treatment solution used for at least one of developing and cleaning a resist film obtained from a sensitizing ray or a radiation-sensitive composition, and containing an organic solvent for patterning a resist film A liquid containing: a first organic solvent that satisfies the following condition A and a second organic solvent that satisfies the following condition B. Condition A: The SP value is 18.7 MPa ^1/2 or less, and the ΔP represented by the following formula (1) is a hydrocarbon solvent, ether solvent, or ester solvent of 15.0 or less, or the SP value is 18.7 MPa ^1/2 Hereinafter, the ketone-based solvent whose ΔP represented by the following formula (1) is 20.0 or less. Condition B: An alcohol solvent with an SP value of 19.0 MPa ^1/2 or more and a ClogP of 1.6 or more, or an SP value of 19.0 MPa ^{1 1/2} or more, ΔH represented by the following formula (2) of 20.0 or more, and containing Ester solvent with two or more carbonyl groups. Formula (1): ΔP =δp/(δd+δp+δh)×100 Formula (2): ΔH =δh/(δd+δp+δh)×100 In formulas (1) and (2), δd represents Han The dispersion term of the Sen solubility parameter. δp represents the polarity term of the Hansen solubility parameter. δh represents the hydrogen bond term of the Hansen solubility parameter. [2] The treatment liquid according to [1], wherein in the condition B, the alcohol-based solvent includes an acyclic alcohol-based solvent, and the ester-based solvent includes an acyclic ester-based solvent. [3] The treatment liquid according to [2], wherein the acyclic ester-based solvent contains one or more selected from the group consisting of ethyl acetate, dimethyl malonate, pyruvate and diethyl oxalate . [4] The treatment liquid according to [2], wherein the acyclic alcohol-based solvent contains selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1- Hexanol, 3-ethyl-3-pentanol, 2,6-dimethyl-4-heptanol, 2-ethyl-1-hexanol, 1-heptanol, 2-octanol, 1-octanol And one or more of 1-hexanol. [5] The treatment liquid according to [2], wherein the acyclic alcohol-based solvent contains any one or more of 2,6-dimethyl-4-heptanol and 3-octanol. [6] The treatment liquid according to [2], wherein the acyclic alcohol-based solvent has a triple bond in the molecule. [7] The treatment liquid according to [6], wherein the acyclic alcohol-based solvent contains a solvent selected from the group consisting of 1-octyn-3-ol and 3,5-dimethyl-1-hexyn-3-ol , 1-heptyn-3-ol and 7-octyn-1-ol. [8] The treatment liquid according to any one of [1] to [7], wherein in the first organic solvent, the hydrocarbon-based solvent contains a hydrocarbon-based solvent having 7 or more carbon atoms. [9] The treatment liquid according to any one of [1] to [8], wherein in the first organic solvent, the hydrocarbon-based solvent contains a solvent selected from the group consisting of ethylcyclohexane, symmetric trimethylbenzene, 1,5- At least one of cyclooctadiene, undecane, and decane. [10] The treatment liquid according to any one of [1] to [9], wherein in the first organic solvent, the ether-based solvent contains selected from the group consisting of amyl ethers, butyl ethers, and diisopropyl ethers At least one or more. [11] The treatment liquid according to any one of [1] to [10], wherein in the first organic solvent, the ether-based solvent contains at least one of diisoamyl ether and diisobutyl ether. [12] The treatment liquid according to any one of [1] to [11], wherein in the first organic solvent, the ester-based solvent contains a solvent selected from the group consisting of isobutyl isobutyrate, butyl butyrate, 2- At least one of methyl-valerate ethyl, hexyl acetate, isobutyl butyrate, and butyl isobutyrate. [13] The treatment liquid according to any one of [1] to [12], wherein in the first organic solvent, the ketone-based solvent contains at least one of diisobutyl ketone and 3-octanone. [14] The treatment liquid according to any one of [1] to [13], wherein the treatment liquid is a rinse liquid. [15] The treatment liquid according to any one of [1] to [14], wherein the sensitizing radiation or radiation-sensitive composition includes a resin having a repeating unit represented by the general formula (1) described later. [16] A pattern forming method, comprising: a resist film forming step, using sensitizing rays or a radiation-sensitive composition to form a resist film; an exposure step, exposing the above resist film; and a processing step, by [1] The processing liquid described in any one of [14] processes the exposed resist film. [17] A pattern forming method, comprising: a resist film forming step, using sensitizing rays or a radiation-sensitive composition to form a resist film; an exposing step, exposing the above resist film; and a processing step, which will go through The exposed resist film is processed. In the pattern forming method, the processing step includes: a developing step, which is developed by a developer; and a washing step, which is washed by a washing liquid, and the washing liquid is [1]~ [14] The treatment liquid of any one of. [18] The pattern forming method according to [17], wherein the developer contains an ester solvent. [19] The pattern forming method according to [18], wherein the ester-based solvent is selected from the group consisting of butyl acetate, pentyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate , Hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, butyl butyrate, butyl isobutyrate and isobutyl isobutyrate. [20] The pattern forming method according to any one of [16] to [19], wherein the sensitizing radiation or radiation-sensitive composition includes a resin having a repeating unit represented by the general formula (1) described later. [Effects of the invention]

According to the present invention, it is possible to provide a treatment solution for patterning a resist film and a pattern forming method capable of simultaneously suppressing the occurrence of pattern collapse and film loss in the exposed portion.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be completed based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In the label of the group (atomic group) in this specification, as long as it does not violate the purpose of the present invention, the label not labeled with substituted and unsubstituted also includes groups without substituents and groups with substituents. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl). In addition, the "organic group" in this specification means a group containing at least one carbon atom. The “actinic rays” or “radiation rays” in this specification means, for example, the bright-line spectrum of mercury lamps, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays and electron beams (EB : Electron Beam) etc. "Light" in this specification means actinic rays or radiation. The "exposure" in this manual, unless otherwise specified, not only includes the use of the obvious spectrum of mercury lamps, extreme ultraviolet, extreme ultraviolet, X-ray and EUV light represented by excimer lasers, but also the use of electrons Description of particle beams such as beams and ion beams. In this specification, "～" is used in the meaning including the numerical value described before and after it as a lower limit and an upper limit. Unless otherwise specified, the bonding direction of the divalent groups marked in this specification is not limited. For example, when Y in the compound represented by the general formula "X-Y-Z" is -COO-, Y may be -CO-O- or -O-CO-. In addition, the above-mentioned compound may be "X-CO-O-Z" or "X-O-CO-Z".

In this specification, (meth)acrylate means acrylate and methyl acrylate, and (meth)acryl means acryl and methacryl. In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion (also called molecular weight distribution) (Mw/Mn) of the resin are defined as yes, based on GPC (Gel Permeation Chromatography: gel permeation layer) Analysis) GPC measurement (solvent: tetrahydrofuran (THF); flow rate (sample injection volume): 10μL; column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION; column temperature: 40℃; Flow rate: 1.0mL/min; Detector: Refractive Index Detector (Refractive Index Detector) conversion value of polystyrene.

The acid dissociation constant pKa in this specification means the acid dissociation constant pKa in an aqueous solution, and is defined in the Handbook of Chemistry (II) (Revised 4th Edition, 1993, The Chemical Society of Japan, Maruzen. Inc.), for example. The lower the value of the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in the aqueous solution can be actually measured by measuring the acid dissociation constant at 25° C. using an infinitely diluted aqueous solution. Alternatively, the following software package 1 can be used to obtain values in a database based on Hammett's substituent constants and well-known literature values through calculations. The pKa values described in this manual all represent the values obtained by calculation using the package software. Package 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

1Å is 1×10 ^-10 m.

In this specification, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

[Treatment liquid] The treatment liquid of the present invention is used to process at least one of developing and cleaning a resist film obtained from a sensitizing radiation or a radiation-sensitive composition (hereinafter also referred to as "resist composition") and contains Organic solvent resist film patterning treatment liquid. The treatment liquid of the present invention contains a first organic solvent that satisfies the condition A described later and a second organic solvent that satisfies the condition B described later.

EUV light (wavelength 13.5 nm) has a shorter wavelength than ArF excimer laser light (wavelength 193 nm), for example, and therefore has the following feature: in the exposure of the resist film, when the sensitivity is the same, the number of incident photons is small. As a result, in the lithography performed by EUV light, the probabilistic "photon shot noise" caused by the scattered number of photons has a greater influence, and it becomes one of the factors that produce high-polarity residues such as polymer residues. . This high-polarity residue component becomes a cause of defects on the pattern (especially, bridging defects). This time, the inventors of the present invention found that the protic polar solvents and ester solvents with high hydrogen-bonding interaction energy are effective for reducing the components of highly polar residues. However, if these solvents are used alone, the volatility is lower. In particular, it becomes a factor that deteriorates the resolution in the dense pattern (in other words, causes the pattern in the dense pattern to collapse). The inventors of the present invention conducted further studies based on the above-mentioned research results, and the results confirmed that the formation of pattern defects (especially, bridging defects) and pattern collapse can be suppressed by the treatment liquid containing the above-mentioned first organic solvent and the above-mentioned second organic solvent. In addition, the film loss of the exposed part will also be suppressed. In addition, the above-mentioned first organic solvent mainly plays a role in reducing high-polarity residue components.

In addition, it was confirmed that in the above-mentioned treatment liquid, when a solvent with more excellent volatility is used as the second organic solvent to increase the volatility of the whole treatment liquid, the drying time after treatment (for example, rinsing treatment) by the above-mentioned treatment liquid can be reduced. , And the suppression effect of pattern collapse in dense patterns becomes more significant.

Hereinafter, first, the first organic solvent and the second organic solvent will be described separately.

[First Organic Solvent] The treatment liquid of the present invention contains a first organic solvent that satisfies the following condition A. Condition A: The SP value is 18.7MPa ^1/2 or less, and the ΔP represented by the following formula (1) is a hydrocarbon solvent, ether solvent, or ester solvent (hereinafter, also referred to as "solvent A-1 ".), or, a ^{ketone-based solvent having an SP value of 18.7 MPa 1/2} or less and a ΔP of 20.0 or less represented by the following formula (1) (hereinafter, also referred to as "solvent A-2"). Formula (1): ΔP = δp/(δd+δp+δh)×100 In formula (1), δd represents the dispersion term of the Hansen solubility parameter. δp represents the polarity term of the Hansen solubility parameter. δh represents the hydrogen bond term of the Hansen solubility parameter. Among them, from the viewpoint of further suppressing pattern collapse, the smaller ΔP and the larger ΔD (represented by δd/(δd+δp+δh)) is more preferable.

<SP value> The "SP value" in this manual is calculated using the Fedors method described in "PROPERTIES OF POLYMERS, second edition, published in 1976" and based on the following formula. In addition, unless otherwise specified, the unit of SP value is MPa ^1/2 . SP value (Fedors method)=[(sum of cohesive energy of each substituent)/(sum of volume of ^{each substituent)] 0.5} The parameters of each substituent (cohesive energy and volume) except for "PROPERTIES OF POLYMERS" In addition to the values recorded in the second edition, published in 1976, document values and other records can be used. In addition, the smaller the SP value, the lower the polarity of the solvent. That is, the smaller the SP value, the lower the affinity of the solvent with the resist film, and therefore the excessive penetration into the resist film can be suppressed, that is, the swelling can be suppressed.

<Hansen solubility parameter> The Hansen solubility parameter (δ) is defined by the three-dimensional parameters (δd, δp, δh), and is expressed by the following formula (3). In addition, the details related to the Hansen solubility parameters described in "PROPERTIES OF POLYMERS" (Author: DWVAN KREVELEN, Publisher: ELSEVIER SCIENTIFIC PUBLISHING COMPANY, 1989 annual circulation, 5th edition). Equation (3) δ ² = (δd) ² + (δp) ² + (δh) ² δd represents the dispersion term (also known as the London dispersion power term.). δp represents the polar term (also known as the molecular polar term.). δh represents a hydrogen bond term. δd, δp, and δh can be calculated using the program HSPiP (Hansen Solubility Parameters in Practice: Hansen Solubility Parameters in Practice) developed by the team of Dr. Hansen who proposed the Hansen solubility parameters. In addition, δd, δp, and δh in this specification are values calculated using HSPiP 5th Edition 5.2.06.

In this specification, the meanings of δd, δp, and δh in the above-mentioned formula (1) and the following formula (2) are the same as δd, δp, and δh in the above-mentioned formula (3), respectively.

<Solvent A-1> The solvent A-1 is a ^{hydrocarbon solvent, an ether solvent, or an ester solvent having an SP value of 18.7 MPa 1/2} or less and ΔP represented by the above formula (1) of 15.0 or less. By containing the solvent A-1 in the treatment liquid of the present invention, pattern collapse of the formed pattern is suppressed, and film deterioration in the exposed portion is suppressed. In addition, the lower limit of the SP value is, for example, 14.0 MPa ^1/2 or more, and the lower limit of ΔP is, for example, 0.0 or more. Hereinafter, the solvent A-1 will be described.

(Hydrocarbon solvent 18.7MPa ^1/2 or less and a SP value of 15.0 or less of ΔP) as the SP value of ΔP 18.7MPa ^1/2 or less and 15.0 or less of the hydrocarbon-based solvent, and the SP value as long as the value satisfies the predetermined ΔP, the It may be any of an aliphatic hydrocarbon-based solvent and an unsaturated aliphatic hydrocarbon-based solvent. The number of double bonds or triple bonds possessed by the unsaturated hydrocarbon solvent is not particularly limited, and it may be located at any position in the hydrocarbon chain. In addition, when the unsaturated hydrocarbon solvent has a double bond, the cis isomer and the trans isomer may be mixed. In addition, as the carbon number of the above-mentioned hydrocarbon-based solvent, from the viewpoint of further improving the suppression of pattern collapse of the formed pattern and/or the suppression of film loss in the exposed portion, 7 or more is preferable. The upper limit is not particularly limited. For example, 16 or less can be mentioned, preferably 14 or less, and more preferably 12 or less.

Specific examples of hydrocarbon solvents having an SP value of 18.7 MPa ^1/2 or less and a ΔP of 15.0 or less are shown below. In addition, the unit of each numerical value is omitted. Examples include ethyl cyclohexane (SP value: 16.4, ΔP: 0.0), symmetric trimethylbenzene (SP value: 18.6, ΔP: 3.1), 1,5-cyclooctadiene (SP value: 14.3, ΔP: 12.9) , Undecane (SP value: 15.9, ΔP: 0.0) and decane (SP value: 15.8, ΔP: 0.0).

As the above-mentioned hydrocarbon solvent, among them, ethylcyclohexane (SP value: 16.4, ΔP: 0.0), symmetric trimethylbenzene (SP value: 18.6, ΔP: 3.1), 1,5-cyclooctadiene (SP Value: 14.3, ΔP: 12.9), undecane (SP value: 15.9, ΔP: 0.0) and decane (SP value: 15.8, ΔP: 0.0) are preferred, selected from ethylcyclohexane, symmetric Trimethylbenzene, 1,5-cyclooctadiene, and undecane are more preferable, and those selected from ethylcyclohexane, symmetric trimethylbenzene and 1,5-cyclooctadiene are more preferable.

(18.7MPa ^1/2 or less and a SP value ΔP is less of an ether-based solvent, 15.0) as the SP value of ΔP 18.7MPa ^1/2 or less and 15.0 or less of an ether-based solvent, and the SP value as long as the value satisfies the predetermined ΔP, the There are no special restrictions. In addition, the ether-based solvent means a solvent having at least one ether bond in the molecule. For example, when the solvent has an ether bond and a functional group other than the ether bond, as long as the SP value and ΔP satisfy the predetermined value, it is regarded as the ether-based solvent of the solvent A-1.

As the above-mentioned ether-based solvent, ^{an alcohol-based solvent having an SP value of 18.7 MPa 1/2} or less, ΔP of 13.5 or less, and ΔD of 73.0 or more is preferable. In addition, the upper limit of ΔD is, for example, 100.0 or less.

Specific examples of ether solvents having an SP value of 18.7 MPa ^1/2 or less and ΔP of 15.0 or less are shown below. In addition, the unit of each numerical value is omitted. Examples include dipentyl ether (alternative name: di-n-pentyl ether, SP value: 16.2, ΔP: 14.3) and diisoamyl ether (SP value: 15.6, ΔP: 12.1) and other pentyl ethers; dibutyl ether (alternative name: two Butyl ethers such as n-butyl ether, SP value: 15.9, ΔP: 14.2) and diisobutyl ether (SP value: 15.2, ΔP: 12.2); and diisopropyl ether (SP value: 14.6, ΔP: 14.9).

As the ether solvent, among them, diisoamyl ether (SP value: 15.6, ΔP: 12.1) or diisobutyl ether (SP value: 15.2, ΔP: 12.2) is preferable, and diisoamyl ether is more preferable.

(18.7MPa ^1/2 or less and a SP value ΔP is 15.0 or less of the ester solvent) as 18.7MPa ^1/2 or less and a SP value of 15.0 or less of ΔP ester solvents, and long ΔP SP value satisfies the predetermined value, There are no special restrictions. In addition, the ester-based solvent means a solvent having one or more ester bonds in the molecule. For example, when the solvent has an ester bond and a functional group other than the ester bond, as long as the SP value and ΔP satisfy a predetermined value, it is regarded as the ester-based solvent of the solvent A-1.

Specific examples of ester solvents having an SP value of 17.8 MPa ^1/2 or less and ΔP of 15.0 or less are shown below. In addition, the unit of each numerical value is omitted. Examples include isobutyl isobutyrate (SP value: 17.1, ΔP: 14.2), butyl butyrate (SP value: 17.8, ΔP: 12.0), 2-methyl-ethyl valerate (SP value: 17.4, ΔP : 14.8), hexyl acetate (SP value: 17.8, ΔP: 11.8), isobutyl butyrate (SP value: 16.8, ΔP: 14.3), butyl isobutyrate (SP value: 16.8, ΔP: 14.5), Isobutyl isovalerate (SP value: 17.7, ΔP: 13.1), isoamyl isobutyrate (SP value: 17.7, ΔP: 13.5), and isoamyl acetate (SP value: 17.4, ΔP: 12.2), etc.

As the above-mentioned ester solvent, the carbon number is preferably 8 or more, and the carbon number is 8 or 9 more preferably, selected from isobutyl isobutyrate (SP value: 17.1, ΔP: 14.2), butyl butyrate (SP Value: 17.8, ΔP: 12.0), 2-methyl-ethyl valerate (SP value: 17.4, ΔP: 14.8), hexyl acetate (SP value: 17.8, ΔP: 11.8), isobutyl butyrate (SP Value: 16.8, ΔP: 14.3), butyl isobutyrate (SP value: 16.8, ΔP: 14.5), isobutyl isovalerate (SP value: 17.7, ΔP: 13.1), isoamyl isobutyrate (SP Value: 17.7, ΔP: 13.5) and isoamyl acetate (SP value: 17.4, ΔP: 12.2) are more preferred, selected from isobutyl isobutyrate, butyl butyrate, 2-methyl-pentane Ethyl acetate, hexyl acetate, isobutyl butyrate, and butyl isobutyrate are particularly preferred. From the viewpoint of carbon number 8 or more and smaller ΔP, butyl butyrate is the most preferred.

As the above-mentioned ester solvent, from the viewpoint of further suppressing pattern collapse of the formed pattern, ΔD is preferably 64.5 MPa ^1/2 or more.

<Solvent A-2> The solvent A-2 is a ^{ketone-based solvent having an SP value of 17.8 MPa 1/2} or less and ΔP represented by the following formula (1) of 20.0 or less. By containing the solvent A-2 in the treatment liquid of the present invention, the pattern collapse of the formed pattern is suppressed, and the film loss in the exposed portion is suppressed. In addition, the lower limit of the SP value is, for example, 17.0 MPa ^1/2 or more, and the lower limit of ΔP is, for example, 0.0 or more. Hereinafter, the solvent A-2 will be described.

(1) represented by the [Delta] P (ketone-based solvents represented by the following formula and an SP value of [Delta] P (1) 17.8MPa ^1/2 or less of 20.0 or less) and the following formula as a SP value of less 17.8MPa ^1/2 If the ketone solvent is 20.0 or less, as long as the SP value and ΔP satisfy the specified value, there is no particular limitation. In addition, the ketone-based solvent means a solvent having at least one ketone group in the molecule. For example, when the solvent has a ketone group and a functional group other than the ketone group, as long as the SP value and ΔP satisfy the predetermined value, it is regarded as the ketone solvent of the solvent A-2.

Specific examples of ketone solvents having an SP value of 17.8 MPa ^1/2 or less and ΔP of 20.0 or less are shown below. In addition, the unit of each numerical value is omitted. Examples include diisobutyl ketone (SP value: 17.4, ΔP: 18.6) and 3-octanone (SP value: 17.5, ΔP: 18.1).

As the solvent A, the solvent A-1 selected from hydrocarbon solvents and ether solvents is preferred from the viewpoint of further suppressing pattern collapse and/or the viewpoint of further suppressing film loss in the exposed portion.

In the treatment liquid of the present invention, the first organic solvent may be used alone, or two or more of them may be used in combination.

[Second Organic Solvent] The treatment liquid of the present invention contains a second organic solvent that satisfies the following condition B. Condition B: An alcoholic solvent with an SP value of 19.0 MPa ^1/2 or more and a ClogP of 1.6 or more (hereinafter, also referred to as "solvent B-1"), or an SP value of 19.0 MPa ^{1 1/2} or more and the following The ΔH represented by the formula (2) is an ester-based solvent containing two or more carbonyl groups (hereinafter, also referred to as "solvent B-2") of 20.0 or more. Formula (2): ΔH =δh/(δd+δp+δh)×100

＜SP value, Hansen solubility parameter＞ The definition of SP value and the definition of Hansen solubility parameters (δd, δp, δh) are as described above.

＜ClogP＞ In this specification, the ClogP of the solvent is the value obtained by calculating the common logarithm logP of the partition coefficient P for 1-octanol and water. Regarding the methods and software used in the calculation of ClogP values, known ones can be used. Unless otherwise specified, the ClogP program incorporated in PerkinElmer, Inc.'s ChemDraw ver 16.0.1.4 (77) is used in this manual. In addition, a high ClogP indicates that the affinity between water molecules and hydrophobic molecules (1-octanol as an index) is higher than that of water molecules.

<Solvent B-1> The solvent B-1 is ^{an alcohol solvent having an SP value of 19.0 MPa 1/2} or more and a ClogP of 1.6 or more. By containing the solvent B-1, the processing liquid of the present invention has excellent suppression of defects (especially, bridging defects) of the formed pattern. In addition, the upper limit of the SP value is, for example, 21.0 MPa ^1/2 or less, and the upper limit of ClogP is, for example, 4.0 or less. As the solvent B-1, among them, ^{an alcohol-based solvent having an SP value of 19.0 MPa 1/2} or more and a ClogP of more than 1.6 is preferable.

As an alcohol-based solvent having an SP value of 19.0 MPa ^1/2 or more and a ClogP of 1.6 or more, as long as the SP value and ClogP satisfy predetermined values, there is no particular limitation. In addition, the alcohol-based solvent means a solvent having at least one alcohol group in the molecule. For example, when the solvent has an alcohol group and a functional group other than the alcohol group, as long as the SP value and ΔP satisfy the predetermined value, it is regarded as the alcohol solvent of the solvent B-1.

Specific examples of alcoholic solvents having an SP value of 19.0 MPa ^1/2 or more and a ClogP of 1.6 or more are shown below. In addition, the unit of each numerical value is omitted. Examples include 3,7-dimethyl-3-octanol (SP value: 19.7, ClogP: 3.5), 3,5,5-trimethyl-1-hexanol (SP value: 20.5, ClogP: 3.1), 3-ethyl-3-pentanol (SP value: 20.8, ClogP: 2.1), 2,6-dimethyl-4-heptanol (SP value: 19.9, ClogP: 3.0), 2-ethyl-1- Hexanol (SP value: 20.7, ClogP: 2.8), 1-heptanol (SP value: 21.4, ClogP: 2.4), 2-octanol (SP value: 20.7, ClogP: 2.7), 1-octanol (SP value : 21.0, ClogP: 4.0), 1-hexanol (SP value: 21.9, ClogP: 2.4), 3-octanol (SP value: 20.7.0, ClogP: 2.7), 1-octyn-3-ol (SP Value: 26.9, ClogP: 2.1), 3,5-dimethyl-1-hexyn-3-ol (SP value: 26.1, ClogP: 1.8), 1-heptyn-3-ol (SP value: 20.5, ClogP: 1.6) and 7-octyn-1-ol (SP value: 20.3, ClogP: 1.6) and so on.

As the above-mentioned alcohol-based solvent, an acyclic alcohol-based solvent is preferable from the viewpoint of suppressing the dissolution of the resist in the exposed portion. The acyclic alcohol-based solvent includes, for example, one or more selected from the solvents belonging to the first group, one or more selected from the solvents belonging to the second group, or one or more selected from the solvents belonging to the third group as shown below One or more of the group of solvents is preferable. ･Group 1: 3,7-dimethyl-3-octanol (SP value: 19.7, ClogP: 3.5), 3,5,5-trimethyl-1-hexanol (SP value: 20.5, ClogP : 3.1), 3-ethyl-3-pentanol (SP value: 20.8, ClogP: 2.1), 2,6-dimethyl-4-heptanol (SP value: 19.9, ClogP: 3.0), 2-ethyl 1-hexanol (SP value: 20.7, ClogP: 2.8), 1-heptanol (SP value: 21.4, ClogP: 2.4), 2-octanol (SP value: 20.7, ClogP: 2.7), 1-octyl alcohol Alcohol (SP value: 21.0, ClogP: 4.0) and 1-hexanol (SP value: 21.9, ClogP: 2.4). As a solvent of the first group, among them, 3,7-dimethyl-3-octanol, 3,5, 5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6-dimethyl-4-heptanol, 2-ethyl-1-hexanol and 2-octanol are more Best, 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6-dimethyl-4- Heptanol and 2-octanol are more preferable.

･Group 2: 2,6-Dimethyl-4-heptanol (SP value: 19.9, ClogP: 3.0) and 3-octanol (SP value: 20.7.0, ClogP: 2.7). Among the solvents of the second group, 3-octanol is preferred from the viewpoint of being able to further suppress pattern collapse and/or from the viewpoint of being able to further suppress film loss in the exposed portion.

･Group 3: Acyclic alcohol solvents with triple bonds in the molecule. The acyclic alcohol-based solvent having a triple bond in the molecule is not particularly limited. The number of triple bonds possessed by the alcohol-based solvent is not particularly limited. As the above-mentioned alcohol solvent, a linear or branched aliphatic alcohol solvent is preferred. As the carbon number of the above-mentioned alcohol-based solvent, from the viewpoint of further improving the suppression of pattern collapse of the formed pattern and/or the suppression of film loss of the exposed portion, 7 or more is preferable. The upper limit is not particularly limited. For example, 14 or less may be mentioned, preferably 12 or less, and more preferably 10 or less. As the third group of solvents, among them, 1-octyn-3-ol (SP value: 26.9, ClogP: 2.1 ), 3,5-dimethyl-1-hexyn-3-ol (SP value: 26.1, ClogP: 1.8), 1-heptyn-3-ol (SP value: 20.5, ClogP: 1.6) and 7- Octyn-1-ol (SP value: 20.3, ClogP: 1.6) is preferred.

<Solvent B-2> The solvent B-2 is ^{an ester-based solvent having an SP value of 19.0 MPa1 1/2} or more and a ΔH of 20.0 or more, and containing two or more carbonyl groups. By containing the solvent B-2, the processing liquid of the present invention has excellent suppression of defects (especially, bridging defects) of the formed pattern. In addition, the upper limit of the SP value is, for example, 21.0 MPa ^1/2 or less, and the upper limit of ΔH is, for example, 30.0 or less.

As an ester solvent having an SP value of 19.0 MPa1 ^1/2 or more and ΔH of 20.0 or more, and containing two or more carbonyl groups, as long as the SP value and ΔH satisfy the specified values and contain two or more carbonyl groups, there is no particular limitation. In addition, the ester-based solvent means a solvent having at least one ester bond in the molecule. For example, when the solvent has an ester bond and a functional group other than the ester bond, as long as the SP value and ΔH satisfy predetermined values and contain two or more carbonyl groups, it is regarded as an ester solvent of solvent B-2. In addition, the above-mentioned carbonyl group may be a carbonyl group contained in an ester bond.

The following shows a specific example of an ester solvent having an SP value of 19.0 MPa1 ^1/2 or more and a ΔH of 20.0 or more, and containing two or more carbonyl groups. In addition, the unit of each numerical value is omitted. Examples include ethyl acetate (SP value: 20.7, ΔH: 25.9), dimethyl malonate (SP value: 20.6, ΔH: 29.1), methyl pyruvate (SP value: 21.6, ΔH: 24.5) and Pyruvate esters such as ethyl pyruvate (SP value: 21.1, ΔH: 23.3), and diethyl oxalate (SP value: 21.75, ΔH: 26.7), etc.

As the above-mentioned ester solvent, from the viewpoint of both suppressing the dissolution of the resist in the exposed area and removing the residue, an acyclic ester solvent is preferred, selected from ethyl acetate (SP value: 20.7, ΔH: 25.9) , Dimethyl malonate (SP value: 20.6, ΔH: 29.1), methyl pyruvate (SP value: 21.6, ΔH: 24.5), ethyl pyruvate (SP value: 21.1, ΔH: 23.3) and two oxalate Ethyl acetate (SP value: 21.75, ΔH: 26.7) is preferred. From the viewpoint that pattern collapse can be further suppressed and/or the film loss of the exposed part can be further suppressed, ethyl acetylacetate, methyl pyruvate Ester or ethyl pyruvate is more preferred.

As the solvent B, the solvent B-1 is preferred from the viewpoint of being able to further suppress pattern collapse and/or from the viewpoint of being able to further suppress film deterioration in the exposed portion.

In the treatment liquid of the present invention, one kind of second organic solvent may be used alone, or two or more kinds may be used in combination.

[Contents of the first organic solvent and the second organic solvent] The content of the first organic solvent is preferably 10% by mass or more relative to the total mass of the treatment liquid, more preferably 20% by mass or more, more preferably 40% by mass or more, and particularly preferably 60% by mass or more. In addition, the upper limit is not particularly limited. For example, 95% by mass or less is preferable, 90% by mass or less is more preferable, and 80% by mass or less is more preferable. The content of the second organic solvent is preferably 10% by mass or more with respect to the total mass of the treatment liquid, more preferably 20% by mass or more, more preferably 40% by mass or more, and particularly preferably 60% by mass or more. In addition, the upper limit is not particularly limited. For example, it is preferably 95% by mass or less, more preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 60% by mass or less. The content of the first organic solvent relative to the total content of the first organic solvent and the second organic solvent is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more To be even more preferable, 50% by mass or more is particularly preferable, and 60% by mass or more is most preferable. Moreover, as an upper limit, 90 mass% or less is preferable, 80 mass% or less is more preferable, 60 mass% or less is more preferable, and 50 mass% or less is especially preferable.

In the treatment liquid of the present invention, the total content of the first organic solvent and the second organic solvent relative to the total mass of the treatment liquid is preferably 95.0% by mass or more, more preferably 98.0% by mass or more, and 99.0% by mass or more More preferably, 99.5% by mass or more is particularly preferable, and 99.9% by mass or more is most preferable. In addition, the upper limit is, for example, 100% by mass.

[Preferable aspects of the first organic solvent and the second organic solvent] Hereinafter, specific preferable aspects of the first organic solvent and the second organic solvent will be described. In addition, as the best combination of the first organic solvent and the second solvent, the first organic solvent is solvent A-1 selected from hydrocarbon solvents and ether solvents, and the second organic solvent is alcohol solvent B-1. The way.

<The case where the treatment liquid contains the ether solvent of solvent A-1 as the first organic solvent and the alcohol solvent of solvent B-1 as the second organic solvent> When the treatment liquid contains the ether solvent of solvent A-1 as the first organic solvent and the alcohol solvent of solvent B-1 as the second organic solvent, the first organic solvent and the second organic solvent satisfy the following A1 to the following At least one of A8 is preferable. A1: The second organic solvent contains selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6 -One or more of dimethyl-4-heptanol, 2-ethyl-1-hexanol and 2-octanol or any of 2,6-dimethyl-4-heptanol and 3-octanol One or more, or an acyclic alcohol solvent with triple bonds in the molecule (preferably selected from 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1 -More than one of heptyn-3-ol and 7-octyn-1-ol). In A1, the second organic solvent contains selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2, One or more of 6-dimethyl-4-heptanol and 2-octanol, or any one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or containing three Non-cyclic alcohol solvent (preferably selected from 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-heptyn-3-ol and 7 -At least one of octyne-1-ol) is preferred. A2: ΔP of the first organic solvent is 13.5 or less and ΔD is 73.0 or more (preferably diisoamyl ether). A3: The ΔP of the first organic solvent is 13.5 or less and the ΔD is 73.0 or more, the second organic solvent contains 3,7-dimethyl-3-octanol, and the content of the first organic solvent is relative to the first organic solvent and the first organic solvent. The total content of the two organic solvents is 20 to 80% by mass. A4: The ΔP of the first organic solvent is 13.5 or less and the ΔD is 73.0 or more, and the second organic solvent contains any of 3,5,5-trimethyl-1-hexanol and 3-ethyl-3-pentanol And the content of the first organic solvent is 40 to 80% by mass relative to the total content of the first organic solvent and the second organic solvent. A5: The second organic solvent contains 2,6-dimethyl-4-heptanol, and the content of the first organic solvent is 80% by mass or less with respect to the total content of the first organic solvent and the second organic solvent. A6: The second organic solvent is 2-ethyl-1-hexanol, and the content of the first organic solvent is 40% by mass or more with respect to the total content of the first organic solvent and the second organic solvent. A7: The second organic solvent is 2-ethyl-1-hexanol, and the content of the first organic solvent is less than 40% by mass relative to the total content of the first organic solvent and the second organic solvent. A8: ΔP of the first organic solvent is 13.5 or less and ΔD is 73.0 or more, the second organic solvent contains 2-octanol, and the content of the first organic solvent is relative to the sum of the content of the first organic solvent and the second organic solvent 20 to 80% by mass.

<The case where the treatment liquid contains the ether solvent of solvent A-1 as the first organic solvent and the ester solvent of solvent B-2 as the second organic solvent> When the treatment liquid contains the ether solvent of solvent A-1 as the first organic solvent and the ester solvent of solvent B-2 as the second organic solvent, the first organic solvent and the second organic solvent satisfy the following B1 and/or The following B2 is preferable. B1: The content of the first organic solvent is 50% by mass or more (preferably 80% by mass or more) with respect to the total of the contents of the first organic solvent and the second organic solvent. B2: The second organic solvent is ethyl acetate, and the content of the first organic solvent is 80% by mass or more with respect to the total content of the first organic solvent and the second organic solvent.

<The case where the treatment liquid contains the hydrocarbon solvent of solvent A-1 as the first organic solvent and the alcohol solvent of solvent B-1 as the second organic solvent> When the treatment liquid contains a hydrocarbon solvent containing solvent A-1 as the first organic solvent and an alcohol solvent containing solvent B-1 as the second organic solvent, the first organic solvent and the second organic solvent satisfy the following C1 to the following At least one of C6 is preferred. C1: The second organic solvent contains selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2,6 -One or more of dimethyl-4-heptanol and 2-octanol (preferably 2,6-dimethyl-4-heptanol) or including 2,6-dimethyl-4-heptanol and Any one or more of 3-octanol, or an acyclic alcohol solvent containing a triple bond in the molecule (preferably selected from 1-octyn-3-ol, 3,5-dimethyl-1-hexyl) One or more of alkyn-3-ol, 1-heptyn-3-ol and 7-octyn-1-ol). In C1, the second organic solvent contains selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2, One or more of 6-dimethyl-4-heptanol and 2-octanol, or any one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or containing three Non-cyclic alcohol solvent (preferably selected from 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-heptyn-3-ol and 7 -At least one of octyne-1-ol) is preferred. C2: The second organic solvent contains 3,7-dimethyl-3-octanol, and the content of the first organic solvent is 40 to 80% by mass (relative to the total content of the first organic solvent and the second organic solvent). Preferably, it is 60 to 80% by mass). C3: The second organic solvent contains one or more selected from 3,5,5-trimethyl-1-hexanol and 3-ethyl-3-pentanol, and the content of the first organic solvent is relative to that of the first organic solvent. The total content of the solvent and the second organic solvent is 20 to 80% by mass (preferably 40 to 80% by mass). C4: The second organic solvent contains 2-octanol, and the content of the first organic solvent is 20 to 80% by mass relative to the total content of the first organic solvent and the second organic solvent.

C5: The second organic solvent contains 2-ethyl-1-hexanol, and the content of the first organic solvent is less than 40% by mass relative to the total content of the first organic solvent and the second organic solvent. C6; the first organic solvent contains 1,5-cyclooctadiene, the second organic solvent contains 2-ethyl-1-hexanol, and the content of the first organic solvent is relative to that of the first organic solvent and the second organic solvent The total content is less than 40% by mass.

<The case where the treatment liquid contains the hydrocarbon solvent of solvent A-1 as the first organic solvent and the ester solvent of solvent B-2 as the second organic solvent> When the treatment liquid contains a hydrocarbon solvent containing solvent A-1 as the first organic solvent and an ester solvent containing solvent B-2 as the second organic solvent, the first organic solvent and the second organic solvent satisfy the following D1 and/or The following D2 is preferable. D1: The content of the first organic solvent is 50% by mass or more (preferably 80% by mass or more) with respect to the total of the contents of the first organic solvent and the second organic solvent. D2: The second organic solvent is ethyl acetate, and the content of the first organic solvent is 80% by mass or more with respect to the total content of the first organic solvent and the second organic solvent.

<The case where the treatment liquid contains the ester solvent of the solvent A-1 as the first organic solvent and the alcohol solvent of the solvent B-1 as the second organic solvent> The treatment liquid contains the ester of the solvent A-1 as the first organic solvent When the second organic solvent contains an alcoholic solvent of solvent B-1, it is preferable that the first organic solvent and the second organic solvent satisfy at least one of the following E1 to E5. E1: The second organic solvent contains selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2-octyl alcohol One or more of alcohol and 2,6-dimethyl-4-heptanol (preferably 2-octanol or 2,6-dimethyl-4-heptanol) or 2,6-dimethyl-4-heptanol Any one or more of 4-heptanol and 3-octanol, or an acyclic alcohol solvent containing a triple bond in the molecule (preferably selected from 1-octyn-3-ol, 3,5-dimethyl One or more of 1-hexyn-3-ol, 1-heptyn-3-ol and 7-octyn-1-ol). In E1, the second organic solvent contains 2-octanol or contains any one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or contains an acyclic alcohol having a triple bond in the molecule Solvent (preferably selected from 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-heptyn-3-ol and 7-octyn-1-ol One or more of them) is preferred. As E1, the second organic solvent contains any one or more of 2,6-dimethyl-4-heptanol and 3-octanol or an acyclic alcohol solvent with a triple bond in the molecule (preferably selected From more than one of 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-heptyn-3-ol and 7-octyn-1-ol), In addition, the content of the first organic solvent is preferably 60% by mass or more with respect to the total content of the first organic solvent and the second organic solvent. E2: The first organic solvent contains an organic solvent with an SP value of 18.7 MPa ^1/2 or less, and a ΔP of 15.0 or less and a ΔD of 64.5 or more, and the second organic solvent contains 3,7-dimethyl-3-octanol, and The content of the first organic solvent is 40 to 80% by mass with respect to the total content of the first organic solvent and the second organic solvent. E3: The first organic solvent contains an organic solvent with an SP value of 18.7 MPa ^1/2 or less, and a ΔP of 15.0 or less and a ΔD of 64.5 or more, and the second organic solvent contains an organic solvent selected from 3,5,5-trimethyl-1- One or more of hexanol and 3-ethyl-3-pentanol, and the content of the first organic solvent is 20 to 80% by mass relative to the total content of the first organic solvent and the second organic solvent. E4: The first organic solvent contains an organic solvent with an SP value of 18.7 MPa ^1/2 or less, and a ΔP of 15.0 or less and a ΔD of 64.5 or more, and the second organic solvent contains an organic solvent selected from 2-octanol or 2,6-dimethyl One or more of -4-heptanol. E5: The first organic solvent contains an organic solvent with an SP value of 18.7 MPa ^1/2 or less, ΔP of 15.0 or less and ΔD of 64.5 or more, the second organic solvent is 2-ethyl-1-hexanol, and the first organic solvent The content of the solvent is less than 40% by mass relative to the total content of the first organic solvent and the second organic solvent.

<The case where the treatment liquid contains the ketone solvent of solvent A-2 as the first organic solvent and the alcohol solvent of solvent B-1 as the second organic solvent> When the treatment liquid contains the ketone solvent of solvent A-2 as the first organic solvent and the alcohol solvent of solvent B-1 as the second organic solvent, the first organic solvent and the second organic solvent satisfy the following F1 to the following At least one of F4 is preferable. F1: The second organic solvent contains selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2-octyl alcohol One or more of alcohol and 2,6-dimethyl-4-heptanol, or any one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or having a triple bond in the molecule The acyclic alcohol solvent (preferably selected from 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-heptyn-3-ol and 7- One or more of octyn-1-ol). In F1, the second organic solvent contains 2-octanol or contains any one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or contains an acyclic alcohol having a triple bond in the molecule Solvent (preferably selected from 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-heptyn-3-ol and 7-octyn-1-ol One or more of them) is preferred. F2: The second organic solvent contains 3,7-dimethyl-3-octanol, and the content of the first organic solvent is 40 to 80% by mass relative to the total content of the first organic solvent and the second organic solvent. F3: The second organic solvent contains at least one selected from 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol and 2-octanol, and the content of the first organic solvent The total content with respect to the first organic solvent and the second organic solvent is 20 to 80% by mass. F4: The second organic solvent is 2-ethyl-1-hexanol, and the content of the first organic solvent is less than 40% by mass relative to the total content of the first organic solvent and the second organic solvent.

[Other ingredients] The treatment liquid of the present invention only needs to contain at least one of the above-mentioned first organic solvent and the above-mentioned second organic solvent, respectively, and may also contain other components other than the above-mentioned first organic solvent and the above-mentioned second organic solvent.

<Ionic liquid> In addition, the treatment liquid of the present invention may contain the following ionic liquid. In addition, when the treatment liquid contains an ionic liquid, it is considered that the ionic liquid is not contained in the first organic solvent and the second organic solvent. The ionic liquid includes, for example, aromatic ions such as pyridinium ion or imidazolium ion, or aliphatic amine ions such as trimethylhexylammonium ion as cations, and it has NO ₃ ^- and CH ₃ CO ₂ ^{-as anions.} , BF ₆ ^- or PF ₆ ^- ions and organic-based, or _{(CF 3 SO 2) 2 N} -, CF 3 CO 2 -, or CF ₃ SO ₂ ^- containing organic anion of an ionic liquid; quaternary ammonium Salt-based ionic liquids are preferred.

Examples of commercially available ionic liquids include IL-P14 and IL-A2 (the above are manufactured by KOEI CHEMICAL INDUSTRY CO., LTD.); Elegan SS-100, which is a quaternary ammonium salt-based ionic liquid (manufactured by NOF CORPORATION) )Wait. An ionic liquid may be used individually by 1 type, and may use 2 or more types together.

When the treatment liquid of the present invention contains an ionic liquid, the content of the ionic liquid relative to the total mass of the treatment liquid is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, and more preferably 1 to 5% by mass. good.

＜Surface active agent＞ The treatment liquid of the present invention may also contain a surfactant. When the treatment liquid contains a surfactant, the wettability of the treatment liquid to the resist film is improved, and development and/or washing can be carried out more effectively. As the surfactant, the same surfactants as those that can be contained in the resist composition described later can be used. The surfactant may be used singly, or two or more of them may be used in combination. When the treatment liquid of the present invention contains a surfactant, the content of the surfactant relative to the total mass of the treatment liquid is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.

＜Antioxidant＞ The treatment liquid of the present invention may also contain an antioxidant. As the antioxidant, an amine-based antioxidant or a phenol-based antioxidant is preferred. One type of antioxidant may be used alone, or two or more types may be used in combination. When the treatment liquid of the present invention contains an antioxidant, the content of the antioxidant relative to the total mass of the treatment liquid is preferably 0.0001 to 1% by mass, more preferably 0.0001 to 0.1% by mass, and still more preferably 0.0001 to 0.01% by mass.

＜Basic compound＞ The treatment liquid of the present invention may also contain a basic compound. As a specific example of a basic compound, the compound exemplified as an acid diffusion control agent which can be contained in the resist composition mentioned later can be mentioned. One kind of basic compound may be used alone, or two or more kinds may be used in combination. When the treatment liquid of the present invention contains a basic compound, the content of the basic compound relative to the total treatment liquid is preferably 10% by mass or less, preferably 0.5 to 5% by mass. In addition, in the present invention, only one kind of the above-mentioned basic compound may be used, or two or more kinds of different chemical structures may be used in combination.

＜Other solvents＞ The treatment liquid of the present invention may also contain other solvents. When the treatment liquid of the present invention is used as a developer, the treatment liquid of the present invention may contain other organic solvents other than the first organic solvent and the second organic solvent. The other organic solvent is not particularly limited, and examples thereof include solvents such as ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. When the treatment liquid of the present invention is used as a rinsing liquid, the treatment liquid of the present invention may also contain the above-mentioned first organic solvent and the above-mentioned second organic solvent. The other organic solvent is not particularly limited, and examples thereof include solvents such as hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents.

[Pattern Formation Method] The present invention also relates to a pattern forming method using the above-mentioned treatment liquid. The pattern forming method of the present invention includes: (I) A resist film forming step, using a resist composition to form a resist film; (Ii) Exposure step, exposing the above-mentioned resist film; and (Iii) The processing step, the exposed resist film is processed by the processing liquid.

Hereinafter, each step of the pattern forming method of the present invention will be described. In addition, as an example of the processing steps, the development step and the rinsing step will be described separately.

[(I) Resist film formation step] The resist film forming step is a step of forming a resist film using the resist composition, and can be performed by the following method, for example. In order to use the resist composition to form a resist film on the substrate, each component described below is dissolved in a solvent to prepare the resist composition, filtered as needed, and then coated on the substrate. As the pore size of the filter, the pore size is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. As the material of the filter, polytetrafluoroethylene, polyethylene or nylon is preferable.

The resist composition is coated on a substrate (e.g., silicon, silicon dioxide coating film) used in the manufacture of integrated circuit components by an appropriate coating method such as a spin coater. After that, drying is performed to form a resist film. Various undercoating films (inorganic film, organic film, anti-reflection film) can also be formed on the lower layer of the resist film as needed.

As a drying method, heating and drying are generally used. As the heating temperature, 80 to 180°C is preferred, 80 to 150°C is more preferred, 80 to 140°C is more preferred, and 80 to 130°C is particularly preferred. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and more preferably 60 to 600 seconds.

The thickness of the resist film is generally 200 nm or less, preferably 100 nm or less. For example, in order to analyze 1:1 line and space patterns with a size of 30 nm or less, the thickness of the resist film is preferably 50 nm or less. As long as the film thickness is 50 nm or less, it is less likely to cause pattern collapse when the development step described later is applied, and better resolution performance can be obtained. From the viewpoint of more excellent etching resistance and resolution, the film thickness is preferably 15 to 45 nm, and more preferably 15 to 40 nm.

[(Ii) Exposure Step] In the pattern forming method of the present invention, the exposure method in the (ii) exposure step may also be liquid immersion exposure. In the pattern forming method of the present invention, it is preferable to include (iv) a preheating (PB: PreBake) step before the (ii) exposure step. In the pattern forming method of the present invention, it is preferable to include (v) Post Exposure Bake (PEB: Post Exposure Bake) step after (ii) the exposure step and before (iii) the development step. The pattern forming method of the present invention may also include a plurality of (ii) exposure steps. The pattern forming method of the present invention may also include a plurality of (iv) preheating steps. The pattern forming method of the present invention may also include multiple (v) post-exposure heating steps.

In the pattern forming method of the present invention, the above-mentioned (i) film forming step, (ii) exposure step, and (iii) processing step can be performed by a well-known method. In addition, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and anti-reflection film) may be formed between the resist film and the support as required. As the material constituting the resist underlayer film, a known organic or inorganic material can be suitably used. It is also possible to form a protective film (top coat layer) on the upper layer of the resist film. As a protective film, a well-known material can be used suitably. For example, the specification of U.S. Patent Application Publication No. 2007/0178407, the specification of U.S. Patent Application Publication No. 2008/0085466, the specification of U.S. Patent Application Publication No. 2007/0275326, and the specification of U.S. Patent Application Publication No. 2016/0299432 can be preferably used. The composition for forming a protective film disclosed in the specification of U.S. Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016/157988A. As the composition for forming a protective film, those containing the above-mentioned acid diffusion control agent are preferred. The thickness of the protective film is preferably 10 to 200 nm, more preferably 20 to 100 nm, and even more preferably 40 to 80 nm.

The support for forming the resist film is not particularly limited. In addition to the manufacturing steps of semiconductors such as ICs or the manufacturing steps of circuit boards such as liquid crystals or thermal heads, it can also be used in other photolithographic steps of photosensitive etching processing. The substrate. Specific examples of the support include inorganic substrates such as _{silicon, SiO 2 and SiN.}

The heating temperature is preferably 80-150°C in both (iv) the pre-heating step and (v) the post-exposure heating step, more preferably 80-140°C, and even more preferably 80-130°C. The heating time is preferably 30-1000 seconds in both (iv) the pre-heating step and (v) the post-exposure heating step, more preferably 60-800 seconds, and still more preferably 60-600 seconds. The heating can be performed using mechanisms installed in the exposure device and the developing device, or can be performed using a heating plate or the like.

The wavelength of the light source used in the exposure step is not limited. For example, infrared light, visible light, ultraviolet light, extreme ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams can be cited. Among them, far-ultraviolet light is preferred, and its wavelength is preferably 250 nm or less, more preferably 220 nm or less, and more preferably 1 to 200 nm. Specifically, it is KrF excimer laser (248nm), ArF excimer laser (193nm), F ₂ excimer laser (157nm), X-ray, EUV (13nm) or electron beam, etc., KrF excimer laser , ArF excimer laser, EUV or electron beam is preferable, EUV or electron beam is more preferable.

[(Iii) The step of processing the exposed film] (Iii) The step of processing the exposed film usually includes: (vi) a developing step, which is developed by a developer (developing step); and (vii) a washing step, which is washed by a washing liquid (rinsing step) . The treatment liquid of the present invention can be used as a developer in the development step and can also be used as a rinse in the washing step. Among them, it is preferably used as a rinsing liquid in the rinsing step. When the processing liquid of the present invention is used as the rinse liquid in the rinsing step, it is preferable to use a processing liquid other than the processing liquid of the present invention as the developer in the development step.

<Development step> The developing step is a step of developing the exposed resist film with a developing solution.

As the development method, for example, a method of immersing the substrate in a tank filled with developer for a period of time (dipping method), and a method of raising the developer to the surface of the substrate by surface tension and staying for a period of time (puddle) Method), the method of spraying the developer on the surface of the substrate (spraying method) or the method of continuously spraying the developer while scanning the nozzle of the developer on a substrate rotating at a certain speed (dynamic distribution method), etc. In addition, after the development step, a step of stopping the development while substituting for another solvent may be implemented. The development time is usually 10 to 300 seconds, preferably 20 to 120 seconds. As the temperature of the developer, 0 to 50°C is preferable, and 15 to 35°C is more preferable.

As the developer, the above-mentioned treatment liquid may be used, or other developer may be used, and it is preferable to use other developer. In addition to the development using the treatment liquid, an alkaline developer can also be used for development (so-called double development).

(Other developer) Hereinafter, other developing solutions will be described. The vapor pressure of the organic solvent used in the developer (the overall vapor pressure when the solvent is mixed) is preferably 5kPa or less at 20°C, more preferably 3kPa or less, and even more preferably 2kPa or less. By setting the vapor pressure of the organic solvent to 5 kPa or less, the evaporation of the developer on the substrate or in the developing cup is suppressed, the temperature uniformity in the substrate surface is improved, and as a result, the dimensional uniformity in the substrate surface becomes good. The organic solvent used in the developer is not particularly limited, and examples thereof include solvents such as ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

Among them, the developer preferably contains one or more solvents selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, and ether-based solvents.

Examples of ester-based solvents include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, propyl acetate, isopropyl acetate, and amyl acetate (Amyl acetate (amyl acetate) Pentyl acetate), isoamyl acetate (isopentyl acetate), 3-methylbutyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate Ester, isohexyl acetate, heptyl acetate, octyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA; alias 1-methoxy-2-acetoxy Propane), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether Acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene two Alcohol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxy Butyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4- Ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl ethyl Ester, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate , 4-Methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate , Ethyl Carbonate, Propyl Carbonate, Butyl Carbonate, Methyl Pyruvate, Ethyl Pyruvate, Propyl Pyruvate, Butyl Pyruvate, Methyl Acetate, Ethyl Acetate, Methyl Propionate, Ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, pentyl propionate, hexyl propionate, heptyl propionate, butyl butyrate, isobutyl butyrate, pentyl butyrate Ester, hexyl butyrate, isobutyl isobutyrate, propyl valerate, isopropyl valerate, butyl valerate, pentyl valerate, ethyl caproate, propyl caproate, butyl caproate, Isobutyl caproate, methyl heptanoate, ethyl heptanoate, propyl heptanoate, cyclohexyl acetate, cycloheptyl acetate, 2-ethylhexyl acetate, cyclopentyl propionate, 2-hydroxypropionic acid Methyl ester, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate and propyl- 3-methoxypropionate and the like. Among them, butyl acetate, pentyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate or Butyl butyrate is preferred, and isoamyl acetate is more preferred.

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, Diisobutyl ketone, cyclohexanone, methyl cyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetone, acetonyl acetone, ionone, diacetone alcohol, acetyl methanol , Acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, etc., 2-heptanone is preferred.

Examples of alcohol solvents include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, 3-methyl-3-pentanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, 5-methyl-2-hexanol, 4-methyl-2-hexanol, 4,5-dimethyl-2-hexanol, 6-methyl 2-heptanol, 7-methyl-2-octanol, 8-methyl-2-nonanol, 9-methyl-2-decanol and 3-methoxy-1-butanol and other alcohols ( Monovalent alcohol); glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; alias 1-methoxy-2-propanol ), diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol Glycol ether solvents containing hydroxyl groups such as monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, etc., glycol ether solvents are preferred.

As ether solvents, for example, in addition to glycol ether solvents containing the above-mentioned hydroxyl groups, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and other non-hydroxyl-free solvents can be cited. Glycol ether-based solvents, aromatic ether solvents such as anisole and phenyl ethyl ether, di-molecules, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-molecules Koushan and isopropyl ether, etc. Among them, glycol ether solvents and aromatic ether solvents such as anisole are preferred.

Examples of amide-based solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethyltriamide phosphate, 1,3-Dimethyl-2-imidazolidinone, etc.

Examples of hydrocarbon solvents include pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2 , 3-Trimethylhexane, perfluorohexane and perfluoroheptane and other aliphatic hydrocarbon solvents; toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methyl Aromatic hydrocarbon solvents such as propylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, and dipropylbenzene. In addition, as the hydrocarbon-based solvent, unsaturated hydrocarbon-based solvents can also be used, and examples thereof include unsaturated hydrocarbon-based solvents such as octene, nonene, decene, undecene, dodecene, and hexadecene. The number of double bonds or triple bonds possessed by the unsaturated hydrocarbon solvent is not particularly limited, and it may be located at any position in the hydrocarbon chain. In addition, when the unsaturated hydrocarbon solvent has a double bond, the cis isomer and the trans isomer may be mixed. In addition, the aliphatic hydrocarbon solvent as the hydrocarbon solvent may be a mixture of compounds having the same carbon number and different structures. For example, when decane is used as an aliphatic hydrocarbon solvent, 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isooctane are compounds with the same carbon number and different structures The aliphatic hydrocarbon solvent may also be included. In addition, the above-mentioned compounds having the same carbon number and different structures may include only one type, or may include a plurality of types as described above.

From the viewpoint that when EUV light and electron beam are used in the above exposure step, the swelling of the resist film can be further suppressed, as the developer, the carbon number is 6 or more (6-14 is preferable, 6-12 is more preferable , 6-10 is more preferable) and ester-based solvents having 2 or less heteroatoms are preferable. As said hetero atom, what is necessary is just an atom other than a carbon atom and a hydrogen atom, For example, an oxygen atom, a nitrogen atom, a sulfur atom, etc. are mentioned. The number of heteroatoms is preferably 2 or less. Specific examples of ester solvents having 6 or more carbon atoms and 2 or less heteroatoms are selected from the group consisting of butyl acetate, pentyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate Ester, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, butyl butyrate, butyl isobutyrate and isobutyl isobutyrate are preferred, isoamyl acetate or isobutyl Butyl butyrate is more preferable.

From the viewpoint of further suppressing the swelling of the resist film when EUV light and electron beam are used in the above exposure step, it can be used as a developer instead of the above-mentioned ester solvent with 6 or more carbon atoms and 2 or less heteroatoms. A mixed solvent of an ester solvent and a hydrocarbon solvent or a mixed solvent of a ketone solvent and a hydrocarbon solvent is used.

In the above-mentioned mixed solvent, the content of the hydrocarbon-based solvent depends on the solvent solubility of the resist film, and therefore is not particularly limited, as long as it is appropriately prepared to determine the required amount.

Among the mixed solvents of the ester solvent and the hydrocarbon solvent, isoamyl acetate is preferred as the ester solvent. From the viewpoint of easy adjustment of the solubility of the resist film, as the hydrocarbon solvent, saturated hydrocarbon solvents (for example, nonane, octane, decane, dodecane, undecane, hexadecane, etc.) are preferred.

In the mixed solvent of the ketone solvent and the hydrocarbon solvent, examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, and 2-heptanone (methylpentanone). Ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, 2,5-dimethyl-4-hexanone, cyclohexanone, methylcyclohexanone, phenylacetone , Methyl ethyl ketone, methyl isobutyl ketone, acetone, acetonyl acetone, ionone, diacetone alcohol, acetol, acetophenone, methyl naphthyl ketone, isophorone and propylene carbonate As esters, diisobutyl ketone or 2,5-dimethyl-4-hexanone is preferred. From the viewpoint of easy adjustment of the solubility of the resist film, as the hydrocarbon solvent, saturated hydrocarbon solvents (for example, nonane, octane, decane, dodecane, undecane, hexadecane, etc.) are preferred.

The above-mentioned solvents may be mixed with plural kinds, and may be mixed with solvents or water other than the above. The water content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and it is particularly preferable that it contains substantially no water. The content of the organic solvent relative to the organic developer is preferably 50-100% by mass relative to the total amount of the developer, more preferably 80-100% by mass, more preferably 90-100% by mass, 95-100 The quality% is particularly good.

The developer may contain an appropriate amount of a known surfactant as needed.

The content of the surfactant relative to the total amount of the developer is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.

The developer may also contain alkaline compounds. As a specific example of a basic compound, the compound exemplified as an acid diffusion control agent which can be contained in the resist composition mentioned later can be mentioned.

As the organic solvent used as the developer, in addition to the above-mentioned ester-based solvent, an ester-based solvent represented by the following general formula (S1) or the following general formula (S2) is also preferable. As the above-mentioned ester-based solvent, the ester-based solvent represented by the general formula (S1) is more preferred, and alkyl acetate is even more preferred, butyl acetate, amyl acetate (pentyl acetate) (pentyl acetate) Or isoamyl acetate (isopentyl acetate) is particularly preferred.

R-C(=O)-O-R’ general formula (S1)

In the general formula (S1), R and R'each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group, or a halogen atom. R and R'may be bonded to each other to form a ring. The number of carbon atoms in the alkyl group, alkoxy group, and alkoxycarbonyl group represented by R and R'is preferably 1-15, and the number of carbon atoms in the cycloalkyl group is preferably 3-15. The alkyl group, cycloalkyl group, alkoxy group and alkoxycarbonyl group represented by R and R', and the ring formed by bonding R and R'to each other may have a substituent. The substituent is not particularly limited, and examples thereof include a hydroxyl group, a carbonyl group-containing group (for example, an acyl group, an aldehyde group, and an alkoxycarbonyl group, etc.), a cyano group, and the like. As R and R', among them, a hydrogen atom or an alkyl group is preferred.

Examples of the solvent represented by the general formula (S1) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, and methyl formate. Ester, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, pyruvic acid Propyl ester, butyl pyruvate, methyl acetylacetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate and 2 -Ethyl hydroxypropionate, etc.

Among these, as R and R', an unsubstituted alkyl group is preferred. As the solvent represented by the general formula (S1), alkyl acetate is preferred, butyl acetate, amyl acetate (pentyl acetate) or isoamyl acetate (acetic acid) Isopentyl acetate is more preferable, and isoamyl acetate is still more preferable.

When the developer contains the solvent represented by the general formula (S1), the developer may further contain one or more other organic solvents (hereinafter also referred to as "combined solvent"). The combined solvent is not particularly limited as long as it can be mixed in the solvent represented by the general formula (S1) without separation. Examples include ester-based solvents and ketone-based solvents other than the solvent represented by the general formula (S1) , Alcohol-based solvents, amide-based solvents, ether-based solvents and solvents in hydrocarbon-based solvents. There may be either one or two types of solvents used in combination. From the viewpoint of obtaining stable performance, one type is preferred. When the developer is a mixed solvent of the solvent represented by the general formula (S1) and a combined solvent, the mixing ratio of the solvent represented by the general formula (S1) and the combined solvent is calculated by mass ratio, usually 20:80～99:1 , 50:50～97:3 is preferable, 60:40～95:5 is more preferable, and 60:40～90:10 is still more preferable.

As the organic solvent used as the developer, a solvent represented by the following general formula (S2) is also preferable.

R’’-C(=O)-O-R’’’-O-R’’’’ General formula (S2)

In the general formula (S2), R’’ and R’’’’ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom. R'' and R'''' may be bonded to each other to form a ring. As R'' and R'''', a hydrogen atom or an alkyl group is preferable. As the carbon number of the alkyl group, alkoxy group, and alkoxycarbonyl group represented by R'’ and R’’’’, 1 to 15 are preferred, and as the carbon number of the cycloalkyl group, 3 to 15 are preferred. R’’’ represents an alkylene group or a cycloalkylene group, and an alkylene group is preferred. The number of carbon atoms in the alkylene group represented by R''' is preferably from 1 to 10, and the number of carbon atoms in the cycloalkylene group represented by R''' is preferably from 3 to 10. In addition, the alkylene group represented by R''' may have an ether bond in the alkylene chain. Alkyl, cycloalkyl, alkoxy and alkoxycarbonyl represented by R'' and R'''', alkylene and cycloalkylene represented by R''', and R'' and R ""The ring formed by bonding to each other may have a substituent. The substituent is not particularly limited, and examples thereof include groups including a hydroxyl group and a carbonyl group (for example, an acyl group, an aldehyde group, an alkoxycarbonyl group, etc.), a cyano group, and the like.

Examples of the solvent represented by the general formula (S2) include propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate. , Ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl Ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3-methoxypropionate, ethyl-3-methoxy Propionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl ethyl Ester, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxy Butyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate , 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate Ethyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, etc., propylene glycol monomethyl ether acetate is preferred. Among these, R'' and R'''' are unsubstituted alkyl groups, R''' is preferably an unsubstituted alkylene group, and R'' and R'''' are methyl groups and Either of the ethyl groups is more preferable, and R" and R"" are more preferably methyl groups.

When the developer contains the solvent represented by the general formula (S2), the developer may further contain one or more other organic solvents (hereinafter also referred to as "combined solvent"). The combined solvent is not particularly limited as long as it can be mixed in the solvent represented by the general formula (S2) without separation, and examples include ester-based solvents and ketone-based solvents other than the solvent represented by the general formula (S2) , Alcohol-based solvents, amide-based solvents, ether-based solvents and solvents in hydrocarbon-based solvents. There may be either one or two types of solvents used in combination. From the viewpoint of obtaining stable performance, one type is preferred. When the developer is a mixed solvent of the solvent represented by the general formula (S2) and a combined solvent, the mixing ratio of the solvent represented by the general formula (S2) and the combined solvent is calculated by mass ratio, usually 20:80～99:1 , 50:50～97:3 is preferable, 60:40～95:5 is more preferable, and 60:40～90:10 is still more preferable.

In addition, as the organic solvent used as the developer, an ether solvent containing one or more aromatic rings is also preferable, and the solvent represented by the following general formula (S3) is more preferable, and anisole is still more preferable.

[Chemical formula 1]

In the general formula (S3), R _S represents an alkyl group. As the alkyl group, a carbon number of 1 to 4 is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is more preferable.

(Rinse step) The rinsing step is a step of washing (rinsing) with a rinsing liquid after the above-mentioned development step.

In the rinsing step, the developed substrate is cleaned using the above-mentioned rinsing liquid. The method of cleaning treatment is not particularly limited. For example, it can be applied to a method of continuously spraying a rinse liquid on a substrate rotating at a certain speed (rotary spray method), and a method of immersing the substrate for a period of time in a tank filled with rinse liquid (dipping Method), a method of spraying a rinsing liquid on the surface of the substrate (spraying method), etc., in which a rotary jet method is used for cleaning, and after cleaning, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm to remove the rinsing liquid from the substrate. good. The rinsing time is usually 10 seconds to 300 seconds, preferably 10 seconds to 180 seconds, and more preferably 20 seconds to 120 seconds. As the temperature of the rinse liquid, 0-50°C is preferred, and 15-35°C is more preferred.

Furthermore, after the development process or the rinsing process, a process of removing the developer or rinsing liquid adhering to the pattern by the supercritical fluid can be performed. Moreover, after the development process, the rinsing process, or the supercritical fluid-based process, a drying process may be performed in order to remove the solvent remaining in the pattern. The drying temperature is usually 40 to 160°C, preferably 50 to 150°C, and more preferably 50 to 110°C. The drying time is usually 15 to 300 seconds, preferably 15 to 180 seconds.

In the pattern forming method of the present invention, the treatment liquid of the present invention is used as at least one of a developer and a rinse liquid. Among them, the treatment liquid of the present invention is preferably used as a rinsing liquid.

For example, when an ester solvent is used as the developer in the development step, and the processing liquid of the present invention is used as the rinsing liquid in the rinsing step to perform pattern formation, the interval between the supply of the developer and the rinsing liquid to the exposed resist film is set It is preferably 1 second or more. Setting the supply interval of the developer and the rinsing liquid to a predetermined time or longer can suppress the deterioration of the solubility of the unexposed area of the resist film after exposure, and can suppress the increase in defects due to the solvent casting method.

In addition, the developer and the rinse liquid are usually stored in a general-purpose waste liquid tank through a pipe after use. At this time, if an ester-based solvent is used as the developer in the development step and the treatment liquid of the present invention is used as the rinse in the rinsing step, the resist dissolved in the developer is precipitated, resulting in adhesion to the back of the substrate and The side of the piping, etc., may contaminate the device. In order to solve the above problems, there is a method of passing the solvent for dissolving the resist through the piping again. As a method of passing through the piping, a method of washing the back or side surface of the substrate with a solvent that dissolves the resist after washing with a rinse solution and a method of flowing out through the piping so that the solvent that dissolves the resist does not contact the resist. method. The solvent passing through the piping is not particularly limited as long as it can dissolve the resist. For example, organic solvents used as the above-mentioned developer can be cited. Specifically, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol mono Ethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol mono Methyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone, etc. Among them, PGMEA, PGME or cyclohexanone are preferred.

In addition, as another method to solve the above problems, in order to prevent the precipitation of the resist in the waste liquid flowing into the waste liquid tank through the pipe after use, the amount ratio of the developer and the rinse liquid flowing into the pipe after use can be adjusted. It is a method of preventing the precipitation of the amount of the resist and a method of further mixing a solvent with high solubility to the resist in the developer and rinse liquid that is discharged into the piping after use. As a specific method, for example, between the development step and the rinsing step, an organic solvent having an SP value higher than the first organic solvent contained in the processing solution of the present invention is continuously supplied to the back surface of the wafer to suppress the use of The method of precipitation/precipitation of the resist in the waste liquid flowing into the waste liquid tank through the piping.

Moreover, it is also preferable that the developer and the rinse liquid are separately contained in different waste liquid tanks after use. For example, when an ester solvent is used as the developer in the development step and the processing liquid of the present invention is used as the rinsing liquid in the rinsing step to perform pattern formation, if it is stored in the same waste liquid tank through piping after use, it will cause The components contained in the resist composition such as resin dissolved in the developer are analyzed (precipitation/solidification), which may cause device contamination. Specifically, due to the precipitated components, not only the clogging of the waste liquid piping but also the contamination of the processing chamber occurs. In order to solve the above-mentioned problems, it is preferable that the developer and the rinsing liquid are separately contained in different waste liquid tanks by pipe replacement or processing chamber replacement after use. In addition, in order to remove the resist component that may adhere to the processing chamber, it is better to clean the interior of the processing chamber with a solvent with a higher SP value than the first organic solvent contained in the processing liquid of the present invention after the processing is completed.

[Resist composition] Next, the resist composition which is preferable to use the treatment liquid of the present invention in combination will be described in detail.

＜Resin (A)＞ The resist composition contains a resin that is decomposed by the action of an acid to increase its polarity (hereinafter, also referred to as "acid-decomposable resin" or "resin (A)"). That is, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed . The resin (A) usually contains a group that decomposes by the action of an acid to increase its polarity (hereinafter, also referred to as an "acid-decomposable group"), and preferably contains a repeating unit having an acid-decomposable group.

"Repeating unit with acid-decomposable group" The acid-decomposable group refers to a group that decomposes by the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which the polar group is protected by a leaving group that is detached by the action of an acid. That is, the resin (A) has a repeating unit having a group that decomposes by the action of an acid to generate a polar group. The resin having the repeating unit increases in polarity due to the action of the acid, so that the solubility with respect to the alkaline developer increases, and the solubility with respect to the organic solvent decreases. As the polar group, an alkali-soluble group is preferred, and examples include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, phosphoric acid groups, sulfonamide groups, sulfonamide groups, (alkylsulfonyl groups). Group) (alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imino, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imino, double (Alkylsulfonyl)methylene, bis(alkylsulfonyl)imino, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene and other acidic groups, and Alcoholic hydroxyl and so on. Among them, as the polar group, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferred.

Examples of the leaving group to be released by the action of an acid include groups represented by formulas (Y1) to (Y4). Formula (Y1): -C (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) Formula (Y2): -C (=O) OC (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) Formula (Y3): -C (R ₃₆ ) (R ₃₇ ) (OR ₃₈ ) Formula (Y4): -C (Rn) (H) (Ar)

In formula (Y1) and formula (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched) or cycloalkyl (monocyclic or polycyclic), alkenyl (linear or Branched) or aryl (monocyclic or polycyclic). In addition, when Rx ₁ to Rx ₃ are all alkyl groups (linear or branched), it is preferable that at least two of _{Rx 1} to Rx _{3 are methyl groups.} Wherein, Rx ₁ ~ Rx ₃ each independently represents a linear or branched alkyl group is preferred, Rx ₁ ~ Rx ₃ each independently represent a linear alkyl group is more preferred. Two of Rx ₁ to Rx ₃ may also be bonded to form a monocyclic ring or a polycyclic ring. As _{the alkyl group of Rx 1} to Rx ₃ , alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tertiary butyl are preferred. As Rx ₁ to Rx ₃ cycloalkyl, monocyclic cycloalkyl such as cyclopentyl and cyclohexyl, and polycyclic cycloalkane such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl The base is better. As _{the aryl group of Rx 1} to Rx _3, an aryl group having 6 to 10 carbon atoms is preferred, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. As _{the alkenyl group of Rx 1} to Rx ₃ , a vinyl group is preferred. As the ring formed by bonding two of _{Rx 1} to Rx _{3, a cycloalkyl group is preferred.} As _{a cycloalkyl group formed by bonding two of Rx 1} to Rx ₃ , monocyclic cycloalkyl such as cyclopentyl or cyclohexyl, or norbornyl, tetracyclodecyl, tetracyclododecyl or A polycyclic cycloalkyl group such as an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable. The cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ may also be substituted by a group having a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group in a methylene group constituting the ring, or by a group having a hetero atom such as an oxygen atom or a carbonyl group. Vinylidene substitution. In addition, these cycloalkyl groups may be substituted with ethylene groups in one or more of the ethylene groups constituting the cycloalkane. The group represented by the formula (Y1) or the formula (Y2) is preferably such that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx _{3 are} bonded to form the above-mentioned cycloalkyl group.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may also be bonded to each other to form a ring. As a monovalent organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned. It is also preferable that R _{36 is a hydrogen atom.} In addition, the above-mentioned alkyl group, cycloalkyl group, aryl group, and aralkyl group may also include groups having heteroatoms such as oxygen atoms and/or heteroatoms such as carbonyl groups. For example, the above-mentioned alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with a group having a hetero atom such as an oxygen atom and/or a hetero atom such as a carbonyl group in one or more of the methylene groups. In addition, R ₃₈ may be bonded to another substituent of the main chain of the repeating unit to form a ring. The _{group formed by bonding R 38} and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.

As the formula (Y3), a group represented by the following formula (Y3-1) is preferred.

[Chemical formula 2]

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining them (for example, a group formed by combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group that may contain a hetero atom, a cycloalkyl group that may contain a hetero atom, an aryl group that may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination of these groups ( For example, a group formed by combining an alkyl group and a cycloalkyl group). The alkyl group and the cycloalkyl group may be substituted with a group having a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group in one of the methylene group. In addition, it is preferable that one of L ₁ and L ₂ is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group. At least two of Q, M, and L ₁ may be bonded to form a ring (preferably, a 5-membered or 6-membered ring). From the viewpoint of miniaturization of the pattern, L ₂ is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of the secondary alkyl group include isopropyl, cyclohexyl, or norbornyl, and examples of the tertiary alkyl group include tertiary butyl or adamantyl. In these aspects, Tg (Glass Transition Temperature) and activation energy become high, so it is possible to ensure the film strength while suppressing rust.

In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may also be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

From the viewpoint of excellent acid decomposability of the repeating unit, when a non-aromatic ring is directly bonded to the polar group (or its residue) in the leaving group for protecting the polar group, the non-aromatic ring and the direct It is also preferable that the adjacent ring member atoms bonded to the above-mentioned polar group (or its residue) do not have halogen atoms such as fluorine atom as a substituent.

The leaving group that is detached by the action of an acid can also be a 2-cyclopropenyl group having a substituent such as 3-methyl-2-cyclopropenyl group (alkyl etc.) and a group having such as 1,1,4 , 4-tetramethylcyclohexyl such as cyclohexyl substituents (alkyl etc.).

As the repeating unit having an acid-decomposable group, the repeating unit represented by formula (A) is also preferable.

[Chemical formula 3]

L ₁ represents a divalent linking group that may have a fluorine atom or an iodine atom, and R ₁ represents an alkyl group that may have a hydrogen atom, a fluorine atom, an iodine atom, a fluorine atom, or an iodine atom, or an aromatic that may have a fluorine atom or an iodine atom. A group, R ₂ represents a leaving group that is released by the action of an acid and may have a fluorine atom or an iodine atom. Among them, _{at least one of L 1} , R ₁ and R ₂ has a fluorine atom or an iodine atom. L ₁ represents a divalent linking group which may have a fluorine atom or an iodine atom. Examples of the divalent linking group that may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO ₂ -, and a hydrocarbon group that may have a fluorine atom or an iodine atom (for example, Alkylene, cycloalkylene, alkenylene, arylalkylene, etc.) and linking groups formed by connecting a plurality of these. Among them, as L ₁ , -CO- or an alkylene group having an -arylene group-fluorine atom or iodine atom- is preferable. As the aryl group, phenyl group is preferred. The alkylene group may be linear or branched. The carbon number of the alkylene group is not particularly limited, and 1-10 is preferred, and 1-3 is more preferred. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, and 2 or more is preferable, 2-10 is more preferable, and 3-6 is still more preferable.

R ₁ represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. The alkyl group may be linear or branched. The carbon number of the alkyl group is not particularly limited, and 1-10 is preferred, and 1-3 is more preferred. The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom is not particularly limited, and 1 or more is preferable, 1 to 5 are more preferable, and 1 to 3 are more preferable. The above-mentioned alkyl group may contain heteroatoms such as oxygen atoms other than halogen atoms.

R ₂ represents a leaving group that is released by the action of an acid and may have a fluorine atom or an iodine atom. Among them, examples of the leaving group include groups represented by formulas (Z1) to (Z4). Formula (Z1): -C (Rx ₁₁ ) (Rx ₁₂ ) (Rx ₁₃ ) Formula (Z2): -C (=O) OC (Rx ₁₁ ) (Rx ₁₂ ) (Rx ₁₃ ) Formula (Z3): -C (R ₁₃₆ ) (R ₁₃₇ ) (OR ₁₃₈ ) Formula (Z4): -C (Rn ₁ ) (H) (Ar ₁ )

In the formulas (Z1) and (Z2), Rx ₁₁ to Rx ₁₃ each independently represent an alkyl group (linear or branched) that may have a fluorine atom or an iodine atom, and a cycloalkyl group that may have a fluorine atom or an iodine atom (Monocyclic or polycyclic), an alkenyl group (linear or branched) which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom (monocyclic or polycyclic). In addition, when Rx ₁₁ to Rx ₁₃ are all alkyl groups (linear or branched), it is preferred that at least two of _{Rx 11} to Rx _{13 are methyl groups.} Rx ₁₁ to Rx _{13 are the same as Rx 1} to Rx _{3 in} (Y1) and (Y2) above, except that they may have a fluorine atom or an iodine atom, and have the same definitions as alkyl, cycloalkyl, alkenyl and aryl groups And the preferred range is the same.

In formula (Z3), R ₁₃₆ to R ₁₃₈ each independently represent a hydrogen atom or a monovalent organic group that may have a fluorine atom or an iodine atom. R ₁₃₇ and R ₁₃₈ may also be bonded to each other to form a ring. Examples of the monovalent organic group which may have a fluorine atom or an iodine atom include an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, and an aryl group which may have a fluorine atom or an iodine atom. , Aralkyl groups that may have a fluorine atom or an iodine atom and a group formed by combining them (for example, a group formed by combining an alkyl group and a cycloalkyl group). In addition, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain heteroatoms such as oxygen atoms in addition to fluorine atoms and iodine atoms. That is, the aforementioned alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with a group having a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group, for example, of a methylene group. In addition, R ₁₃₈ may be bonded to another substituent of the main chain of the repeating unit to form a ring. In this case, _{the group formed by bonding R 138} and another substituent of the main chain of the repeating unit to each other is preferably a methylene isoalkylene group.

As the formula (Z3), a group represented by the following formula (Z3-1) is preferred.

[Chemical formula 4]

Here, L ₁₁ and L ₁₂ each independently represent a hydrogen atom; an alkyl group that may have a hetero atom selected from a fluorine atom, an iodine atom, and an oxygen atom; and may have a hetero atom selected from a fluorine atom, an iodine atom, and an oxygen atom Atom cycloalkyl group; an aryl group which may have a heteroatom selected from fluorine atom, iodine atom and oxygen atom; or a group formed by combining them (for example, the combination may have a group selected from fluorine atom, iodine atom and oxygen Heteroatoms in the atom, a group formed by an alkyl group and a cycloalkyl group). M ₁ represents a single bond or a divalent linking group. Q ₁ represents an alkyl group which may have a hetero atom selected from a fluorine atom, an iodine atom and an oxygen atom; a cycloalkyl group which may have a hetero atom selected from a fluorine atom, an iodine atom and an oxygen atom; is selected from a fluorine atom and an iodine atom The aryl group in the atom and the oxygen atom; amine group; ammonium group; mercapto group; cyano group; aldehyde group; or a combination of these groups (for example, the combination may have a fluorine atom, an iodine atom, and an oxygen atom Heteroatomic, alkyl group and cycloalkyl group).

In formula (Y4), Ar ₁ represents an aromatic ring group which may have a fluorine atom or an iodine atom. Rn ₁ represents an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. Rn ₁ and Ar ₁ may also be bonded to each other to form a non-aromatic ring.

As the repeating unit having an acid-decomposable group, the repeating unit represented by the general formula (AI) is also preferable.

[Chemical formula 5]

In the general formula (AI), Xa ₁ represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx ₁ to Rx ₃ each independently represent alkyl (linear or branched), cycloalkyl (monocyclic or polycyclic), alkenyl (linear or branched), or aromatic (monocyclic or polycyclic) Ring) base. Among them, when Rx ₁ to Rx ₃ are all alkyl groups (linear or branched), it is preferred that at least two of _{Rx 1} to Rx _{3 are methyl groups.} Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic or polycyclic ring (monocyclic or polycyclic cycloalkyl group, etc.).

Examples of the optionally substituted alkyl group represented by Xa ₁ include a methyl group or a group represented by _{-CH 2} -R _11. R ₁₁ represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group, for example, an alkyl group with 5 or less carbons that may be substituted by a halogen atom, and an acyl group with 5 or less carbons that may be substituted by a halogen atom A group and an alkoxy group having a carbon number of 5 or less which may be substituted with a halogen atom, an alkyl group having a carbon number of 3 or less is preferable, and a methyl group is more preferable. As Xa ₁ , a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group is preferable.

Examples of the divalent linking group of T include alkylene groups, aromatic ring groups, -COO-Rt- groups, and -O-Rt- groups. In the formula, Rt represents an alkylene group or a cycloalkylene group. Preferably T is a single bond or -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and -CH ₂ -group, -(CH ₂ ) ₂ -group or -(CH ₂ ) ₃ -group is Better.

As _{the alkyl group of Rx 1} to Rx ₃ , alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tertiary butyl are preferred. As Rx ₁ to Rx ₃ cycloalkyl, monocyclic cycloalkyl such as cyclopentyl and cyclohexyl, or polycyclic ring such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl Alkyl is preferred. As _{the aryl group of Rx 1} to Rx _3, an aryl group having 6 to 10 carbon atoms is preferred, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. As _{the alkenyl group of Rx 1} to Rx ₃ , a vinyl group is preferred. As _{the cycloalkyl group formed by bonding two of Rx 1} to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl are preferred. In addition, norbornyl, tetracyclodecyl, Polycyclic cycloalkyls such as tetracyclododecyl and adamantyl are preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. The cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ may also be substituted by a group having a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group in a methylene group constituting the ring, or by a group having a hetero atom such as an oxygen atom or a carbonyl group. Vinylidene substitution. In addition, these cycloalkyl groups may be substituted with ethylene groups in one or more of the ethylene groups constituting the cycloalkane. Among the repeating units represented by the general formula (AI), for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx _{3 are} bonded to form the above-mentioned cycloalkyl group.

When each of the above groups has a substituent, examples of the substituent include an alkyl group (with carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (with a carbon number of 1 to 4), a carboxyl group, and an alkoxycarbonyl group. (The carbon number is 2-6) and so on. The number of carbon atoms in the substituent is preferably 8 or less.

The repeating unit represented by the general formula (AI) is preferably an acid-decomposable (meth)acrylate tertiary alkyl ester repeating unit (where Xa ₁ represents a hydrogen atom or a methyl group and T represents a single bond) .

The content of the repeating unit having an acid-decomposable group is preferably 15 mol% or more with respect to the total repeating units in the resin (A), more preferably 20 mol% or more, and even more preferably 25 mol% or more, More than 30 mol% is particularly good. There is no particular limitation on the upper limit, but 90 mol% or less is preferable, 80 mol% or less is more preferable, and 70 mol% is still more preferable.

Although the specific example of the repeating unit which has an acid-decomposable group is shown below, this invention is not limited to this. In addition, in the formula, Xa ₁ represents any one of H, CH ₃ , CF ₃ and CH ₂ OH, or Rxa and Rxb each represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[Chemical formula 6]

[Chemical formula 7]

[Chemical formula 8]

[Chemical formula 9]

[Chemical formula 10]

The resin (A) may contain repeating units other than the above repeating units. For example, the resin (A) may also include at least one repeating unit selected from the group including the following A group and/or at least one repeating unit selected from the group including the following B group. Group A: A group that includes the following repeating units (20) to (29). (20) Repeating unit with acid group mentioned later (21) Repeating unit with fluorine atom or iodine atom mentioned later (22) The repeating unit having a lactone group, a sultone group or a carbonate group mentioned later (23) Repeating unit with photoacid generating group mentioned later (24) Repeating units represented by the following general formula (V-1) or the following general formula (V-2) (25) Repeating unit represented by formula (A) described later (26) Repeating unit represented by formula (B) described later (27) Repeating unit represented by formula (C) described later (28) Repeating unit represented by formula (D) described later (29) Repeating unit represented by formula (E) described later Group B: A group that includes the following repeating units (30) to (32). (30) The following repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group (31) The repeating unit that has an alicyclic hydrocarbon structure and does not show acid decomposability described later (32) The repeating unit represented by the general formula (III) that does not have any of a hydroxyl group and a cyano group as described later

When the resist composition is used for EUV purposes, it is preferable that the resin (A) has at least one repeating unit selected from the group including the aforementioned A group. Moreover, when the resist composition is used for EUV applications, it is preferable that the resin (A) contains at least one of a fluorine atom and an iodine atom. When the resin (A) contains both fluorine atoms and iodine atoms, the resin (A) may have a repeating unit including both fluorine atoms and iodine atoms, and the resin (A) may also include repeating units with fluorine atoms and The repeating unit of the iodine atom is both. Moreover, when the resist composition is used for EUV applications, it is also preferable that the resin (A) has a repeating unit having an aromatic group. When the resist composition is used for ArF purposes, the resin (A) preferably has at least one repeating unit selected from the group including the above-mentioned B group. In addition, when the resist composition is used for ArF applications, it is preferable that the resin (A) does not contain any of fluorine atoms and silica atoms. Moreover, when the composition is used for ArF purposes, it is preferable that the resin (A) does not have an aromatic group.

"Repeating unit having an acid group" The resin (A) may have a repeating unit having an acid group. As the acid group, an acid group having a pKa of 13 or less is preferable. As the acid group, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group are preferable. In addition, the above-mentioned hexafluoroisopropanol group may be one or more (preferably 1 to 2) of the fluorine atoms substituted by a group other than the fluorine atom (alkoxycarbonyl group, etc.). The thus formed -C(CF ₃ )(OH)-CF ₂ -is preferable as the acid group. In addition, one or more of the fluorine atoms may be substituted with a group other than the fluorine atom to form a _{ring containing -C(CF 3} )(OH)-CF ₂ -. The repeating unit having an acid group is a repeating unit having a structure in which a polar group is detached by the action of the above-mentioned acid, and a repeating unit that is different from the repeating unit having a lactone group, a sultone group, or a carbonate group described later The unit is better.

The repeating unit having an acid group may also have a fluorine atom or an iodine atom.

As the repeating unit having an acid group, the repeating unit represented by the formula (B) is preferred.

[Chemical formula 11]

R ₃ represents a hydrogen atom or a monovalent organic group which may have a fluorine atom or an iodine atom. As the monovalent organic group which may have a fluorine atom or an iodine atom, a group _{represented by -L 4} -R ₈ is preferable. L ₄ represents a single bond or an ester group. As R ₈ , an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a combination of these may be mentioned.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.

L ₂ represents a single bond or an ester group. L ₃ represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. Examples of the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group. The alicyclic hydrocarbon ring group may be a monocyclic ring or a polycyclic ring group, for example, a cycloalkyl ring group. R ₆ represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). In addition, when R ₆ is a hydroxyl group, L ₃ is preferably an aromatic hydrocarbon ring group having a valence of (n+m+1). R ₇ represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. m represents an integer of 1 or more. It is preferable that m is an integer of 1-3, and an integer of 1-2 is more preferable. n represents an integer of 0 or more. Preferably, n is an integer of 1 to 4. In addition, (n+m+1) is preferably an integer of 1 to 5.

As the repeating unit having an acid group, the repeating unit represented by the following general formula (I) is also preferable.

[Chemical formula 12]

In the general formula (I), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Among them, R ₄₂ may also _{bond with Ar 4} to form a ring. In this case, R ₄₂ represents a single bond or an alkylene group. X ₄ represents a single bond, -COO- or -CONR ₆₄ -, and R ₆₄ represents a hydrogen atom or an alkyl group. L ₄ represents a single bond or an alkylene group. Ar ₄ represents an (n+1)-valent aromatic ring group, and _{when it is bonded to R 42} to form a ring, it represents an (n+2)-valent aromatic ring group. n represents an integer of 1-5.

_{As the alkyl group of R 41} , R ₄₂ and R ₄₃ in the general formula (I), methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, An alkyl group with a carbon number of 20 or less such as an octyl group and a dodecyl group is preferable, an alkyl group with a carbon number of 8 or less is more preferable, and an alkyl group with a carbon number of 3 or less is more preferable.

_{The cycloalkyl groups of R 41} , R ₄₂ and R ₄₃ in the general formula (I) may be monocyclic or polycyclic. Among them, monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, and cyclohexyl are preferred. _{Examples of the halogen atom of R 41} , R ₄₂ and R ₄₃ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. _{The alkyl group contained in the alkoxycarbonyl group of R 41} , R ₄₂ and R ₄₃ in the general formula (I) is preferably the same as the alkyl group in the above-mentioned R ₄₁ , R ₄₂ , and R _43.

As preferred substituents in each of the above groups, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, Alkoxy, thioether, acyl, alkoxy, alkoxycarbonyl, cyano and nitro groups. The carbon number of the substituent is preferably 8 or less.

Ar ₄ represents an (n+1)-valent aromatic ring group. The divalent aromatic ring group when n is 1, for example, arylene groups having 6 to 18 carbon atoms such as phenylene, phenylene, methylnaphthyl, and anthrylene, or containing thiophene ring, furan ring, Divalent aromatic rings of heterocycles such as pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, tri-pyrrole ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring and thiazole ring The base is better. In addition, the above-mentioned aromatic ring group may have a substituent.

As a specific example of the (n+1)-valent aromatic ring group when n is an integer of 2 or more, there can be mentioned the removal of (n-1) arbitrary hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group. The formed group is preferred. The (n+1)-valent aromatic ring group may further have a substituent.

Examples of substituents that the aforementioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n+1)-valent aromatic ring group may have include R ₄₁ and R _{42 in the general formula (I)} And alkoxy groups such as alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, butoxy, and the like listed in _{R 43; aryl groups such as phenyl and the like. Examples of the alkyl group of R 64 in -CONR 64-} (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ include methyl, ethyl, propyl, isopropyl, n-butyl, and butyl Alkyl groups having 20 or less carbon atoms, such as hexyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, are preferably alkyl groups having 8 or less carbon atoms. As X ₄ , a single bond, -COO- or -CONH- is preferred, and a single bond or -COO- is more preferred.

As the _{alkylene group in L 4} , alkylene groups having 1 to 8 carbon atoms such as methylene, ethylene, propyl, butyl, hexylene, and octylene are preferred. As Ar ₄ , an aromatic ring group having 6 to 18 carbon atoms is preferred, and a benzene ring group, a naphthalene ring group, and a biphenyl ring group are more preferred. It is preferable that the repeating unit represented by the general formula (I) has a hydroxystyrene structure. That is, Ar ₄ is preferably a benzene ring group.

As the repeating unit represented by the above general formula (I), a repeating unit represented by the following general formula (1) is preferred.

[Chemical formula 13]

In the general formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group. R represents a substituent. As the substituent represented by R, halogen atom, alkyl group, cycloalkyl group, aryl group, alkenyl group, aralkyl group, alkoxy group, alkylcarbonyloxy group, alkylsulfonyloxy group, alkoxycarbonyl group or Aryloxycarbonyl is preferred. In addition, when there are a plurality of Rs in the formula, they may be the same as or different from each other, and a plurality of Rs may be bonded to each other to form a ring. a represents an integer of 1-3. b represents an integer from 0 to (5-a).

Hereinafter, the repeating unit having an acid group is exemplified. In the formula, a represents 1 or 2.

[Chemical formula 14]

[Chemical formula 15]

[Chemical formula 16]

In addition, among the above repeating units, repeating units specifically described below are preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[Chemical formula 17]

[Chemical formula 18]

The content of the repeating unit having an acid group is preferably 5 mol% or more with respect to the total repeating units in the resin (A), and more preferably 10 mol% or more. There is no particular limitation on the upper limit, but 50 mol% or less is preferable, 45 mol% or less is more preferable, and 40 mol% or less is more preferable.

"Repeating unit with fluorine atom or iodine atom" The resin (A) may have a repeating unit having a fluorine atom or an iodine atom in addition to the above-mentioned "repeating unit having an acid-decomposable group" and "repeating unit having an acid group". In addition, the "repeating unit having a fluorine atom or an iodine atom" mentioned here, the "repeating unit having a lactone group, a sultone group, or a carbonate group" and "repeating unit having a photoacid generating group" mentioned later belong to It is preferable that other types of repeating units in the A group are different.

As the repeating unit having a fluorine atom or an iodine atom, the repeating unit represented by the formula (C) is preferred.

[Chemical formula 19]

L ₅ represents a single bond or an ester group. R ₉ represents a hydrogen atom, or an alkyl group which may have a fluorine atom or an iodine atom. R ₁₀ represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a combination of these groups.

The repeating unit having a fluorine atom or an iodine atom is illustrated below.

[Chemical formula 20]

The content of the repeating unit having a fluorine atom or an iodine atom relative to the total repeating units in the resin (A) is preferably 0 mol% or more, more preferably 5 mol% or more, and more preferably 10 mol% or more . Moreover, as the upper limit, 50 mol% or less is preferable, 45 mol% or less is more preferable, and 40 mol% or less is more preferable. In addition, as mentioned above, the repeating unit having a fluorine atom or an iodine atom does not include the "repeating unit having an acid-decomposable group" and the "repeating unit having an acid group", so the above-mentioned repeating unit having a fluorine atom or an iodine atom The content also means the content of the repeating unit having a fluorine atom or an iodine atom except for "repeating unit with acid-decomposable group" and "repeating unit with acid group".

In the repeating units of the resin (A), the total content of the repeating units containing at least one of fluorine atoms and iodine atoms is preferably 20 mol% or more, and 30 mol% or more with respect to the total repeating units of the resin (A) More preferably, it is more preferably 40 mol% or more. The upper limit is not particularly limited, and is, for example, 100 mol% or less. In addition, as the repeating unit containing at least one of a fluorine atom and an iodine atom, for example, a repeating unit having a fluorine atom or an iodine atom and an acid-decomposable group, a repeating unit having a fluorine atom or an iodine atom and an acid group, and Repeating unit with fluorine atom or iodine atom.

"Repeating unit with lactone group, sultone group or carbonate group" The resin (A) may also have a repeating unit having at least one selected from a lactone group, a sultone group, and a carbonate group (hereinafter, also collectively referred to as "the one having a lactone group, a sultone group, or a carbonate group). Repeating unit"). It is also preferable that the repeating unit having a lactone group, a sultone group or a carbonate group does not have an acid group such as a hexafluoropropanol group.

As a lactone group or a sultone group, what is necessary is just to have a lactone structure or a sultone structure. Preferably, the lactone structure or the sultone structure is a 5- to 7-membered cyclic lactone structure or a 5- to 7-membered cyclic sultone structure. Among them, in the form of forming a bicyclic structure or a spiro ring structure, the 5- to 7-membered ring lactone structure is fused with other ring structures, or in the form of forming a bicyclic structure or a spiro ring structure in the form of a 5- to 7-membered ring sultone It is better if the fused ring has other ring structures in the structure. The resin (A) preferably has a repeating unit having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21) or the following general formula (SL1- 1) A lactone group or a sultone group formed by removing one or more hydrogen atoms from the ring member atoms of the sultone structure represented by any one of to (SL1-3). In addition, the lactone group or the sultone group may be directly bonded to the main chain. For example, the ring member atoms of the lactone group or the sultone group may also constitute the main chain of the resin (A).

[Chemical formula 21]

The aforementioned lactone structure or sultone structure part may have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and 1 to 8 carbon atoms. 8. Alkoxycarbonyl group, carboxyl group, halogen atom, hydroxyl group, cyano group, acid decomposable group, etc. n2 represents an integer of 0-4. When n2 is 2 or more, the presence of a plurality of Rb ₂ may not be the same, and the presence of a plurality of Rb ₂ may be bonded to each other to form a ring.

As having a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-21) or a sultone represented by any one of the general formulas (SL1-1) to (SL1-3) Examples of the repeating unit of the group of the structure include repeating units represented by the following general formula (AI).

[Chemical formula 22]

In the general formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom or a methyl group. Ab represents a divalent linking group having a single bond, an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination of these divalent groups. Among them, a single bond or a linking group represented by _{-Ab 1} -CO _{2-is preferred.} Ab ₁ is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group. Methylene, ethylidene, cyclohexylene, adamanthenyl or norbornanyl are more good. V represents a group obtained by removing one hydrogen atom from the ring member atom of the lactone structure represented by any one of the general formulas (LC1-1) to (LC1-21), or from the general formula (SL1-1) ~(SL1-3) is a group formed by removing one hydrogen atom from the ring member atom of the sultone structure represented by any one of ~(SL1-3).

When an optical isomer is present in the repeating unit having a lactone group or a sultone group, any optical isomer may be used. In addition, one kind of optical isomers may be used alone, or plural kinds of optical isomers may be mixed and used. When mainly using one kind of optical isomer, the optical purity (ee) is preferably 90 or more, more preferably 95 or more.

As the carbonate group, a cyclic carbonate group is preferred. As the repeating unit having a cyclic carbonate group, a repeating unit represented by the following general formula (A-1) is preferred.

[Chemical formula 23]

In the general formula (A-1), R _A ¹ represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group). n represents an integer of 0 or more. R _A ² represents a substituent. When n is 2 or more, a plurality of R _A ² may be the same or different. A represents a single bond or a divalent linking group. As the above-mentioned divalent linking group, a divalent linking group having an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination thereof The group is preferred. Z represents an atomic group that forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

The following examples show repeating units having a lactone group, a sultone group, or a carbonate group.

[Chemical formula 24]

[Chemical formula 25]

[Chemical formula 26]

The content of the repeating unit having a lactone group, a sultone group, or a carbonate group is preferably 1 mol% or more with respect to the total repeating units in the resin (A), and more preferably 5 mol% or more. In addition, the upper limit is not particularly limited, but 65 mol% or less is preferable, 30 mol% or less is more preferable, 25 mol% or less is more preferable, and 20 mol% or less is particularly preferable.

"Repeating unit with photoacid generating group" As a repeating unit other than the above, the resin (A) may have a repeating unit having a group that generates acid by irradiation with actinic rays or radiation (hereinafter also referred to as a "photoacid generating group"). In this case, it can be considered that the repeating unit having the photoacid generating group corresponds to a compound (also referred to as a "photoacid generator") that generates an acid by irradiation with actinic rays or radiation, which will be described later. As such a repeating unit, the repeating unit represented by the following general formula (4) is mentioned, for example.

[Chemical formula 27]

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. R ⁴⁰ represents a structural site that decomposes by irradiation with actinic rays or radiation to generate acid in the side chain.

The repeating unit having a photoacid generating group is illustrated below.

[Chemical formula 28]

[Chemical formula 29]

In addition, as the repeating unit represented by the general formula (4), for example, the repeating unit described in paragraphs [0094] to [0105] of JP 2014-041327 A can be cited.

The content of the repeating unit having a photoacid generating group is preferably 1 mol% or more with respect to the total repeating units in the resin (A), and more preferably 5 mol% or more. Moreover, as the upper limit, 40 mol% or less is preferable, 35 mol% or less is more preferable, and 30 mol% or less is more preferable.

"Repeating unit represented by general formula (V-1) or the following general formula (V-2)" The resin (A) may have a repeating unit represented by the following general formula (V-1) or the following general formula (V-2). The repeating unit represented by the following general formula (V-1) and the following general formula (V-2) is preferably a repeating unit different from the above-mentioned repeating unit.

[Chemical formula 30]

In the formula, R ₆ and R ₇ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R Is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group) or a carboxyl group. As the alkyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferred. n ₃ represents an integer of 0-6. n ₄ represents an integer of 0-4. X ₄ is a methylene group, an oxygen atom or a sulfur atom. The following examples illustrate the repeating unit represented by the general formula (V-1) or (V-2).

[Chemical formula 31]

"Repeating Units Used to Reduce the Mobility of the Main Chain" From the viewpoint of being able to suppress excessive diffusion of the generated acid or pattern collapse during development, it is preferable that the glass transition temperature (Tg) of the resin (A) be higher. The Tg is preferably greater than 90°C, more preferably greater than 100°C, more preferably greater than 110°C, and particularly preferably greater than 125°C. In addition, excessively high Tg will result in a decrease in the dissolution rate in the developer. Therefore, the Tg is preferably 400°C or less, and more preferably 350°C or less. In addition, in this specification, the glass transition temperature (Tg) of the polymer, such as resin (A), is calculated by the following method. First, the Tg of a homopolymer including only each repeating unit contained in the polymer is separately calculated by the Bicerano method. Hereinafter, the calculated Tg is referred to as "Tg of the repeating unit". Next, the mass ratio (%) of each repeating unit relative to the total repeating unit in the polymer is calculated. Next, the Tg at each mass ratio is calculated using the formula of Fox (described in Materials Letters 62 (2008) 3152, etc.), and these are added together and used as the Tg (°C) of the polymer. The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993) and others. In addition, the calculation of Tg based on the Bicerano method can be performed using MDL Polymer (MDL Information Systems, Inc.), a software for calculating physical properties of polymers.

In order to increase the Tg of the resin (A) (it is preferable to set the Tg to exceed 90° C.), it is preferable to reduce the mobility of the main chain of the resin (A). As a method of reducing the mobility of the main chain of the resin (A), the following methods (a) to (e) can be cited. (A) Introduce bulky substituents in the main chain (B) Introduce multiple substituents in the main chain (C) Introduce substituents that cause interaction between resins (A) near the main chain (D) The main chain forming the ring structure (E) Connect the ring structure to the main chain In addition, the resin (A) preferably has a repeating unit having a homopolymer Tg of 130°C or higher. In addition, there is no particular limitation on the type of repeating unit whose Tg of the homopolymer is 130°C or higher, as long as it is a repeating unit whose Tg of the homopolymer calculated by the Bicerano method is 130°C or higher. In addition, depending on the type of the functional group in the repeating unit represented by the formula (A) to the formula (E) described later, the homopolymer corresponds to a repeating unit having a Tg of 130° C. or more.

(Repeating unit represented by formula (A)) As an example of the specific realization of the above (a), a method of introducing the repeating unit represented by the formula (A) into the resin (A) can be cited.

[Chemical formula 32]

In the formula _(A), R A represents a group having a polycyclic structures. R _x represents a hydrogen atom, a methyl group or an ethyl group. A group with a polycyclic structure is a group with a plurality of ring structures, and the plurality of ring structures may or may not be fused. As a specific example of the repeating unit represented by formula (A), the following repeating unit can be mentioned.

[Chemical formula 33]

[Chemical formula 34]

[Chemical formula 35]

In the above formula, R represents a hydrogen atom, a methyl group, or an ethyl group. Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR'"Or-COOR"':R'" is an alkyl group having 1 to 20 carbons or a fluorinated alkyl group) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by Ra may be substituted with a fluorine atom or an iodine atom. In addition, R'and R'' each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, and a halogen atom. , Ester group (-OCOR''' or -COOR''': R''' is an alkyl or fluorinated alkyl group with 1 to 20 carbons) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R′ and R″ may be substituted with a fluorine atom or an iodine atom. L represents a single bond or a divalent linking group. As the divalent linking group, for example, -COO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene, cycloalkylene, alkenylene and connected A plurality of these connecting bases, etc. m and n each independently represent an integer of 0 or more. The upper limit of m and n is not particularly limited, and most of them are 2 or less, and more are 1 or less.

(Repeating unit represented by formula (B)) As an example of the specific realization of the above (b), a method of introducing the repeating unit represented by the formula (B) into the resin (A) can be cited.

[Chemical formula 36]

In formula (B), R _b1 to R _b4 each independently represent a hydrogen atom or an organic group, and at least two of _{R b1} to R _{b4 represent an organic group.} In addition, when at least one of the organic groups is a group in which a ring structure is directly connected to the main chain in the repeating unit, the types of other organic groups are not particularly limited. In addition, when none of the organic groups is a group in which a ring structure is directly connected to the main chain of the repeating unit, at least two of the organic groups have at least 3 constituent atoms other than hydrogen atoms. Substituents.

As specific examples of the repeating unit represented by the formula (B), the following repeating units can be cited.

[Chemical formula 37]

In the above formula, R each independently represents a hydrogen atom or an organic group. Examples of the organic group include organic groups such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group which may also have a substituent. R'each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR "Or -COOR": R" is an alkyl group having 1 to 20 carbons or a fluorinated alkyl group) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R'may be substituted by a fluorine atom or an iodine atom. m represents an integer of 0 or more. The upper limit of m is not particularly limited, and it is often 2 or less, and more is 1 or less.

(Repeating unit represented by formula (C)) As an example of the specific realization of the above (c), a method of introducing the repeating unit represented by the formula (C) into the resin (A) can be cited.

[Chemical formula 38]

In formula (C), R _c1 to R _c4 each independently represent a hydrogen atom or an organic group, _{and at least one of R c1} to R _c4 is a group having a hydrogen bonding hydrogen atom within 3 atoms of the main chain carbon . Among them, in order to cause interaction between the main chains of the resin (A), a hydrogen atom having a hydrogen bond within 2 atoms (closer to the main chain side) is preferred.

As a specific example of the repeating unit represented by formula (C), the following repeating unit can be mentioned.

[Chemical formula 39]

In the above formula, R represents an organic group. Examples of the organic group include optionally substituted alkyl, cycloalkyl, aryl, aralkyl, alkenyl, and ester groups (-OCOR or -COOR: R is an alkyl group having 1 to 20 carbons or Fluorinated alkyl) and so on. R'represents a hydrogen atom or an organic group. Examples of the organic group include organic groups such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. In addition, the hydrogen atom in the organic group may be substituted with a fluorine atom or an iodine atom.

(Repeating unit represented by formula (D)) As an example of a specific realization of the above (d), a method of introducing the repeating unit represented by formula (D) into the resin (A) can be cited.

[Chemical formula 40]

In formula (D), "cylic" means a group formed by forming a main chain with a cyclic structure. The number of atoms constituting the ring is not particularly limited.

As a specific example of the repeating unit represented by formula (D), the following repeating unit can be mentioned.

[Chemical formula 41]

In the above formula, R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, and a halogen atom , Ester group (-OCOR" or -COOR": R" is an alkyl or fluorinated alkyl group with 1 to 20 carbons) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom. In the above formula, R'each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester Group (-OCOR" or -COOR": R" is an alkyl group or fluorinated alkyl group having 1 to 20 carbons) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R'may be substituted by a fluorine atom or an iodine atom. m represents an integer of 0 or more. The upper limit of m is not particularly limited, and it is often 2 or less, and more is 1 or less.

(Repeating unit represented by formula (E)) As an example of the specific realization of the above (e), a method of introducing the repeating unit represented by formula (E) into the resin (A) can be cited.

[Chemical formula 42]

In formula (E), Re each independently represents a hydrogen atom or an organic group. As an organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. which may also have a substituent are mentioned. "Cylic" is a cyclic group containing carbon atoms of the main chain. The number of atoms contained in the cyclic group is not particularly limited.

As specific examples of the repeating unit represented by the formula (E), the following repeating units can be cited.

[Chemical formula 43]

[Chemical formula 44]

In the above formula, R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, and a halogen atom , Ester group (-OCOR" or -COOR": R" is an alkyl or fluorinated alkyl group with 1 to 20 carbons) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom. R'each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, and an ester group (-OCOR" or -COOR": R" is an alkyl group or fluorinated alkyl group having 1 to 20 carbons) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R'may be substituted by a fluorine atom or an iodine atom. m represents an integer of 0 or more. The upper limit of m is not particularly limited, and it is often 2 or less, and more is 1 or less. In addition, in formula (E-2), formula (E-4), formula (E-6), and formula (E-8), two Rs may be bonded to each other to form a ring.

The content of the repeating unit represented by the formula (E) is preferably 5 mol% or more with respect to the total repeating units in the resin (A), and more preferably 10 mol% or more. Moreover, as the upper limit, 60 mol% or less is preferable, and 55 mol% or less is more preferable.

"Repeating unit having at least one group selected from lactone group, sultone group, carbonate group, hydroxyl group, cyano group and alkali-soluble group" The resin (A) may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, and a cyano alkali soluble group. The repeating unit having a lactone group, a sultone group or a carbonate group contained in the resin (A) includes the repeating unit described in the above "Repeating unit having a lactone group, sultone group or carbonate group" . The preferable content is also as described in the above "Repeating Unit with Lactone Group, Sultone Group or Carbonate Group".

The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. Thereby, substrate adhesion and developer affinity are improved. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group. It is preferable that the repeating unit having a hydroxyl group or a cyano group does not have an acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include repeating units represented by the following general formulas (AIIa) to (AIId).

[Chemical formula 45]

In the general formulas (AIIa) to (AIId), R _1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R _2c to R _4c each independently represent a hydrogen atom, a hydroxyl group, or a cyano group. Among them, _{at least one of R 2c} to R _4c represents a hydroxyl group or a cyano group. Preferably, one or two of R _2c to R _4c are hydroxyl groups, and the remainder are hydrogen atoms. More preferably _{, two of R 2c} to R _4c are hydroxyl groups, and the remainder are hydrogen atoms.

The content of the repeating unit having a hydroxyl group or a cyano group is preferably 5 mol% or more with respect to the total repeating units in the resin (A), and more preferably 10 mol% or more. Moreover, as the upper limit, 40 mol% or less is preferable, 35 mol% or less is more preferable, and 30 mol% or less is more preferable.

Specific examples of repeating units having a hydroxyl group or a cyano group are listed below, but the present invention is not limited to these.

[Chemical formula 46]

The resin (A) may have a repeating unit having an alkali-soluble group. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonamide groups, bissulfonamide groups, and aliphatic alcohols substituted with electron withdrawing groups at the α position (for example, hexafluoroisopropyl Alcohol group), carboxyl group is preferred. Resin (A) contains repeating units having alkali-soluble groups, so that the resolution when used for contact hole applications is increased. Examples of the repeating unit having an alkali-soluble group include repeating units based on acrylic acid and methacrylic acid, which are directly bonded to the main chain of the resin with an alkali-soluble group, or are bonded to the main chain of the resin via a linking group. Repeating units with alkali-soluble groups. In addition, the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. As the repeating unit having an alkali-soluble group, a repeating unit based on acrylic acid or methacrylic acid is preferred.

The content of the repeating unit having an alkali-soluble group is preferably 0 mol% or more with respect to the total repeating units in the resin (A), more preferably 3 mol% or more, and even more preferably 5 mol% or more. As the upper limit, 20 mol% or less is preferable, 15 mol% or less is more preferable, and 10 mol% or less is more preferable.

Although the specific example of the repeating unit which has an alkali-soluble group is shown below, this invention is not limited to this. In specific examples, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .

[Chemical formula 47]

As a repeating unit having at least one group selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group, a repeating unit having at least two selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group is Preferably, a repeating unit having a cyano group and a lactone group is more preferred, and a repeating unit having a structure in which a cyano group is substituted on the lactone structure represented by the general formula (LC1-4) is even more preferred.

"Repeating units that have an alicyclic hydrocarbon structure and do not show acid decomposability" The resin (A) may have an alicyclic hydrocarbon structure and a repeating unit that does not show acid decomposability. This can reduce the elution of low-molecular components from the resist film into the liquid immersion liquid during liquid immersion exposure. Examples of such repeating units include 1-adamantyl (meth)acrylate, diamond alkyl (meth)acrylate, tricyclodecyl (meth)acrylate, or cyclohexyl (meth)acrylate. Repeating units of acrylates, etc.

"A repeating unit represented by general formula (III) that does not have any of a hydroxyl group and a cyano group" The resin (A) may not have any one of a hydroxyl group and a cyano group and may have a repeating unit represented by the general formula (III).

[Chemical formula 48]

In the general formula (III), R ₅ represents a hydrocarbon group having at least one cyclic structure and not having any one of a hydroxyl group and a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH ₂ -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group.

The cyclic structure of R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include cycloalkyl groups having 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) or cycloalkenyl groups having 3 to 12 carbon atoms.

Examples of the polycyclic hydrocarbon group include a ring assembly hydrocarbon group and a crosslinked cyclic hydrocarbon group. Examples of the crosslinked cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a 4-cyclic hydrocarbon ring. In addition, the crosslinked cyclic hydrocarbon ring also includes a fused ring in which a plurality of 5- to 8-membered cycloalkane rings are fused. As the cross-linked cyclic hydrocarbon group, norbornyl, adamantyl, bicyclooctyl or tricyclic [ ^{5 , 2, 1, 0 2, 6} ]decyl is preferred, norbornyl or adamantyl is more preferred .

The alicyclic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protective group, and an amine group protected by a protective group. As the halogen atom, a bromine atom, a chlorine atom or a fluorine atom is preferred. As the alkyl group, methyl, ethyl, butyl or tertiary butyl is preferred. The above-mentioned alkyl group may further have a substituent. Examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protective group, or an amino group protected by a protective group.

Examples of the protective group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkoxycarbonyl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferred. As the substituted methyl group, methoxymethyl, methoxythiomethyl, benzyloxymethyl, tert-butoxymethyl, or 2-methoxyethoxymethyl is preferred. As the substituted ethyl group, 1-ethoxyethyl or 1-methyl-1-methoxyethyl is preferred. As the acyl group, aliphatic acyl groups having 1 to 6 carbon atoms, such as formyl, acetyl, propyl, butyryl, isobutyryl, pentanyl, and trimethyl acetyl, are preferred. As the alkoxycarbonyl group, an alkoxycarbonyl group having 1 to 4 carbon atoms is preferred.

It does not have any one of a hydroxyl group and a cyano group and the content of the repeating unit represented by the general formula (III) is preferably 0-40 mol% relative to the total repeating units in the resin (A), 0-20 mol% % Is better. Specific examples of the repeating unit represented by the general formula (III) are listed below, but the present invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH or CF ₃ .

[Chemical formula 49]

"Other Repeating Units" Furthermore, the resin (A) may have repeating units other than the above repeating units. For example, the resin (A) may also have a repeating unit selected from the group having an oxothione ring group, a repeating unit having an oxazolidinone ring group, a repeating unit having a dioxazolinone ring group, and a hydantoin The repeating unit in the repeating unit of the cyclic group. Examples of such repeating units are shown below.

[Chemical formula 50]

In addition to the above repeating structural units, the resin (A) can also have various repeating structural units for the purpose of adjusting dry etching resistance, standard developer compatibility, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

As the resin (A), (in particular, when the composition is used for ArF applications), all repeating units are preferably composed of (meth)acrylate-based repeating units. In this case, it is possible to use those whose repeating units are all methacrylate-based repeating units, those whose repeating units are all acrylate-based repeating units, and those whose repeating units are all based on methacrylate-based repeating units and acrylate-based repeating units. In either case, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating unit.

The resin (A) can be synthesized according to a conventional method (for example, radical polymerization). As a polystyrene conversion value by the GPC method, the weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and more preferably 5,000 to 15,000. By setting the weight average molecular weight of the resin (A) to 1,000 to 200,000, it is possible to further suppress the deterioration of heat resistance and dry etching resistance. In addition, it is possible to further suppress deterioration of developability and deterioration of film forming properties due to increased viscosity. The degree of dispersion (molecular weight distribution) of the resin (A) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.0. The smaller the degree of dispersion, the better the resolution and the shape of the resist, and the sidewalls of the resist pattern are smoother and the roughness is better.

In the resist composition, the content of the resin (A) relative to the total solid content of the composition is preferably 50 to 99.9% by mass, and more preferably 60 to 99.0% by mass. In addition, the solid content means a component other than the solvent in the composition, and as long as it is a component other than the solvent, it may be a liquid component or a solid component. In addition, one kind of resin (A) may be used, or a plurality of kinds may be used in combination.

>A compound that generates acid by actinic rays or radiation (photoacid generator)> The resist composition preferably contains a compound that generates acid by actinic rays or radiation (hereinafter, also referred to as "photo acid generator "PAG: Photo Acid Generator"). The photoacid generator may be in the form of a low-molecular compound, or may be incorporated in a part of the polymer. In addition, the form of a low-molecular compound and the form of a part incorporated in the polymer may be used in combination. When the photoacid generator is in the form of a low-molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. When the photoacid generator is incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) or may be incorporated in a resin different from the resin (A). In the present invention, it is preferable that the photoacid generator is a low-molecular-weight compound. The photoacid generator is not particularly limited as long as it is a well-known one, but it is preferable that actinic rays or radiation are irradiated with electron beams or extreme ultraviolet to generate organic acids such as sulfonic acid, bis(alkylsulfonyl sulfonyl) ) A compound of at least any one of imidine or tris(alkylsulfonyl) methide is preferred. More preferably, compounds represented by the following general formulas (ZI), (ZII), and (ZIII) can be cited.

[Chemical formula 51]

In the above general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. The carbon number of the organic group of R ₂₀₁ , R ₂₀₂ and R _{203 is usually 1-30, preferably 1-20.} In addition, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, or an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbonyl group may be contained in the ring. Examples of the group formed by bonding two of R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, a butylene group and a pentenyl group). Z ^- represents a non-nucleophilic anion (an anion whose ability to cause a nucleophilic reaction is significantly lower).

Examples of non-nucleophilic anions include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphorsulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, aromatic sulfonic acid anions, etc.). Alkyl carboxylic acid anion, etc.), sulfonylimide anion, bis(alkylsulfonylimide) anion, tri(alkylsulfonylimide) methide anion, etc.

The aliphatic part in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number of 3-30 cycloalkyl.

The aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, cycloalkyl group, and aryl group exemplified above may have a substituent. As specific examples thereof, halogen atoms such as nitro group and fluorine atom, carboxyl group, hydroxyl group, amino group, cyano group, alkoxy group (preferably carbon number 1-15), cycloalkyl group (preferably carbon number 3 ~15), aryl (preferably carbon number 6-14), alkoxycarbonyl (preferably carbon number 2-7 is preferred), acyl group (preferably carbon number 2-12), alkoxy Alkylcarbonyloxy (preferably carbon number 2-7), alkylthio (preferably carbon number 1-15), alkylsulfonyl group (preferably carbon number 1-15), alkylimino group Sulfonyl (preferably carbon number 1-15), aryloxysulfonyl group (preferably carbon number 6-20), alkylaryloxysulfonyl group (preferably carbon number 7-20), Cycloalkylaryloxysulfonyl (preferably with 10 to 20 carbons), alkoxyalkoxy (preferably with 5 to 20 carbons), cycloalkylalkoxyalkoxy (preferably with Carbon number 8-20) and so on. Regarding the aryl group and ring structure possessed by each group, an alkyl group (preferably having 1 to 15 carbon atoms) can also be mentioned as a substituent.

The aralkyl group in the aralkylcarboxylic acid anion is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutane. Base and so on.

As the sulfonylimine anion, for example, a saccharin anion can be cited.

The alkyl group in the bis(alkylsulfonyl)imide anion and the tri(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents of these alkyl groups include halogen atoms, alkyl groups substituted by halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxy groups. For the sulfonyl group and the like, a fluorine atom or an alkyl group substituted with a fluorine atom is preferred. In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure. With this, the acid strength increases.

As another non-affinity anion, and examples thereof include phosphorus fluoride (e.g., PF ₆ ^-), boron trifluoride (e.g., BF ₄ ^-), antimony fluoride (e.g., SbF ₆ ^-) and the like.

As non-affinity anions, aliphatic sulfonic acid anions in which at least the α-position in sulfonic acid is substituted by fluorine atoms, aromatic sulfonic acid anions substituted by fluorine atoms or groups with fluorine atoms, and double alkyl groups substituted by fluorine atoms The (alkylsulfonyl) iminium anion and the tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom are preferred. The non-affinity anion is more preferably a perfluoroaliphatic sulfonic acid anion (further preferably a carbon number of 4-8), a benzenesulfonic acid anion having a fluorine atom, more preferably a nonafluorobutanesulfonic acid anion, Fluorooctanesulfonic acid anion, pentafluorobenzenesulfonic acid anion, 3,5-bis(trifluoromethyl)benzenesulfonic acid anion.

From the viewpoint of acid strength, in order to increase sensitivity, the pKa of the generated acid is preferably -1 or less.

Moreover, as a non-affinity anion, the anion represented by the following general formula (AN1) can also be mentioned as a preferable aspect.

[Chemical formula 52]

In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when a plurality of R ¹ and R ^{2 are present, they} may be the same or different. L represents a divalent linking group, and when there are plural, L may be the same or different from each other. A represents a cyclic organic group. x represents an integer of 1-20, y represents an integer of 0-10, and z represents an integer of 0-10.

The general formula (AN1) is described in further detail. The alkyl group in the alkyl group substituted with a fluorine atom of Xf preferably has 1 to 10 carbon atoms, and more preferably has 1 to 4 carbon atoms. Furthermore, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ , among which fluorine atom and CF ₃ are preferred. In particular, it is preferable that two Xf are fluorine atoms.

The alkyl group of R ¹ and R ² may also have a substituent (preferably a fluorine atom), and the carbon number is preferably 1 to 4. More preferred is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having substituents for R ¹ and R ² _{include CF 3} , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ , of which CF ₃ is preferred. As R ¹ and R ² , a fluorine atom or CF _{3 is} preferable.

It is preferable that x is 1-10, and it is more preferable that it is 1-5. It is preferable that y is 0-4, and 0 is more preferable. It is preferable that z is 0-5, and it is more preferable that it is 0-3. The divalent linking group of L is not particularly limited, and examples include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene, ring extension An alkyl group, an alkenylene group or a linking group connecting a plurality of these, etc., a linking group having a total carbon number of 12 or less is preferred. Among them, -COO-, -OCO-, -CO-, -O- are preferred, and -COO- and -OCO- are more preferred.

In the above general formula (AN1), as a combination of partial structures other than A, preferred examples include SO ^3- -CF ₂ -CH ₂ -OCO-, SO ^3- -CF ₂ -CHF-CH ₂ -OCO- , SO ^3- -CF ₂ -COO-, SO ^3- -CF ₂ -CF ₂ -CH ₂ -, SO ^3- -CF ₂ -CH (CF ₃ ) -OCO-.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and examples include alicyclic groups, aryl groups, and heterocyclic groups (not only those having aromatic properties, but also those that do not have aromatic properties.者) etc. As an alicyclic group, it can be monocyclic or polycyclic, monocyclic cycloalkyl, norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclodecyl, such as cyclopentyl, cyclohexyl, and cyclooctyl. Polycyclic cycloalkyl groups such as dialkyl and adamantyl are preferred. Among them, from the viewpoint of suppressing the diffusibility in the film in the heating step after exposure and improving the MEEF (mask error enhancement factor), norbornyl, tricyclodecyl, tetracyclodecyl, and tetracyclodecyl Alicyclic groups having a bulky structure with a carbon number of 7 or more, such as dodecyl and adamantyl, are preferred. Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Among them, those derived from furan ring, thiophene ring, and pyridine ring are preferred.

In addition, as the cyclic organic group, a lactone structure can also be cited. As a specific example, a lactone structure represented by the following general formulas (LC1-1) to (LC1-17) can be cited.

[Chemical formula 53]

The above-mentioned cyclic organic group may also have a substituent. Examples of the above-mentioned substituent include an alkyl group (any one of linear, branched and cyclic, and carbon number is preferably 1-12), cycloalkane Group (monocyclic, polycyclic, spiro ring, any one, carbon number is 3-20 is preferable), aryl group (carbon number is 6-14 is preferable), hydroxyl, alkoxy, ester group , Amide group, urethane group, urea group, thioether group, sulfonamide group, sulfonate group, etc. In addition, the carbon constituting the cyclic organic group (the carbon that contributes to the formation of the ring) may be a carbonyl carbon. _{In addition, the aforementioned substituent corresponds to Rb 2} in the aforementioned (LC1-1) to (LC1-17). In addition, in the above (LC1-1) to (LC1-17), n2 represents an integer of 0-4. When n2 is 2 or more, the presence of a plurality of Rb ₂ may be the same or different, and the presence of a plurality of Rb ₂ may be bonded to each other to form a ring.

In the general formula (ZI) _{, examples of the organic group of R 201} , R ₂₀₂ and R ₂₀₃ include an aryl group, an alkyl group, and a cycloalkyl group. It _{is preferable that at least one of R 201} , R ₂₀₂ and R ₂₀₃ is an aryl group, and it is more preferable that all three of R 201, R 202 and R 203 are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, etc., a heteroaryl group such as an indole residue and a pyrrole residue may also be used. As _{the alkyl group and cycloalkyl group of R 201} to R ₂₀₃ , a straight or branched chain alkyl group having 1 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms are preferable. As an alkyl group, methyl, ethyl, n-propyl, isopropyl, n-butyl, etc. can be mentioned more preferably. As a cycloalkyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. can be mentioned more preferably. These groups may further have substituents. Examples of substituents that may be further include halogen atoms such as nitro group and fluorine atom, carboxyl group, hydroxyl group, amino group, cyano group, alkoxy group (preferably carbon number 1-15), cycloalkyl group (preferably Carbon number 3-15), aryl group (preferably carbon number 6-14), alkoxycarbonyl group (preferably carbon number 2-7), acyl group (preferably carbon number 2-12), alkoxy Group carbonyloxy (preferably carbon number 2-7) and the like, but not limited to these.

Next, the general formulas (ZII) and (ZIII) will be described. In general formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group, or a cycloalkyl group. As _{the aryl group of R 204} to R ₂₀₇ , phenyl and naphthyl are preferred, and phenyl is more preferred. The aryl group of R ₂₀₄ to R ₂₀₇ may also be an aryl group having a heterocyclic structure including an oxygen atom, a nitrogen atom, a sulfur atom, and the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like. As _{the alkyl group and cycloalkyl group in R 204} to R ₂₀₇ , it is preferable to be a straight or branched chain alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, propyl, butyl, pentylene, etc.). Group), C3-10 cycloalkyl (cyclopentyl, cyclohexyl, norbornyl).

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R _{207 may have a substituent.} Examples of substituents that the aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include an alkyl group (for example, a carbon number of 1 to 15), a cycloalkyl group (for example, a carbon number of 3 to 15), Aryl group (for example, carbon number is 6-15), alkoxy group (for example, carbon number is 1-15), halogen atom, hydroxyl group, thiophenyl group, etc.

In the general formula (ZII), Z ^- represents a non-nucleophilic anion. ^{Specifically, it is the same as that described as Z-} in the general formula (ZI), and the preferred form is also the same.

Below, although the specific example of general formula (ZI)-(ZIII) is shown, it is not limited to this.

[Chemical formula 54]

In the present invention, the acid generated from the diffusion suppressing the exposure the non-exposed portion and to optimize the viewpoint of resolution of the photoacid generator is irradiated by an electron beam or extreme ultraviolet generated volume greater than 130Å ³ acid (more preferably sulfonic acid) of the compound, to produce a volume of greater than 190Å ³ acid (more preferably sulfonic acid) is more preferably the compound, to produce a volume of greater than 270Å ³ acid (more preferably sulfonic acid) of compound For further preference, compounds that generate acids (more sulfonic acids) with a volume of 400 Å ^{3 or more are particularly preferred.} Wherein, sensitivity and coating solvent solubility from the viewpoint of the volume of 2000Å ³ or less is preferred, 1500Å ³ or less is further preferred. The value of the above-mentioned volume was obtained using "WinMOPAC" manufactured by FUJITSU LIMITED. That is, first input the chemical structure of the acid of each example, and then use the structure as the initial structure to determine the most stable three-dimensional configuration of each acid by using the molecular force field calculation of the MM3 method. The configuration is calculated by the molecular orbital calculation using PM3 method, so that the "accessible volume" of each acid can be calculated. In addition, 1Å means 0.1nm. In the present invention, a photoacid generator which generates an acid exemplified below by irradiation with actinic rays or radiation is preferred. In addition, mark the calculated value of the volume (unit Å ³ ) for some examples. In addition, the calculated value obtained here is the value of the volume of the acid bound to the proton at the anion part.

[Chemical formula 55]

[Chemical formula 56]

[Chemical formula 57]

As the photoacid generator, paragraphs <0368> to <0377> of Japanese Patent Application Publication No. 2014-041328, paragraphs <0240> to <0262> of Japanese Patent Application Publication No. 2013-228681 (corresponding to U.S. Patent Application Publication No. 2015 /0004533 manual <0339>), and these contents are incorporated in this manual. In addition, as preferred specific examples, the following compounds can be cited, but they are not limited to these.

[Chemical formula 58]

[Chemical formula 59]

[Chemical formula 60]

[Chemical formula 61]

The photoacid generator can be used individually by 1 type or in combination of 2 or more types. The content of the photoacid generator in the resist composition is based on the total solid content of the composition, preferably 0.1-50% by mass, more preferably 5-50% by mass, and even more preferably 8-40% by mass . In particular, in order to achieve both high sensitivity and high resolution during electron beam or extreme ultraviolet exposure, it is preferable that the content of the photoacid generator is relatively high. From the above viewpoint, 10 to 40% by mass is preferable, and 10 to 35% by mass is more preferable.

＜Solvent＞ When the above-mentioned components are dissolved to prepare the resist composition, a solvent can be used. As the solvent that can be used, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxy propionate, and carbon number 4 can be mentioned. Organic solvents such as cyclic lactones of ∼10, monoketone compounds having a carbon number of 4 to 10 that may contain a ring, alkylene carbonate, alkyl alkoxy acetate, alkyl pyruvate, and the like.

As alkylene glycol monoalkyl ether carboxylates, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate are preferably mentioned. , Propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate. As alkylene glycol monoalkyl ethers, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether are preferred. good.

Examples of the alkyl lactate include preferably methyl lactate, ethyl lactate, propyl lactate, and butyl lactate. As the alkyl alkoxypropionate, for example, ethyl 3-ethoxypropionate, 3-methoxypropionate, 3-ethoxymethylpropionate, 3-methoxypropionate Ethyl propionate.

Examples of cyclic lactones having 4 to 10 carbon atoms include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, and β-butyrolactone. Methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-capryrolactone, α-hydroxy-γ-butyrolactone.

As the monoketone compound having 4 to 10 carbon atoms which may contain a ring, for example, 2-butanone, 3-methylbutanone, tertiary butyl ethyl ketone, 2-pentanone, and 3-pentanone can be mentioned. , 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl 3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3 -Heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone Ketone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one, Cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3- Methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6- Trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcycloheptanone.

As the alkylene carbonate, for example, propylene carbonate, ethylene carbonate, ethylene carbonate, and ethylene carbonate are preferable. As the alkyl alkoxyacetate, for example, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, and 2-methoxyethyl acetate are preferred. Ester, 3-methoxy-3-methylbutyl acetate, 1-methoxy-2-propyl acetate. As the alkyl pyruvate, for example, methyl pyruvate, ethyl pyruvate, and propyl pyruvate are preferably cited. As a solvent that can be preferably used, a solvent having a boiling point of 130°C or higher at normal temperature and normal pressure can be cited. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate , Ethyl pyruvate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy) ethyl acetate, propylene carbonate. In the present invention, the above-mentioned solvents may be used alone, or two or more of them may be used in combination.

In the present invention, as an organic solvent, a mixed solvent in which a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group are mixed in the structure can also be used. As a solvent containing a hydroxyl group, for example, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, etc. can be cited. Among these, propylene glycol monomethyl ether , Ethyl lactate is particularly good. Examples of solvents that do not contain hydroxyl groups include propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, and N-methyl Pyrrolidone, N,N-dimethylacetamide, dimethyl sulfide, etc., among these, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ- Butyrolactone, cyclohexanone, and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, and 2-heptanone are the most preferred. The mixing ratio (mass ratio) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and still more preferably 20/80 to 60 /40. A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferable in terms of coating uniformity.

The solvent is preferably a mixed solvent of two or more types including propylene glycol monomethyl ether acetate. Among them, the combination of γ-butyrolactone and butyl acetate is particularly preferred.

As the solvent, for example, the solvents described in paragraphs 0013 to 0029 of JP 2014-219664 A can also be used.

＜Basic compound＞ In order to reduce the time-dependent performance change from exposure to heating, the resist composition preferably contains (E) a basic compound. As a basic compound, the compound which has a structure represented by following formula (A1)-(E1) can be mentioned preferably.

[Chemical formula 62]

In the general formulas (A1) and (E1), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and represent a hydrogen atom, an alkyl group (preferably carbon number 1-20), a cycloalkyl group (preferably It is a carbon number of 3-20) or an aryl group (preferably a carbon number of 6-20). Here, R ²⁰¹ and R ²⁰² may also be bonded to each other to form a ring.

With regard to the aforementioned alkyl group, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms or a cyanoalkyl group having 1 to 20 carbon atoms are preferred. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different from each other, and represent an alkyl group having 1 to 20 carbon atoms. It is more preferable that the alkyl group in these general formulas (A1) and (E1) is unsubstituted.

As preferred compounds, in addition to guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminopyrrolidine, aminoalkylaminoline, and piperidine, there can be enumerated those having an imidazole structure, Diazabicyclic structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure compound, alkylamine derivative with hydroxyl and/or ether linkage, hydroxyl and/or ether The bond of aniline derivatives and so on.

As a compound containing an imidazole structure, imidazole, 2,4,5-triphenylimidazole, benzimidazole, etc. are mentioned. Examples of compounds having a diazabicyclic structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene , 1,8-diazabicyclo[5,4,0]undec-7-ene, etc. Examples of compounds having an onium hydroxide structure include triaryl sulfonium hydroxide, benzyl methyl sulfonium hydroxide, and sulfonium hydroxide having 2-oxoalkyl groups, and specific examples include triphenyl sulfonium hydroxide, hydrogen Tris(tertiary butyl phenyl) sulfonium oxide, bis(tertiary butyl phenyl) iodonium hydroxide, benzyl methyl thiophenium hydroxide, 2-oxopropyl thiophenium hydroxide, etc. Examples of compounds having an onium carboxylate structure where the anion portion of a compound having an onium hydroxide structure becomes a carboxylate include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. As the compound having a trialkylamine structure, tri(n-butyl)amine, tri(n-octyl)amine, etc. can be cited. As the aniline compound, 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, N,N-dihexylaniline, etc. can be cited. Examples of alkylamine derivatives having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, tris(methoxyethoxyethyl)amine, and the like. Examples of aniline derivatives having a hydroxyl group and/or ether bond include N,N-bis(hydroxyethyl)aniline and the like.

As a preferable basic compound, an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group can also be cited.

As the amine compound, one-stage, two-stage, and three-stage amine compounds can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferred. The amine compound is more preferably a tertiary amine compound. As long as the amine compound has at least one alkyl group (preferably carbon number 1-20) bonded to the nitrogen atom, in addition to the alkyl group, it may also be a cycloalkyl group (preferably carbon number 3-20) or an aryl group ( Preferably, 6-12 carbon atoms are bonded to a nitrogen atom. In addition, the amine compound has an oxygen atom in the alkyl chain, and it is preferable to form an oxyalkylene group. The number of oxyalkylene groups in the molecule is one or more, preferably 3-9, more preferably 4-6. Among the oxyethylene groups, oxyethylene (-CH ₂ CH ₂ O-) or oxypropylene (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) are preferred, More preferred is oxyethylene.

As the ammonium salt compound, ammonium salt compounds of 1, 2, 3, and 4 levels can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferred. As long as the ammonium salt compound has at least one alkyl group (preferably carbon number 1-20) bonded to a nitrogen atom, in addition to the alkyl group, it may also be a cycloalkyl group (preferably carbon number 3-20) or an aryl group (Preferably carbon number 6-12) is bonded to a nitrogen atom. The ammonium salt compound has an oxygen atom in the alkyl chain, and it is preferable to form an oxyalkylene group. The number of oxyalkylene groups in the molecule is one or more, preferably 3-9, more preferably 4-6. Among the oxyalkylene groups, oxyethylene (-CH ₂ CH ₂ O-) or oxypropylene (-CH(CH ₃ )CH ₂ O- or CH ₂ CH ₂ CH ₂ O-) is preferred, and further Preferably it is oxyethylene. Examples of the anion of the ammonium salt compound include a halogen atom, sulfonate, borate, and phosphate. Among them, halogen atom and sulfonate are preferred. As the halogen atom, chloride, bromide, and iodide are particularly preferred, and as the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferred. Examples of organic sulfonates include alkyl sulfonates and aryl sulfonates having 1 to 20 carbon atoms. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy, acyl, and aryl. As the alkyl sulfonate, specifically, methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane Sulfonate, pentafluoroethane sulfonate, nonafluorobutane sulfonate, etc. Examples of the aryl group of the arylsulfonate include a benzene ring, a naphthalene ring, and an anthracene ring. The benzene ring, naphthalene ring, and anthracene ring may also have a substituent. As the substituent, a linear or branched alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms are preferred. Specific examples of linear or branched alkyl groups and cycloalkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-hexyl, and cycloalkyl groups. Hexyl etc. Examples of other substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an acyl group, and an acyloxy group.

The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group refer to those having a phenoxy group at the end of the alkyl group of the amine compound or the ammonium salt compound on the opposite side to the nitrogen atom. The phenoxy group may have a substituent. As the substituent of the phenoxy group, for example, an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylate group, a sulfonate group, an aryl group, an aralkyl group, an acyloxy group, Aryloxy and so on. The substitution position of the substituent may be any one of 2 to 6 positions. The number of substituents may be any one in the range of 1-5.

It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups in the molecule is one or more, preferably 3-9, more preferably 4-6. Among the oxyethylene groups, oxyethylene (-CH ₂ CH ₂ O-) or oxypropylene (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) are preferred, More preferred is oxyethylene.

The amine compound having a phenoxy group can be obtained by heating the primary or secondary amine having a phenoxy group and the haloalkyl ether to make these reactions, and then adding sodium hydroxide, potassium hydroxide, and tetraalkyl group. After an aqueous solution of strong salts such as ammonium, extraction is performed with organic solvents such as ethyl acetate and chloroform. Or it can be obtained by heating the primary or secondary ammonium and the haloalkyl ether with a phenoxy group at the end to make these reactions, and then adding strong salts such as sodium hydroxide, potassium hydroxide, tetraalkylammonium, etc. After the aqueous solution, extraction is performed with organic solvents such as ethyl acetate and chloroform.

(Compounds (PA) that produce compounds with proton-accepting functional groups that are decomposed by the irradiation of actinic rays or radiation to decrease, disappear, or change from proton-accepting to acidic properties) The composition of the present invention, as a basic compound, may further include a functional group that generates proton-accepting properties and is decomposed by irradiation with actinic rays or radiation, so that the proton-accepting properties are decreased, disappeared, or changed from proton-accepting properties to acidity. Compound compound [hereinafter, also referred to as compound (PA)].

The proton-accepting functional group is a functional group with a group or electrons capable of electrostatically interacting with protons, for example, it means a functional group with a macrocyclic structure such as cyclic polyether, or it has no effect on π conjugation. The functional group of the nitrogen atom that does not share the electron pair. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure shown in the following general formula.

[Chemical formula 63]

Examples of preferable partial structures of the proton-accepting functional group include crown ethers, aza crown ethers, 1-3 amines, pyridine, imidazole, and pyridine structures.

The compound (PA) produces a compound that is decomposed by irradiation with actinic rays or radiation to decrease or disappear proton acceptor properties, or change from proton acceptor properties to acidity. Here, the decrease, disappearance, or change of proton-accepting property from proton-accepting property to acidity is the change in proton-accepting property caused by the addition of protons to the proton-accepting functional group. Specifically, it means the change in proton-accepting property from having a proton-accepting property. When the compound of the body functional group (PA) and the proton form the proton adduct, the equilibrium constant in the chemical equilibrium decreases.

As a specific example of a compound (PA), the following compounds can be mentioned, for example. Furthermore, as specific examples of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP 2014-041328 and paragraphs 0108 to 0116 of JP 2014-134686 can be cited, and these contents are incorporated In this manual.

[Chemical formula 64]

[Chemical formula 65]

[Chemical formula 66]

These basic compounds can be used alone or in combination of two or more kinds.

The amount of the basic compound used is based on the solid content of the resist composition, and is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass.

The use ratio of the photoacid generator and the basic compound in the composition is preferably that the photoacid generator/basic compound (molar ratio)=2.5 to 300. That is, from the viewpoint of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing the decrease in resolution due to the thickening of the resist pattern over time until the heat treatment after exposure, it is 300 or less For better. The photoacid generator/basic compound (mole ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

As the basic compound, for example, the compounds described in paragraphs 0140 to 0144 of JP 2013-011833 A (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.) can be used.

＜Hydrophobic resin＞ The resist composition may have a hydrophobic resin (A') in addition to the above-mentioned resin (A). It is better that the hydrophobic resin is designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it is not necessary to have a hydrophilic group in the molecule, and it may not be effective for the uniform mixing of polar/non-polar substances. As an effect of adding a hydrophobic resin, control of the static/dynamic contact angle of the surface of the resist film with respect to water, suppression of outgassing, etc. can be cited.

From the viewpoint of uneven distribution on the surface of the film, it _{is preferable that the hydrophobic resin has any one or more of "fluorine atom", "silicon atom" and "CH 3} partial structure contained in the side chain part of the resin", and it has two More than one species is more preferable. Moreover, it is preferable that the said hydrophobic resin contains a C5 or more hydrocarbon group. These groups may exist in the main chain of the resin, or they may be substituted in the side chain.

When the hydrophobic resin contains fluorine atoms and/or silicon atoms, the above-mentioned fluorine atoms and/or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or may be contained in the side chain.

When the hydrophobic resin contains a fluorine atom, as a partial structure having a fluorine atom, a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom is preferable. The alkyl group having a fluorine atom (preferably with a carbon number of 1 to 10, more preferably a carbon number of 1 to 4) is a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and may further have a fluorine atom的Substituents. The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and may have a substituent other than a fluorine atom. As the aryl group having a fluorine atom, at least one hydrogen atom of an aryl group such as a phenyl group and a naphthyl group is substituted with a fluorine atom, and it may have a substituent other than a fluorine atom. As an example of the repeating unit having a fluorine atom or a silicon atom, those exemplified in paragraph 0519 of US2012/0251948A1 can be cited.

In addition, as described above, it is preferable _{that the hydrophobic resin includes a CH 3 partial structure in the side chain portion.} Here, the hydrophobic side chain moiety in the resin having a partial structure of the system comprises a CH ₃ group, a propyl group or the like having the partial structure are CH _3. On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (for example, the α-methyl group having a repeating unit of methacrylic acid structure) is affected by the main chain and causes unevenness on the surface of the hydrophobic resin. It plays a small role and is therefore regarded as a part _{of the CH 3 structure included in the present invention.}

Regarding the hydrophobic resin, the description in <0348> to <0415> of JP 2014-010245 A can be referred to, and these contents are incorporated in this specification.

In addition, as the hydrophobic resin, those described in Japanese Patent Application Publication No. 2011-248019, Japanese Patent Application Publication No. 2010-175859, and Japanese Patent Application Publication No. 2012-032544 can also be preferably used.

＜Surface active agent＞ The resist composition may further contain a surfactant. By containing a surfactant, when using an exposure light source with a wavelength of 250 nm or less, especially 220 nm or less, a pattern with less adhesion and development defects can be formed with good sensitivity and resolution. As the surfactant, it is particularly preferable to use a fluorine-based and/or silicon-based surfactant. As the fluorine-based and/or silicon-based surfactants, for example, the surfactants described in >0276> of US Patent Application Publication No. 2008/0248425 can be cited. In addition, EFTOP EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Fluorad FC430, 431 or 4430 (manufactured by Sumitomo 3M Limited); MEGAFAC F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by ASAHI GLASS CO., LTD.); TroySol S-366 (manufactured by Troy Chemical Industriesm, Inc.); GF-300 or GF-150 (manufactured by TOAGOSEI CO., LTD.), Surflon S-393 (manufactured by SEIMI CHEMICAL CO., LTD.); EFTOP EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801 , EF802 or EF601 (manufactured by Gemco Co., Ltd); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA Solutions Inc.); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (Neos Corporation). In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

Furthermore, in addition to the well-known surfactants shown above, the surfactant can also be used by a short-chain polymerization (telomerization) method (also known as a short-chain polymer (telomer) method) or an oligomerization method (also known as It is synthesized by fluorine aliphatic compound produced by oligomer method. Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound can also be used as a surfactant. The fluoroaliphatic compound can be synthesized, for example, by the method described in JP 2002-090991 A. In addition, surfactants other than the fluorine-based and/or silicon-based surfactants described in >0280> in the specification of U.S. Patent Application Publication No. 2008/0248425 may also be used.

These surfactants may be used alone or in combination of two or more.

When the resist composition contains a surfactant, its content is based on the total solid content of the composition, and is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and still more preferably 0.0005 to 1% by mass.

＜Other additives＞ The resist composition may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and/or a compound that promotes solubility in the developer (for example, a phenol compound with a molecular weight of 1000 or less, or a compound containing a carboxyl group). The alicyclic or aliphatic compounds).

The resist composition may further contain a dissolution inhibiting compound. Here, the "dissolution inhibiting compound" is a compound having a molecular weight of 3000 or less that is decomposed by the action of an acid to reduce the solubility in an organic developer.

[Upper film] In the pattern forming method of the present invention, an upper layer film (top coating film) can be formed on the upper layer of the resist film. The upper layer film is not mixed with the resist film, and it is better to be able to further coat the upper layer uniformly on the resist film. The upper film is not particularly limited, and a conventionally known upper film can be formed by a conventionally known method. For example, the upper film can be formed in accordance with the description in paragraphs 0072 to 0082 of JP 2014-059543 A.

[Content of organic impurities] When a treatment solution containing an organic solvent containing organic impurities is applied to the semiconductor device manufacturing process, among the organic impurities, the organic impurities with a boiling point above 300°C, especially those with a high boiling point, do not volatilize and remain in it, which tends to cause significant defects in the substrate. Bad cause. In particular, as the above-mentioned organic impurities with a boiling point of 300°C or higher, specifically, it is considered to be a resin component or a plasticizer contained in a plastic material (for example, an O-ring, etc.) used to manufacture a member of a device, and it is presumed to be Dissolved in liquid at some point in the manufacturing process. It was confirmed that if the content of the organic impurities with a boiling point of 300°C or higher relative to the total mass of the treatment liquid is 0.001 mass ppm to 50 mass ppm, when used in the semiconductor device manufacturing process, it becomes the treatment condition by development treatment or rinse treatment. The improvement can reduce the number of defects within the defect defect range. In the treatment liquid, the content of the organic impurities with a boiling point of 300°C or higher is more preferably 0.001-30 mass ppm relative to the total mass of the treatment liquid. From the viewpoint of suppressing defects of the substrate when used in the semiconductor device manufacturing process, 0.001 Mass ppm to 15 mass ppm is more preferable, 0.001 mass ppm to 10 mass ppm is still more preferable, and 0.001 mass ppm to 1 mass ppm is most preferable.

For example, when the above-mentioned treatment liquid is used as a developing solution and contacts the substrate, the above-mentioned organic impurities are prevented from being volatilized and remain on the surface of the substrate to become defects. The content of the above-mentioned organic impurities with a boiling point of 300°C or higher is relative to the total treatment liquid. The mass is preferably 30 mass ppm or less. From the viewpoint of preventing the organic impurities with a boiling point of 300°C or higher from remaining on the substrate after the baking step and suppressing the cause of defects (defective development), the above boiling point It is more preferable that the content of organic impurities at 300°C or higher is 5 ppm by mass or less with respect to the total mass of the treatment liquid. In the treatment solution, as organic impurities above 300°C, components such as dioctyl phthalate (DOP, boiling point 385°C) eluted from O-rings, and diisononyl phthalate (DINP, boiling point 403) were confirmed ℃), dioctyl adipate (DOA, boiling point 335℃), dibutyl phthalate (DBP, boiling point 340℃) and EPDM (EPDM, boiling point 300-450℃), etc.

The content of organic impurities with a boiling point of 300° C. or higher in the treatment solution was measured by DI-MS (Direct Injection Mass Chromatography). As a method of setting the content of organic impurities having a boiling point of 300° C. or higher in the treatment liquid within the above-mentioned range, the method listed in the purification step described later can be cited.

<Metal components (metal impurities) containing elements selected from Fe, Cr, Ni and Pb> It is better that the content of metal impurities in the treatment liquid of the present invention is less. In particular, the content of each metal component containing elements selected from Fe, Cr, Ni, and Pb in the treatment liquid is preferably 0.001 to 100 mass ppt relative to the total mass of the treatment liquid. A certain degree of metal components are present in the organic solvent, and sometimes they are mixed into the treatment liquid solution. This time, it is known that the metal components contained in the treatment solution containing elements selected from Fe, Cr, Ni, and Pb have a particularly large impact on the defect performance. As long as the content of the metal component containing elements selected from Fe, Cr, Ni, and Pb is less than 100 mass ppt relative to the total mass of the treatment liquid, the defect suppression ability is excellent, and when it is less than 1 mass ppt, more significant defects can be obtained A more excellent suppressive effect. In addition, when the content of the metal component containing elements selected from Fe, Cr, Ni, and Pb exceeds 100 mass ppt relative to the total mass of the treatment solution, it causes metal particles (defect deterioration), and if it exceeds 0.001 mass ppt, it can be stabilized Carrying out manufacturing management, so the quality of each manufacturing batch is stable. When a plurality of metal components containing elements selected from Fe, Cr, Ni, and Pb are contained, the total amount is preferably less than the above-mentioned range. The content of metal impurities in the treatment liquid is measured by ICP-MS (Inductively Coupled Plasma Mass Analyzer). In addition, when the measurement is less than 1 mass ppt, it is difficult to measure with a stock solution, so it is possible to perform measurement after concentrating the treatment solution as needed. As a method of setting the metal impurity content in the treatment liquid within the above-mentioned range, the method listed in the purification step described later (for example, filtration treatment using an ion exchange resin or a metal adsorption member, etc.) can be cited.

(Substrate) The "substrate" mentioned in the present invention includes, for example, a semiconductor substrate composed of a single layer and a semiconductor substrate composed of multiple layers. The material constituting the semiconductor substrate composed of a single layer is not particularly limited, and it is usually preferably composed of a group III-V compound such as silicon, silicon germanium, GaAs, or any combination thereof. When it is a semiconductor substrate composed of multiple layers, its composition is not particularly limited. For example, a semiconductor substrate of silicon or the like may have an integrated body with exposed interconnect features such as metal wires and dielectric materials. Circuit configuration. As metals and alloys used in the interconnect structure, for example, aluminum and copper, alloy aluminum, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten can be cited, but are not limited to these . In addition, the semiconductor substrate may also have layers of interlayer dielectric layer, silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide.

＜Manufacturing method of treatment liquid＞ In order to set the content of metal components, organic impurities with a boiling point of 300° C. or higher, and water within the desired range, the treatment solution of the present invention is preferably subjected to the following purification steps.

(Purification step) The purification step can be carried out at any time. As the purification step, for example, the following purification treatments I to IV can be cited. That is, the purification treatment I is a treatment for purifying the raw materials used in the production of the above-mentioned organic solvent before the organic solvent constituting the treatment liquid is produced. In addition, the purification treatment II is a treatment for purifying the organic solvent that constitutes the treatment liquid when and/or after it is produced. In addition, when the purification treatment III is to produce a treatment liquid, before mixing two or more organic solvents, each component is purified. In addition, when the purification treatment IV is to produce a treatment liquid, after mixing two or more organic solvents, the mixture is purified. As described above, it is preferable to perform purification in order to obtain the target treatment liquid. Regarding the purification, it may be mixed after purifying each organic solvent, or it may be purified after mixing each organic solvent. In particular, from the viewpoint that the blending ratio of the organic solvent can be made constant, the method of blending the purified organic solvent is preferable. The purification treatments I to IV may be carried out only once, respectively, or they may be carried out twice or more. In addition, as the organic solvent used, it is possible to purchase high-purity products (especially those containing less organic impurities, metal impurities, water, etc.), and to further use them after purification treatment as described below.

Hereinafter, an example of the purification step is shown. In the following description, the purification object in the purification step is simply referred to as "purified liquid". As an example of the purification step, the following treatments are sequentially performed: the first ion exchange treatment, ion exchange treatment of the purified liquid; dehydration treatment, dehydration of the purified liquid after the first ion exchange treatment; distillation treatment , The distillation of the purified liquid after the dehydration treatment; the second ion exchange treatment, the ion exchange treatment of the purified liquid after the distillation treatment; and the organic impurity removal treatment, the organic of the purified liquid after the second ion exchange treatment Impurity removal. In addition, the above purification step is described below as an example, but the purification method when preparing the treatment liquid of the present invention is not limited to this. For example, the following treatments may be sequentially performed: first, the dehydration treatment for dehydration of the purified liquid is performed; the distillation treatment for the distillation of the purified liquid after the dehydration treatment is performed; the second ion exchange treatment for the purified liquid is performed. 1 ion exchange treatment; and organic impurity removal treatment for removing organic impurities from the purified liquid after the second ion exchange treatment.

According to the first ion exchange treatment, ion components (for example, metal components, etc.) in the purified liquid can be removed. In the first ion exchange treatment, a first ion exchange mechanism such as an ion exchange resin is used. As the ion exchange resin, there may be one that installs cation exchange resin or anion exchange resin in a single bed, one that installs cation exchange resin and anion exchange resin in multiple beds, and one that installs cation exchange resin and anion exchange resin in mixed beds. Any kind. In addition, as the ion exchange resin, in order to reduce the elution of water from the ion exchange resin, it is preferable to use a dry resin that does not contain water as much as possible. As such dry resin, commercially available products can be used, including 15JS-HG･DRY (trade name, dry cation exchange resin, moisture content 2% or less) manufactured by Organo Corporation and MSPS2-1･DRY (trade name, mixed bed resin) , Moisture content below 10%) and so on.

According to the dehydration treatment, the water in the purified liquid can be removed. In addition, when the zeolite described later (especially, molecular sieve (trade name) manufactured by UNION SHOWA K.K., etc.) is used for the dehydration treatment, olefins can also be removed. Examples of the dehydration mechanism used in the dehydration treatment include a dehydration membrane, a water adsorbent that is insoluble in the purified liquid, an aeration displacement device and heating using a dry inert gas, or a vacuum heating device. When using a dehydration membrane, perform membrane dehydration based on pervaporation (PV) or vapor permeation (VP). The dehydration membrane is, for example, a water-permeable membrane module. As the dehydration membrane, a polyimide-based film, a cellulose-based film, a polyvinyl alcohol-based film, or the like, which is composed of a polymer-based or inorganic-based material such as zeolite, can be used. The water adsorbent is used by adding to the purified liquid. Examples of the water adsorbent include zeolite, phosphorus pentoxide, silica gel, calcium chloride, sodium sulfate, magnesium sulfate, zinc chloride anhydride, oleum, soda lime, and the like.

The distillation process can remove impurities eluted from the dehydration membrane, metal components in the purified liquid that are not easily removed in the first ion exchange treatment, fine particles (including fine particles when the metal component is fine), and water in the purified liquid. The distillation mechanism is constituted by, for example, a single-stage distillation apparatus. Through the distillation process, the impurities are concentrated in the distillation apparatus, etc. However, in order to prevent a part of the concentrated impurities from flowing out, it is preferable to provide a mechanism for regularly or stably discharging a part of the concentrated impurity liquid to the outside on the distillation mechanism.

According to the second ion exchange treatment, when the impurities accumulated in the distillation device flow out, they can be removed or the eluate from stainless steel (SUS) pipes used as liquid delivery pipes can be removed. Examples of the second ion exchange mechanism include those filled with ion exchange resin in a tower-shaped container, and ion adsorption membranes, and ion adsorption membranes are preferred from the viewpoint of being capable of processing at a high flow rate. Examples of the ion adsorption membrane include NEOSEPTA (trade name, manufactured by ASTOM Corporation).

Each of the above treatments is preferably carried out in a closed state and in an inert gas atmosphere where the possibility of mixing water in the purified liquid is low. In addition, in order to suppress the incorporation of moisture as much as possible, each treatment is preferably performed in an inert gas atmosphere with a dew point temperature of -70°C or less. The reason is that in an inert gas atmosphere of -70°C or less, the moisture concentration in the gas phase is 2 mass ppm or less, so the possibility that moisture will be mixed into the (purified liquid) becomes low.

As the purification step, in addition to the above-mentioned treatment, the adsorption purification treatment of the metal component using silicon carbide described in International Publication No. WO2012/043496 can be cited.

According to the organic impurity removal treatment, it is possible to remove high-boiling organic impurities (including organic impurities with a boiling point of 300°C or higher) contained in the purified liquid after the distillation treatment and difficult to remove during the distillation treatment. As the organic impurity removal mechanism, for example, it can be implemented by an organic impurity adsorption member provided with an organic impurity adsorption filter capable of adsorbing organic impurities. In addition, the organic impurity adsorbing member is usually configured by including the organic impurity adsorbing filter and the base material for fixing the impurity adsorbing filter. From the viewpoint of improving the adsorption performance of organic impurities, it is preferable that the organic impurity adsorption filter has an organic skeleton capable of interacting with organic impurities on the surface (in other words, the surface is modified by the organic skeleton capable of interacting with organic impurities) . In addition, the so-called surface having an organic skeleton capable of interacting with organic impurities, as an example, a form in which the surface of the substrate constituting the organic impurity adsorbing filter described later is provided with an organic skeleton capable of interacting with the organic impurities can be cited. As an organic substance skeleton capable of interacting with organic impurities, for example, a chemical structure capable of reacting with organic impurities to capture the organic impurities in the organic impurity adsorption filter can be cited. More specifically, when dioctyl phthalate, diisononyl phthalate, dioctyl adipate, or dibutyl phthalate are contained as organic impurities, a benzene ring skeleton can be cited as the organic skeleton . Moreover, when the ethylene propylene diene rubber is contained as an organic impurity, an alkylene skeleton can be mentioned as an organic skeleton. Moreover, when an n-long-chain alkyl alcohol (a structural isomer when a 1-long-chain alkyl alcohol is used as a solvent) is contained as an organic impurity, an alkyl group can be mentioned as an organic skeleton. As the base material (material) that constitutes the organic impurity adsorption filter, cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, and fluororesin that carry activated carbon can be cited. In addition, as an organic impurity removal filter, a filter in which activated carbon is adhered to a non-woven fabric described in JP 2002-273123 A and JP 2013-150979 A can also be used.

In addition, the above-mentioned organic impurity removal treatment is not limited to the aspect in which an organic impurity adsorption filter capable of adsorbing organic impurities is used as described above, for example, it may be a aspect in which organic impurities are physically captured. Organic impurities with a high boiling point above 250°C are mostly relatively coarse (for example, compounds with a carbon number of 8 or more), so they can also be physically captured by using a filter with a pore size of about 1 nm. For example, when dioctyl phthalate is contained as an organic impurity, the structure of dioctyl phthalate is greater than 10 Å (=1 nm). Therefore, by using an organic impurity removal filter with a pore size of 1 nm, dioctyl phthalate cannot pass through the pores of the filter. That is, dioctyl phthalate is physically captured by the filter, and therefore is removed from the purified substance. In this way, not only chemical interactions can be applied to the removal of organic impurities, but also physical removal methods can be applied. However, in this case, a filter with a pore size of 3 nm or more is used as a "filtering member" described later, and a filter with a pore size of less than 3 nm is used as an "organic impurity removal filter". In this manual, 1Å (Angstrom) is equivalent to 0.1nm.

In addition, the purification step of the present invention may further have, for example, purification treatment V and purification treatment VI described later. The purification treatment V and the purification treatment VI can be carried out at any time, for example, after carrying out the purification step IV, etc. can be mentioned. Purification treatment V is a filtration treatment using a metal ion adsorption member for the purpose of removing metal ions. In addition, the purification treatment VI is a filtration treatment for removing coarse particles. Hereinafter, the purification treatment V and the purification treatment VI will be described.

In the purification treatment VI, as an example of a metal ion removal mechanism, filtration using a metal ion adsorption member equipped with a metal ion adsorption filter can be cited. The metal ion adsorption member is a structure having at least one metal ion adsorption filter, and can also be a structure in which a plurality of metal ion adsorption filters are overlapped according to a desired purification level. The metal ion adsorbing member is generally configured by including the metal ion adsorbing filter and a base material for fixing the metal ion adsorbing filter. The metal ion adsorption filter has the function of adsorbing metal ions in the purified liquid. In addition, the metal ion adsorption filter is preferably a filter capable of ion exchange. Here, there are no particular restrictions on the metal ions to be adsorbed, but from the viewpoint that they are likely to cause defects in semiconductor devices, Fe, Cr, Ni, and Pb are preferable. From the viewpoint of improving the adsorption performance of metal ions, the metal ion adsorption filter preferably has acid groups on the surface. As an acid group, a sulfo group, a carboxyl group, etc. are mentioned. Examples of the base material (material) constituting the metal ion adsorption filter include cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, and fluororesin.

In the purification treatment VI, as an example of the filtering mechanism, an aspect implemented using a filtering member provided with a filter having a particle diameter of 20 nm or less can be cited. The purified liquid can remove particulate impurities from the purified liquid by adding the above-mentioned filter. Here, the "particulate impurities" include dust, dust, organic solid matter, and inorganic solid matter particles contained as impurities in the raw materials used in the production of the purified liquid, and contamination when the purified liquid is purified. Dust, dust, particles of organic solid matter and inorganic solid matter, etc., which are trapped by objects, but are not dissolved in the purified liquid and exist as particles, also belong to this category. In addition, "particulate impurities" also include colloidal impurities containing metal atoms. The metal atom is not particularly limited, and at least one selected from Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn and Pb (preferably Fe, Cr, Ni and Pb) When the content of one type of metal atom is particularly low (for example, when the content of the above-mentioned metal atoms in the purified liquid is 1000 mass ppt or less), impurities containing these metal atoms are likely to colloid. With the aforementioned metal ion adsorption member, it is difficult to remove colloidal impurities. Therefore, by using a filter with a particle size of 20nm or less (for example, a precision filtration membrane with a pore size of 20nm or less), colloidal impurities can be effectively removed. The particulate impurities have a size that can be removed by a filter with a removal diameter of 20 nm or less, and specifically, they are particles with a diameter of 20 nm or more. In addition, in this specification, particulate impurities may be referred to as "coarse particles". Among them, the particle diameter of the filter is preferably 1-15 nm, and more preferably 1-12 nm. If the removal particle size is 15 nm or less, finer particulate impurities can be removed by this, and if the removal particle size is 1 nm or more, the filtration efficiency of the purified liquid can thereby be improved. Here, the removal particle size refers to the smallest size of particles that can be removed by the filter. For example, when the particle diameter of the filter is 20 nm, particles with a diameter of 20 nm or more can be removed. Examples of the material of the filter include 6-nylon, 6,6-nylon, polyethylene, polypropylene, polystyrene, and fluororesin.

The filter member may further have a filter having a particle diameter of 50 nm or more (for example, a precision filtration membrane for removing particles with a pore diameter of 50 nm or more). In addition to colloidal impurities, especially colloidal impurities containing metal atoms such as iron or aluminum, there are also fine particles in the purified liquid. Use a filter with a particle size of 20 nm or less (for example, a precision filter with a pore size of 20 nm or less). Filter membrane) Before filtering, use a filter with a particle size of 50nm or more (for example, a precision filter membrane for removing particles with a pore size of 50nm or more) to filter the purified liquid, thereby removing the filter with a particle size of 20nm or less (For example, a precision filtration membrane with a pore size of 20 nm or less) has improved filtration efficiency, and the removal performance of coarse particles has been further improved.

The purified liquid obtained through each of these treatments can be used in the composition of the treatment liquid of the present invention or directly used as the treatment liquid of the present invention. In addition, as an example of the above-mentioned purification step, a case where all the processes are performed is shown, but it is not limited to this, and each of the above-mentioned processes may be performed independently, or a plurality of the above-mentioned processes may be combined. In addition, each of the above-mentioned processes may be performed once, or may be performed multiple times.

In addition to the above purification steps, as a method of setting the contents of organic impurities, metal components, and water contained in the treatment liquid with a boiling point of 300° C. or higher within the desired range, there can also be exemplified an organic solvent that composes the treatment liquid. A method in which the raw material or the treatment liquid itself is contained in a container where impurities are less eluted. In addition, a method of lining the inner wall of the pipe with a fluorine-based resin in order to prevent the metal component from eluting from the "pipe" or the like when the processing liquid is produced can also be cited.

[Container (Container)] The treatment liquid of the present invention can be filled in any container, stored, transported, and used as long as corrosivity and the like are not a problem. As the container, it is preferable that the container for semiconductors has high cleanliness in the container and less elution of impurities. Specific examples of usable containers include the "clean bottle" series manufactured by AICELLO CORPORATION and the "pure bottle" manufactured by KODAMA PLASTICS Co., Ltd., but are not limited to these. The inner wall of the container (the wetted part in contact with the solution in the container) is preferably made of a non-metallic material. As non-metallic materials, selected from polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, tetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene -Hexafluoropropylene copolymer resin (FEP), ethylene-tetrafluoroethylene copolymer resin (ETFE), ethylene-chlorotrifluoroethylene copolymer resin (ECTFE), polyvinylidene fluoride resin (PVDF), chlorotrifluoroethylene copolymer resin ( At least one of PCTFE) and polyvinyl fluoride resin (PVF) is more preferable. In particular, when a container with an inner wall made of fluorine resin is used in the above, compared with the case of a container with inner wall made of polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin, the elution of ethylene or propylene oligomers can be suppressed And other undesirable situations. As a specific example of such a container whose inner wall is a fluorine-based resin, for example, a FluoroPurePFA composite cylinder manufactured by Entegris Inc. can be cited. In addition, you can also use the 4th page of the Japanese Special Publication No. Hei 3-502677, the 3rd page of the International Publication No. 2004/016526 and the 9th and 16th pages of the International Publication No. 99/046309. The container described in. In addition, when the inner wall is designed as a non-metallic material, it is preferable that the elution of organic components in the non-metallic material in the treatment liquid is suppressed.

In addition, as the inner wall of the container, in addition to the aforementioned non-metallic materials, quartz or metal materials (more preferably electrolytically polished metal materials. As far as possible, electrolytically polished metal materials) can also be preferably used. The above-mentioned metal material (especially, the metal material used in the production of the electrolytically ground metal material) preferably contains more than 25% by mass of chromium relative to the total mass of the metal material. For example, stainless steel can be mentioned. The content of chromium in the metal material is more preferably 30% by mass or more with respect to the total mass of the metal material. In addition, there is no particular limitation on the upper limit, but it is usually preferably 90% by mass or less.

As stainless steel, there is no restriction|limiting in particular, A well-known stainless steel can be used. Among them, an alloy containing 8% by mass or more of nickel is preferable, and an austenitic stainless steel containing 8% by mass or more of nickel is more preferable. As austenitic stainless steel, for example, SUS (Steel Use Stainless) 304 (Ni content 8 mass%, Cr content 18 mass%), SUS304L (Ni content 9 mass%, Cr content 18 mass%), SUS316 ( Ni content 10 mass%, Cr content 16 mass%) and SUS316L (Ni content 12 mass%, Cr content 16 mass%), etc.

There is no particular limitation on the method of electrolytic polishing a metal material, and a known method can be adopted. For example, the method described in paragraphs <0011>-<0014> of Japanese Patent Application Laid-Open No. 2015-227501 and paragraphs <0036>-<0042> of Japanese Patent Application Laid-Open No. 2008-264929 can be adopted.

It is presumed that the content of chromium in the passivation layer on the surface of the metal material by electrolytic polishing becomes more than the content of chromium in the parent phase. Therefore, it is presumed that the metal component is not easy to flow out into the solution from the inner wall covered with the electrolytically polished metal material, so a solution with reduced metal components (metal impurities) can be obtained. In addition, it is preferable that the metal material is polished. The polishing method is not particularly limited, and a known method can be adopted. The size of the abrasive grains used in the fine polishing is not particularly limited. From the viewpoint that the surface irregularities of the metal material are more likely to become smaller, #400 or less is preferable. In addition, polishing is preferably performed before electrolytic polishing. In addition, the metal material may be processed by combining one or two or more stages of polishing, pickling, and magnetic fluid polishing performed by changing the size of the abrasive grains.

In the present invention, the one having the container and the processing liquid contained in the container may be referred to as a solution container.

It is preferable that the inside of these containers is cleaned before being filled with the treatment liquid. When the liquid used for washing is the treatment liquid of the present invention itself or an organic solvent contained in the treatment liquid of the present invention, the effects of the present invention can be remarkably obtained. The treatment liquid of the present invention can also be transported and stored in containers such as gallon bottles or QT bottles after manufacture. Gallon bottles can be those using glass or other materials.

It is also possible to replace the inside of the container with an inert gas (nitrogen, argon, etc.) with a purity of 99.99995% by volume or more for the purpose of preventing changes in the composition of the processing liquid in storage. In particular, a gas with a lower water content is preferable. In addition, normal temperature may be used during transportation and storage, but the temperature may be controlled in the range of -20°C to 20°C in order to prevent deterioration.

(Clean room) It is preferable that all operations, processing analysis, and measurement including the manufacturing of the processing liquid of the present invention, the unsealing and/or washing of the storage container, and the filling of the processing liquid, are performed in a clean room. It is better that the clean room meets the 14644-1 clean room standard. It is better to satisfy any of ISO (International Organization for Standardization) Level 1, ISO Level 2, ISO Level 3, and ISO Level 4, it is more preferable to satisfy ISO Level 1 or ISO Level 2, and it is even more preferable to satisfy ISO Level 1. Operations, processing analysis, and measurement including the manufacturing of the processing liquid, the unsealing and/or washing of the storage container, and the filling of the processing liquid in the examples described later, were performed in a class 2 clean room.

(filter) In order to set the contents of organic impurities, metal components, and water with a boiling point of 300°C or higher within the desired range, or to remove foreign substances and coarse particles, the treatment liquid or the organic solvent contained in the treatment liquid of the present invention is filtered The one is better. As long as the filter used in filtering is used for filtering purposes, there are no special restrictions in use. Examples of materials constituting the filter include fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP). Wait. Among them, polyamide resins, PTFE and polypropylene (containing high-density polypropylene) are preferred. Filters formed from these materials can be used to more effectively remove the cause of particle defects. In addition to foreign matter with high polarity, it can also reduce the amount of metal components (metal impurities) more effectively.

The critical surface tension of the filter is preferably 70 mN/m or more as the lower limit. As the upper limit, 95 mN/m or less is preferable. Among them, it is more preferable that the critical surface tension of the filter is 75 mN/m or more and 85 mN/m or less. In addition, the value of the critical surface tension is the manufacturer's nominal value. By using a filter with a critical surface tension in the above range, it is possible to more effectively remove foreign matter with high polarity that is likely to be a cause of particle defects, and it is also possible to more effectively reduce the amount of metal components (metal impurities).

As long as the filter used in filtering is used for filtering purposes, there are no particular restrictions. Examples of materials constituting the filter include fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP). Wait. Among them, polypropylene (including high-density polypropylene) and nylon are preferred. The pore diameter of the filter is preferably about 0.001 to 1.0 μm, more preferably about 0.01 to 0.5 μm, and even more preferably about 0.01 to 0.1 μm. By setting the pore size of the filter to the above-mentioned range, clogging of filtration can be suppressed, and fine foreign matter contained in the treatment liquid or the organic solvent contained in the treatment liquid can be reliably removed.

When using filters, different filters can also be combined. At this time, the filtration using the first filter may be performed only once, or may be performed twice or more. When combining different filters to perform filtration more than two times, each filter may be of the same type or different types, and it is preferable that the types are different from each other. Typically, it is preferable that the first filter and the second filter are different in at least one of pore size and constituent materials. Compared with the pore size of the first filtration, the pore size after the second filtration is the same or smaller than it. In addition, it is also possible to combine first filters having different pore diameters within the above-mentioned range. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL LTD., Advancec Toyo Kaisha, Ltd., Nihon Entegris K.K. (formerly Nippon micro squirrel Co., Ltd.), KITZMICROFILTER CORPORATION, and the like. In addition, "P-nylon filter (pore size 0.02μm, critical surface tension 77mN/m)" made of polyamide; (manufactured by NIHON PALL LTD.), "PE･clean filter made of high-density polyethylene" can also be used (Pore size 0.02μm)”; (manufactured by NIHON PALL LTD.) and high-density polyethylene “PE･clean filter (pore size 0.01μm)”; (manufactured by NIHON PALL LTD.).

Although there are no particular restrictions, for example, in addition to the more excellent effect of the treatment liquid of the present invention, from the viewpoint of suppressing the increase of particulate metals in the storage of the purified treatment liquid, the purified liquid is used in filtration The relationship between the material of the filter is to satisfy the interaction radius in the Hansen solubility parameter (HSP) space derived from the material of the filter used in the filtration as (R0), from the processing liquid or the processing liquid contained When the radius of the sphere of the Hansen space derived from the liquid contained in the organic solvent is set to (Ra), the relationship between Ra and R0 (Ra/R0)≦1 is a combination, and the filter material that satisfies the relationship is used The filtered treatment liquid or the organic solvent contained in the treatment liquid is preferable. (Ra/R0)≦0.98 is preferable, and (Ra/R0)≦0.95 is more preferable. As the lower limit, 0.5 or more is preferable, 0.6 or more is more preferable, and 0.7 is still more preferable. Although the mechanism is not clear, if it is in this range, the formation of particulate metal or the growth of particulate metal during long-term storage will be suppressed. The combination of these filters and the treatment liquid or the organic solvent contained in the treatment liquid is not particularly limited, and examples include those in U.S. Patent Publication No. 2016/0089622.

As the second filter, a filter made of the same material as the above-mentioned first filter can be used. It is possible to use those with the same pore size as the above-mentioned first filter. When the pore diameter of the second filter is smaller than that of the first filter, the ratio of the pore diameter of the second filter to the pore diameter of the first filter (the pore diameter of the second filter/the pore diameter of the first filter) is 0.01 to 0.99. Preferably, 0.1 to 0.9 is more preferable, and 0.2 to 0.9 is even more preferable. By setting the pore size of the second filter within the above-mentioned range, the fine foreign matter mixed in the solution can be removed more reliably.

Furthermore, in the present invention, the content of one or two or more metal elements selected from Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Pd, and Zn relative to the treatment liquid or When the organic solvent contained in the treatment liquid is particularly low (for example, when the content of the above-mentioned metal elements is less than 1000 mass ppt relative to the treatment liquid or the organic solvent contained in the treatment liquid), impurities containing these metal elements are present Prone to colloidization. Therefore, it is easy to make it difficult to remove colloidal impurities in the ion adsorption membrane. Therefore, the inventors of the present invention have found that by purifying by using a precision filtration membrane with a pore diameter of 20 nm or less, it is possible to remove colloidal impurity components.

Also, when there are particles in the treatment liquid or the organic solvent contained in the treatment liquid in addition to colloidal impurities (especially colloidal impurities containing metal elements such as iron or aluminum), use a precision filter with a pore size of 20 nm or less. Before the membrane is filtered, it is better to use a fine filtration membrane for removing particles with a pore size of 50 nm or more for filtration, and it is better to perform purification by this.

The treatment liquid or the organic solvent contained in the treatment liquid of the present invention is preferably purified by using an ion adsorption mechanism in addition to the above-mentioned filter. The ion adsorption mechanism is cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene or fluororesin, etc. The surface is adsorbed by anionic groups such as sulfo or carboxyl groups, cationic groups or modified by both Organization is better. The ion adsorption mechanism modified by anionic groups can remove cations such as Na ions and Ca ions, and the ion adsorption mechanism modified by cationic groups can remove anions and acid components such as Cl ions. The ion adsorption mechanism can be used by using an anionic group, a cationic group, or a combination of both according to the purpose. The ion adsorption mechanism may also be a filter.

The above filtering step can also be repeated several times depending on the purpose.

In addition, the filter used is preferably treated before filtering the treatment liquid or the organic solvent contained in the treatment liquid. The liquid used in this treatment is not particularly limited. If it is an organic solvent contained in the treatment liquid of the present invention, the desired effect of the present invention can be remarkably obtained.

When performing filtration, the upper limit of the temperature during filtration is preferably room temperature (25°C) or less, more preferably 23°C or less, and even more preferably 20°C or less. In addition, the lower limit of the temperature during filtration is preferably 0°C or higher, more preferably 5°C or higher, and more preferably 10°C or higher. In filtration, particulate foreign matter or impurities can be removed, but if it is performed at the above temperature, the amount of particulate foreign matter or impurities dissolved in the treatment liquid or the organic solvent contained in the treatment liquid is reduced, so it is more effective Perform filtering.

In particular, from the viewpoint of adjusting the content of metal components (metal impurities), it is preferable to perform filtration at the above-mentioned temperature. Although the mechanism is not clear, it is believed that metal components (metal impurities) mostly exist in a particulate colloidal state. It is considered that if the filtration is performed at the above temperature, a part of the metal components (metal impurities) floating in a colloidal form will agglomerate. Therefore, the agglomerates are effectively removed by filtration, and the metal components (metal impurities) are easily removed. The content is adjusted to the prescribed amount.

The filtration pressure affects the filtration accuracy, so it is better to minimize the pressure pulsation during filtration.

In the preparation and purification of the treatment liquid or the organic solvent contained in the treatment liquid of the present invention, the filtration rate is not particularly limited, but from the viewpoint of more excellent effects of the present invention, 0.6 L/min/m ² or more is preferred , 0.75L / min / m ² or more is more preferred, 1.0L / min / m ² or more is further preferred. The filter is set with a pressure difference that guarantees the performance of the filter (the filter is not damaged). When the value is large, the filtration speed can be increased by increasing the filtration pressure. That is, the upper limit of the filtration rate generally depends on the pressure difference of the filter, and it is generally ^{preferably 10.0 L/min/m 2} or less.

In the preparation and purification of the treatment liquid or the organic solvent contained in the treatment liquid of the present invention, from the viewpoint of more excellent effects of the present invention, the filtration pressure is preferably 0.001 MPa or more and 1.0 MPa or less, and 0.003 MPa or more and 0.5 MPa or less is more preferable, and 0.005 MPa or more and 0.3 MPa or less are particularly preferable. In particular, when a filter with a small pore size is used, the amount of particulate foreign matter or impurities dissolved in the solution can be effectively reduced by increasing the filtration pressure. When a filter with a pore diameter of less than 20 nm is used, it is particularly preferable to set the filtration pressure to 0.005 MPa or more and 0.3 MPa or less.

In addition, if the pore size of the filter membrane becomes smaller, the filtration speed decreases. For example, by connecting a plurality of filters equipped with the same type of filtration membrane in parallel, the filtration area expands and the filtration pressure drops, thereby compensating for the filtration speed. decline.

[Static Elimination Step] In the preparation and purification of the treatment liquid or the organic solvent contained in the treatment liquid of the present invention, there may be a further step of removing electricity. The neutralization step is a step of neutralizing at least one selected from raw materials, reactants, and purified products (hereinafter referred to as "purified products, etc."), thereby reducing the electrostatic potential of the purified products and the like. There is no particular limitation on the method of neutralization, and a known neutralization method can be adopted. As a method of removing electricity, for example, a method of contacting the above-mentioned purified liquid or the like with a conductive material can be mentioned. The time for the above-mentioned purified liquid or the like to contact the conductive material is preferably 0.001 to 60 seconds, more preferably 0.001 to 1 second, and still more preferably 0.01 to 0.1 second. Examples of the conductive material include stainless steel, gold, platinum, diamond, and glassy carbon. As a method of bringing the purified liquid or the like into contact with the conductive material, for example, a method of arranging a grounded screen made of a conductive material in the pipeline and passing the purified liquid or the like therein.

The aforementioned neutralization step can also be performed at any time from the supply of the raw material to the filling of the purified product, for example, before at least one step selected from the group consisting of a raw material supply step, a reaction step, a liquid adjustment step, a purification step, a filtration step, and a filling step. For better. In particular, it is preferable to carry out the neutralization step before injecting the purified product or the like into the container used in each of the above steps. Thereby, it is possible to suppress the mixing of impurities from the container and the like into the purified product and the like. [Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to the following examples as long as it does not deviate from its gist. In addition, unless otherwise specified, "part" and "%" are quality standards. In addition, quantitative analysis of sulfur-containing compounds is performed on the processing liquid used in the subsequent development or processing (for example, measured by the method specified in JISK2541-6:2013 "Sulfur component test method (ultraviolet fluorescence method)") And the quantitative analysis of phosphorus compounds (measured as total phosphorus by absorbance spectrophotometry according to the method specified in JISK0102:2013), it can be confirmed that these compounds are not contained substantially. In addition, "substantially not contained" here means that the compounds are not detected (less than the detection limit value) when measured by a method capable of measuring the content (concentration) of the compounds.

[Preparation of resist composition 1] [Various components] <Resin (A) etc.> As the resin (A), the following resin (A-1) was used. In addition, the molar ratio of each repeating unit in the following resin (A-1) is 40/30/30 from left to right. The above-mentioned molar ratio ^{is calculated by 1} H-NMR (Nuclear Magnetic Resonance) measurement. In addition, the weight average molecular weight (Mw) of standard polystyrene in terms of gel permeation chromatography (GPC) (solvent: THF) based on the resin (A) was 12,000, and the molecular weight dispersion (Mw/Mn) was 1.5.

[Chemical formula 67]

＜Photoacid generator＞ As the photoacid generator, the photoacid generator (B-1) shown below was used.

[Chemical formula 68]

＜Acid diffusion control agent＞ As the acid diffusion control agent, the acid diffusion control agent (E-1) shown below was used.

[Chemical formula 69]

＜Solvent＞ As the solvent, the solvent shown below was used. C-1: Propylene glycol monomethyl ether acetate C-2: Ethyl lactate

[Preparation of resist composition 1] Dissolve 0.77 g of the above resin (A-1), 0.2 g of the above photoacid generator (B-1), and 0.03 g of the above acid diffusion control agent (E-1) in 675 g of the above solvent (C-1) and 7.5 g of the above In the solvent (C-2). This was filtered with a polyethylene filter having a pore size of 0.03 μm, and a resist composition 1 was obtained.

[Pattern formation (EUV exposure, negative development) and evaluation 1] [Pattern Formation] ＜Formation of resist film＞ The above-mentioned resist composition 1 was coated on a 12-inch silicon wafer and baked (PB) at 120°C for 60 seconds to form a resist film with a thickness of 40 nm.

＜Exposure＞ The produced wafer with resist film was exposed to EUV with NA (number of lens openings, Numerical Aperture) 0.25, and dipole illumination (Dipole60x, outer sigma 0.81, inner sigma 0.43). Specifically, by including lines and space patterns (equivalent to Table 2, Table 4, Table 6, Table 8, Table 10, and Table 12) on a wafer with a size of (1) a pitch of 40 nm and a width of 20 nm. Mask for forming "dense pattern") or (2) Line and space pattern with a pitch of 108nm and a width of 20nm (equivalent to the "sparse pattern" in Table 2, Table 4, Table 6, Table 8, Table 10, and Table 12 Use the mask of the pattern of the mask) to change the exposure amount to carry out EUV exposure. After the irradiation, the wafer was taken out from the EUV exposure device, and then immediately baked (PEB) at 90°C for 60 seconds.

＜Development＞ After that, using a spray-type developing device (ADE3000S manufactured by ACTES Co., Ltd.), while rotating the wafer at 50 revolutions (rpm), the developer (23°C) was sprayed at a flow rate of 200 mL/min for 30 seconds. Development was carried out by this. In addition, as the developer, butyl acetate was used.

＜Flushing＞ (Preparation of treatment liquid) As described in Table 1, Table 3, Table 5, Table 7, Table 9, and Table 11 described later, each treatment liquid was prepared by mixing the first organic solvent and the second organic solvent at a predetermined ratio. In addition, as the first organic solvent and the second organic solvent used in each treatment liquid, semiconductor grade ones were used. Each of the obtained treatment liquids was used as a rinsing liquid in the rinsing treatment described later.

(Rinse treatment) After that, while rotating the wafer at 50 revolutions (rpm), each treatment solution (23°C) described in Table 1, Table 3, Table 5, Table 7, Table 9 and Table 11 to be described later was added to 200 mL The flow rate per minute is sprayed for 15 seconds, thereby performing a flushing treatment. Finally, the wafer was dried by rotating it at a high speed of 2000 revolutions (rpm) for _{TR seconds.} In addition, the above "T _R seconds" is the drying time (seconds) + 20 seconds described in the "Drying time (seconds)" column in Table 1, Table 3, Table 5, Table 7, Table 9 and Table 11. bell. That is, in the case of Example 1, " _TR second" is 60 seconds (that is, 40 seconds + 20 seconds).

[Evaluation Test] For wafers that have been exposed, developed, and rinsed, the following items have been evaluated for performance.

＜Evaluation of drying time＞ The evaluation related to the drying time of the treatment liquid was carried out in the following order. It is generally believed that the longer the drying time of the treatment liquid, the greater the influence caused by the capillary force and the faster the collapse. Therefore, the shorter the drying time of the treatment liquid, the more the pattern collapse can be suppressed, which is preferable. In the evaluation of the drying time, each treatment solution (23°C) described in Table 1, Table 3, Table 5, Table 7, Table 9 and Table 11 was added to 200 mL with the naked eye while rotating the wafer at 50 revolutions (rpm). The flow rate per minute was sprayed for 5 seconds, and the time taken for the solvent to dry when drying was performed at 2000 revolutions (rpm) was observed. The "drying time (second)" in Table 1, Table 3, Table 5, Table 7, Table 9, and Table 11 shows the results.

<Resolution (pattern collapse performance: dense pattern, sparse pattern)> A scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.) was used to observe the resolution of the line and space patterns exposed with different exposures at a magnification of 200k, and the results were obtained in one field of view. The smallest line width that causes the pattern to collapse, and it is used as an indicator of the pattern collapse. The smaller the value, the better the pattern collapse performance. The minimum line width obtained was evaluated by the following evaluation criteria. In addition, the pattern collapse performance was evaluated for any of the pattern formed using the mask for forming dense patterns and the pattern formed using the mask for forming sparse patterns. In addition, "C" evaluation or higher is preferable in actual use. (Evaluation criteria) "A": The minimum line width is 16nm or less "B": The smallest line width exceeds 16nm and below 18nm "C": The smallest line width exceeds 18nm and is below 20nm "D": The smallest line width exceeds 20nm and is below 22nm "E": The smallest line width exceeds 22nm

＜Film loss of exposure part＞ (Preparation of evaluation samples) In each of the Examples and Comparative Examples, pattern formation was performed in the same manner except that the exposure conditions in the above-mentioned [Pattern Formation]<Exposure> were changed to the conditions described below. In addition, in the following evaluation, a KrF excimer laser scanner was used. "Exposure Conditions" The above-mentioned band stopper film wafer was fully exposed using a KrF excimer laser scanner (made by ASML, PAS5500/850C, wavelength 248nm), with an exposure amount of 40mJ (overexposure). After exposure, they were immersed for 10 minutes in each treatment liquid of the Examples and Comparative Examples, and the dissolved amount (Å) was measured. In addition, the amount of dissolution was measured with an optical film thickness meter Woollam Japan M2000. By dividing the obtained dissolution amount (Å) by the immersion time (10 minutes), the dissolution rate (Å/min) was calculated, and the film loss of the exposed part was evaluated by the following evaluation criteria. The smaller the value, the more suppressed the film loss in the exposed part. In addition, "C" evaluation or higher is preferable in actual use. (Evaluation criteria) "A": less than 3Å/min "B": 3Å/min or more and less than 10Å/min "C": 10Å/min or more and less than 20Å/min "D": 20Å/min or more and less than 40Å/min "E": 40Å/min or more

＜Bridge Defect Inhibition (Poor dot missing)＞ According to the following procedure, a dot pattern for evaluating bridge defect suppression properties was produced. (Formation of resist film) Each resist composition 1 of the Examples and Comparative Examples was coated on a 12-inch silicon wafer, and baked (PB) at 120° C. for 60 seconds to form a resist film with a thickness of 40 nm.

(exposure) The produced wafer with resist film was exposed to EUV with NA (number of lens openings, Numerical Aperture) 0.25, Quasar illumination (Quasar45, outer sigma 0.81, inner sigma 0.51). Specifically, EUV exposure was performed by changing the exposure amount through a mask including a pattern for forming a dot pattern with a pitch of 60 nm and a dot of 30 nm on the wafer. After the irradiation, the wafer was taken out from the EUV exposure device, and then immediately baked (PEB) at 90°C for 60 seconds.

(development) After that, using a spray-type developing device (ADE3000S manufactured by ACTES Co., Ltd.), while rotating the wafer at 50 revolutions (rpm), the developer (23°C) was sprayed at a flow rate of 200 mL/min for 30 seconds. Development was carried out by this. In addition, as the developer, butyl acetate was used.

(Rinse treatment) After that, while rotating the wafer at 50 revolutions (rpm), each treatment solution (23°C) described in Table 1, Table 3, Table 5, Table 7, Table 9 and Table 11 to be described later was added to 200 mL The flow rate per minute is sprayed for 15 seconds, thereby performing a flushing treatment. Finally, the wafer was dried by rotating it at a high speed of 2000 revolutions (rpm) for _{TR seconds.} In addition, _{the definition of "TR} seconds" is as described above.

(Bridge defect inhibition (point missing performance)) Use a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.) to analyze the resolution of the dot pattern at the optimum exposure level when analyzing a dot pattern with a dot size of 30 nm. Observe from the top of the pattern and find The number of bridging defects (specifically, the number of points with missing defects) generated in a 12-inch wafer was calculated and used as an index of bridging defect suppression. The smaller the value, the better the missing performance of dots. (Evaluation criteria) "A": The number of bridge defects is less than 10 "B": The number of bridge defects exceeds 10 and less than 20 "C": The number of bridging defects exceeds 20 and less than 50 "D": The number of bridge defects exceeds 50

＜Resistivity (ESD: Electro-Static Discharge)＞ The electrical resistivity (Ω･m) of the treatment liquid (temperature: 23°C) was measured using a super-insulation meter SM-8220 (manufactured by HIOKI E.E. CORPORATION). The obtained resistivity values were evaluated based on the following evaluation criteria. (Evaluation criteria) "A": Less than 5000Ω･m "B": 5000Ω･m～100,000Ω･m "C": more than 100,000Ω･m

Furthermore, the following resolution (pattern collapse performance: DOT (dot) pattern) evaluation was performed for the treatment liquids of Table 1, Table 5, Table 9, and Table 11.

<Resolution (pattern collapse performance: DOT pattern)> (Formation of resist film) Each resist composition 1 of the Examples and Comparative Examples was coated on a 12-inch silicon wafer, and baked (PB) at 120° C. for 60 seconds to form a resist film with a thickness of 40 nm.

(exposure) The produced wafer with resist film was exposed to EUV with NA (number of lens openings, Numerical Aperture) 0.25, Quasar illumination (Quasar45, outer sigma 0.81, inner sigma 0.51). Specifically, EUV exposure was performed by changing the exposure amount through a mask including a pattern for forming a dot pattern with a pitch of 60 nm and a dot of 30 nm on the wafer. After the irradiation, the wafer was taken out from the EUV exposure device, and then immediately baked (PEB) at 90°C for 60 seconds.

(development) After that, using a spray-type developing device (ADE3000S manufactured by ACTES Co., Ltd.), while rotating the wafer at 50 revolutions (rpm), the developer (23°C) was sprayed at a flow rate of 200 mL/min for 30 seconds. Development was carried out by this. In addition, as the developer, butyl acetate was used.

(Rinse treatment) After that, while rotating the wafer at 50 revolutions (rpm), each treatment solution (23°C) described in Table 1, Table 5, Table 9 and Table 11 described below was sprayed at a flow rate of 200 mL/min. Seconds, to carry out the flushing treatment. Finally, the wafer was dried by rotating it at a high speed of 2000 revolutions (rpm) for _{TR seconds.} In addition, _{the definition of "TR} seconds" is as described above.

A scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.) was used to observe the resolution of dot patterns exposed at different exposures at a magnification of 200k, and no patterns were found in the observed field of view. The minimum point width of collapse is used as an indicator of pattern collapse. The smaller the value, the better the pattern collapse performance. The minimum dot width obtained was evaluated by the following evaluation criteria. In addition, "C" evaluation or higher is preferable in actual use. (Evaluation criteria) "A": The minimum dot width is 16nm or less "B": The minimum dot width is more than 16nm and less than 18nm "C": The minimum dot width exceeds 18nm and less than 20nm "D": The minimum dot width exceeds 20nm and 22nm or less "E": The minimum dot width exceeds 22nm

Below, Table 1-Table 12 are shown. Hereinafter, the composition of each treatment liquid is shown in Table 1, Table 3, Table 5, Table 7, Table 9, and Table 11. In addition, Table 2, Table 4, Table 6, Table 8, Table 10, and Table 12 correspond to the evaluation results of patterns formed using the respective treatment liquids in Table 1, Table 3, Table 5, Table 7, Table 9 and Table 11, respectively . Specifically, Table 2 shows the evaluation results of the pattern formed using the treatment liquid of Table 1, Table 4 shows the evaluation results of the pattern formed using the treatment liquid of Table 3, and Table 6 shows the treatment using Table 5 Table 8 shows the evaluation results of the patterns formed using the treatment liquids in Table 7, Table 10 shows the evaluation results of the patterns formed using the treatment liquids in Table 9, and Table 12 shows the evaluation results of the patterns formed by the liquid Table 11 shows the evaluation results of the pattern formed by the treatment liquid.

Next, each item shown in Table 1, Table 3, Table 5, Table 7, Table 9, and Table 11 will be described. The "SP value" in each table is the value calculated according to the Fedors method, and the unit is MPa ^1/2 . The calculation method of "SP value" is as described above. "Δd" in each table represents the dispersion term of the Hansen solubility parameter. "ΔP" and "ΔH" in each table are calculated by the following formula (1) and the following formula (2), respectively. Formula (1): ΔP =δp/(δd+δp+δh)×100 Formula (2): ΔH =δh/(δd+δp+δh)×100 δd: Dispersion term of Hansen solubility parameter δp: Hansen solubility The polar term of the parameter δh: the hydrogen bond term of the Hansen solubility parameter The calculation method of the Hansen solubility parameter is as described above.

[Table 1] Table 1 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment liquid A-1 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 40 Treatment liquid A-2 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 40 Treatment liquid A-3 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 25 Treatment liquid A-4 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 15 Treatment liquid A-5 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-ethyl-1-hexanol 104-76-6 20.7 66.3 14.6 19.1 2.8 7 3 30 Treatment liquid A-6 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-heptanol 111-70-6 21.4 48.9 15.9 35.2 2.4 7 3 20 Treatment liquid A-7 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 45 Treatment liquid A-8 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 45 Treatment liquid A-9 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 45 Treatment liquid A-10 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 45 Treatment liquid A-11 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 25 Treatment liquid A-12 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment liquid A-13 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 35 Treatment liquid A-14 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 40 Treatment liquid A-15 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 20 Treatment liquid A-16 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment liquid A-17 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment liquid A-18 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment liquid A-19 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 20 Treatment fluid A-20 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment liquid A-21 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 30 Treatment liquid A-22 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 35 Treatment liquid A-23 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 9 1 18 Example A-24 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 7 3 twenty three Example A-25 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 5 5 28 Example A-26 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 3 7 32 Example A-27 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 9 1 20 Example A-28 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 7 3 25 Example A-29 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 5 5 30 Example A-30 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 3 7 35 Example A-31 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 1-octanol 111-87-5 21.0 49.7 15.5 34.8 4.0 7 3 45

[Table 2] Continued Table 1 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid A-32 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 25 Treatment liquid A-33 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 60 Treatment fluid A-34 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 90 Treatment liquid A-35 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 130 Treatment liquid A-36 Dipentyl ether 693-65-2 16.2 71.9 14.3 13.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 50 Treatment liquid A-37 Dibutyl ether 142-96-1 15.9 71.1 14.2 14.7 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment fluid A-38 Diisopropyl ether 108-20-3 14.6 70.2 14.9 14.9 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 15 Treatment fluid A-39 Dipentyl ether 544-01-4 15.6 76.8 12.1 11.1 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 45 Treatment fluid A-40 Dibutyl ether 142-96-1 15.9 71.1 14.2 14.7 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 45 Treatment fluid A-41 Dipentyl ether 693-65-2 16.2 71.9 14.3 13.8 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 45 Treatment fluid A-42 Diisopropyl ether 108-20-3 14.6 70.2 14.9 14.9 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 45 Treatment liquid A-43 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 18 Treatment liquid A-44 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 53 Treatment fluid A-45 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 83 Treatment fluid A-46 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 123 Treatment liquid A-47 Dibutyl ether 142-96-1 15.9 71.1 14.2 14.7 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 43 Treatment liquid A-48 Dipentyl ether 693-65-2 16.2 71.9 14.3 13.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 twenty three Treatment liquid A-49 Diisopropyl ether 108-20-3 14.6 70.2 14.9 14.9 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 8 Treatment fluid A-50 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 20 Treatment liquid A-51 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 60 Treatment fluid A-52 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 90 Treatment liquid A-53 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 130 Treatment fluid A-54 Dibutyl ether 142-96-1 15.9 71.1 14.2 14.7 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 50 Treatment fluid A-55 Dipentyl ether 693-65-2 16.2 71.9 14.3 13.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment fluid A-56 Diisopropyl ether 108-20-3 14.6 70.2 14.9 14.9 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 15 Treatment liquid A-57 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 15 Treatment liquid A-58 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 40 Treatment fluid A-59 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 60 Treatment fluid A-60 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 85 Treatment fluid A-61 Dibutyl ether 142-96-1 15.9 71.1 14.2 14.7 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 35 Treatment fluid A-62 Dipentyl ether 693-65-2 16.2 71.9 14.3 13.8 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 20

[table 3] Continued Table 1 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid A-63 Diisopropyl ether 108-20-3 14.6 70.2 14.9 14.9 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 8 Treatment fluid A-64 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 20 Treatment fluid A-65 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 45 Treatment fluid A-66 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 65 Treatment liquid A-67 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 90 Treatment fluid A-68 Dibutyl ether 142-96-1 15.9 71.1 14.2 14.7 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 40 Example A-69 Dipentyl ether 693-65-2 16.2 71.9 14.3 13.8 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 25 Example A-70 Diisopropyl ether 108-20-3 14.6 70.2 14.9 14.9 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 10 Treatment fluid RA-1 Triethyl orthoformate 122-51-0 16.3 59.9 22.2 17.9 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 40 Treatment fluid RA-2 Diethylene glycol diethyl ether 112-36-7 15.5 60.4 19.6 20.0 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 40 Treatment fluid RA-3 Triethyl Orthopropionate 115-80-0 16.2 66.5 18.7 14.8 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 40 Treatment fluid RA-4 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-butanol 78-92-2 20.7 43.9 15.8 40.3 0.6 9 1 15 Treatment fluid RA-5 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 MIBC 108-11-2 21.1 51.5 14.5 34.0 1.5 9 1 20 Treatment fluid RA-6 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Benzyl alcohol 100-51-6 21.1 47.9 16.4 35.7 1.1 9 1 25

[Table 4] Table 2 Type of treatment liquid Evaluation results Resolution Exposure film loss Bridging defect Resistivity Dense pattern DOT pattern Sparse pattern Example A-1 Treatment liquid A-1 A B A A A A Example A-2 Treatment liquid A-2 A B A A A A Example A-3 Treatment liquid A-3 A B A A A A Example A-4 Treatment liquid A-4 A A A A A C Example A-5 Treatment liquid A-5 A B A A B A Example A-6 Treatment liquid A-6 C C C C A A Example A-7 Treatment liquid A-7 A B A A A A Example A-8 Treatment liquid A-8 A B A A A A Example A-9 Treatment liquid A-9 A C A A A A Example A-10 Treatment liquid A-10 A C A A A A Example A-11 Treatment liquid A-11 A A A A A A Example A-12 Treatment liquid A-12 A A A A A A Example A-13 Treatment liquid A-13 A B A A A A Example A-14 Treatment liquid A-14 A B A A A A Example A-15 Treatment liquid A-15 A A A A A A Example A-16 Treatment liquid A-16 A A A A A A Example A-17 Treatment liquid A-17 A A A A A A Example A-18 Treatment liquid A-18 A B A A A A Example A-19 Treatment liquid A-19 A A A A A A Example A-20 Treatment fluid A-20 A B A A A A Example A-21 Treatment liquid A-21 B B A A A A Example A-22 Treatment liquid A-22 C B B A A A Example A-23 Treatment liquid A-23 A A A A A A Example A-24 Example A-24 A A A A A A Example A-25 Example A-25 A A A A A A Example A-26 Example A-26 A B A A A A Example A-27 Example A-27 A A A A A A Example A-28 Example A-28 A A A A A A Example A-29 Example A-29 A B A A A A Example A-30 Example A-30 B B A A A A Example A-31 Example A-31 B C B B A A Example A-32 Treatment fluid A-32 A B A A B B Example A-33 Treatment liquid A-33 A B A A A A Example A-34 Treatment fluid A-34 A B A A A A Example A-35 Treatment liquid A-35 B C A A A A Example A-36 Treatment liquid A-36 C C B A A A Example A-37 Treatment liquid A-37 C C B A A A Example A-38 Treatment fluid A-38 B C B A A A Example A-39 Treatment fluid A-39 B B B A A A Example A-40 Treatment fluid A-40 B B A A A A

[table 5] Continued Table 2 Type of treatment liquid Evaluation results Resolution Exposure film loss Bridging defect Resistivity Dense pattern DOT pattern Sparse pattern Example A-41 Treatment fluid A-41 B B A A A A Example A-42 Treatment fluid A-42 B B A A A A Example A-43 Treatment liquid A-43 A A A C B B Example A-44 Treatment liquid A-44 A A A C A A Example A-45 Treatment fluid A-45 A A A C A A Example A-46 Treatment fluid A-46 A A A C A A Example A-47 Treatment liquid A-47 A B A C A A Example A-48 Treatment liquid A-48 A B A C A A Example A-49 Treatment liquid A-49 A B A C A A Example A-50 Treatment fluid A-50 A B A A B B Example A-51 Treatment liquid A-51 A B A A A A Example A-52 Treatment fluid A-52 B B A A A A Example A-53 Treatment liquid A-53 C C B A A A Example A-54 Treatment fluid A-54 C C B A A A Example A-55 Treatment fluid A-55 C C B A A A Example A-56 Treatment fluid A-56 B C B A A A Example A-57 Treatment liquid A-57 A B A A B A Example A-58 Treatment liquid A-58 A B A A A A Example A-59 Treatment fluid A-59 B C B A A A Example A-60 Treatment fluid A-60 B C B A A A Example A-61 Treatment fluid A-61 B C B A A A Example A-62 Treatment fluid A-62 B C B A A A Example A-63 Treatment fluid A-63 B C B A A A Example A-64 Treatment fluid A-64 A B A A B A Example A-65 Treatment fluid A-65 A B A A B A Example A-66 Treatment fluid A-66 B B A A A A Example A-67 Treatment liquid A-67 C C A A A A Example A-68 Treatment fluid A-68 C C B A A A Example A-69 Example A-69 C C B A A A Example A-70 Example A-70 B C B A A A Comparative example A-1 Treatment fluid RA-1 E E D B A A Comparative Example A-2 Treatment fluid RA-2 E E E E A A Comparative example A-3 Treatment fluid RA-3 E E D B A A Comparative example A-4 Treatment fluid RA-4 E E E E A A Comparative example A-5 Treatment fluid RA-5 E E E E A A Comparative Example A-6 Treatment fluid RA-6 E E E E A A

It is confirmed from the results in Table 2 that according to the treatment liquid of the example (a treatment liquid containing an ether solvent as the solvent A-1 and an alcohol solvent as the solvent B-1), it is possible to form a film in the exposed area with suppressed pattern collapse A pattern in which impairment is suppressed, and bridging defects are suppressed. In addition, it was confirmed that the treatment liquid of the example has a low electrical resistivity and is excellent in safety. Furthermore, it is confirmed from the results in Table 2 that the second organic solvent contains selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, and 3-ethyl-3 -When one or more of pentanol, 2,6-dimethyl-4-heptanol, 2-ethyl-1-hexanol and 2-octanol, or 2,6-dimethyl-4-heptanol When any one or more of alcohol and 3-octanol, or contains an acyclic alcohol solvent having a triple bond in the molecule (preferably selected from 1-octyn-3-ol, 3,5-dimethyl- When one or more of 1-hexyn-3-ol, 1-heptyn-3-ol, and 7-octyn-1-ol), pattern collapse is further suppressed, and film loss in the exposed portion is further suppressed. Furthermore, it was confirmed that the second organic solvent contains selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2, When one or more of 6-dimethyl-4-heptanol and 2-octanol, or when any one or more of 2,6-dimethyl-4-heptanol and 3-octanol is included, or when it contains a molecule An acyclic alcohol solvent with a triple bond (preferably selected from 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-heptyne-3-ol In the case of one or more of alcohol and 7-octyn-1-ol), pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridging defects are further suppressed. In addition, it was confirmed from the results of Table 2 that when the ΔP of the first organic solvent is 13.5 or less and the ΔD is 73.0 or more (preferably when diisoamyl ether), it is possible to form a pattern in which pattern collapse is further suppressed.

In addition, it was confirmed from the results in Table 2 that the ΔP of the first organic solvent was 13.5 or less and the ΔD was 73.0 or more, the second organic solvent contained 3,7-dimethyl-3-octanol, and the content of the first organic solvent was relatively When the total content of the first organic solvent and the second organic solvent is 20 to 80% by mass, the pattern collapse can be further suppressed, the film loss of the exposed part is suppressed, and the bridging defect is suppressed, and the treatment liquid itself The resistivity is also appropriate.

In addition, it was confirmed from the results in Table 2 that the ΔP of the first organic solvent was 13.5 or less and the ΔD was 73.0 or more, and the second organic solvent contained 3,5,5-trimethyl-1-hexanol and 3-ethyl-3 -Any one of pentanol, and when the content of the first organic solvent is 40 to 80% by mass relative to the total content of the first organic solvent and the second organic solvent, the pattern collapse can be further suppressed and the film of the exposed portion can be formed Deterioration is suppressed, and bridging defects are suppressed patterns, and the resistivity of the treatment liquid itself is also appropriate.

Furthermore, it is confirmed from the results in Table 2 that the second organic solvent contains 2,6-dimethyl-4-heptanol, and the content of the first organic solvent relative to the sum of the content of the first organic solvent and the second organic solvent is At 80% by mass or less, it is possible to form a pattern in which pattern collapse is further suppressed and bridging defects are further suppressed. In addition, it was confirmed from the results in Table 2 that the second organic solvent was 2-ethyl-1-hexanol, and the content of the first organic solvent was 40% by mass relative to the total content of the first organic solvent and the second organic solvent. In the above, pattern collapse can be further suppressed. In addition, when the second organic solvent is 2-ethyl-1-hexanol, and the content of the first organic solvent is less than 40% by mass relative to the total content of the first organic solvent and the second organic solvent, bridging defects can be further formed. A suppressed pattern.

In addition, it is confirmed from the results in Table 2 that the ΔP of the first organic solvent is 13.5 or less and the ΔD is 73.0 or more, the second organic solvent contains 2-octanol, and the content of the first organic solvent is relative to that of the first organic solvent and the second organic solvent. When the total content of the organic solvent is 20 to 80% by mass, it is possible to form a pattern in which pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridge defects are further suppressed.

It was confirmed that the treatment liquid of the comparative example did not meet the desired requirements.

[Table 6] table 3 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid B-1 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Ethyl Acetate 141-97-9 20.7 51.4 22.7 25.9 0.3 7 3 30 Treatment fluid B-2 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 7 3 35 Treatment fluid B-3 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Methyl pyruvate 600-22-6 21.6 47.1 28.4 24.5 -0.37 9 1 25 Treatment fluid B-4 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Ethyl pyruvate 617-35-6 21.1 49.6 27.2 23.3 0.16 9 1 25 Treatment fluid B-5 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Diethyl oxalate 95-92-1 21.8 49.1 24.2 26.7 0.89 9 1 25 Treatment fluid B-6 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 9 1 25 Treatment fluid B-7 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 3 7 45 Treatment fluid B-8 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Ethyl Acetate 141-97-9 20.7 51.4 22.7 25.9 0.3 9 1 20 Treatment fluid B-9 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Ethyl Acetate 141-97-9 20.7 51.4 22.7 25.9 0.3 3 7 40 Treatment fluid RB-1 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Propylene glycol-1-monomethyl ether-2-acetate 108-65-6 17.9 50.3 18.1 31.6 0.6 7 3 25 Treatment fluid RB-2 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 2-ethoxy ethyl acetate 111-15-9 18.2 58.0 20.3 21.7 0.7 7 3 25 Treatment fluid RB-3 Diisoamyl ether 544-01-4 15.6 76.8 12.1 11.1 Methyl benzoate 93-58-3 21.1 59.4 25.8 14.8 2.11 7 3 40

[Table 7] Table 4 Type of treatment liquid Evaluation results Resolution Exposure film loss Bridging defect Resistivity Dense pattern Sparse pattern Example B-1 Treatment fluid B-1 C B B A A Example B-2 Treatment fluid B-2 C B B A A Example B-3 Treatment fluid B-3 B B A B A Example B-4 Treatment fluid B-4 B B A B A Example B-5 Treatment fluid B-5 B B A B A Example B-6 Treatment fluid B-6 B B A B A Example B-7 Treatment fluid B-7 C B C A A Example B-8 Treatment fluid B-8 B B A A A Example B-9 Treatment fluid B-9 C B C A A Comparative Example B-1 Treatment fluid RB-1 E E E A A Comparative Example B-2 Treatment fluid RB-2 E E E D A Comparative Example B-3 Treatment fluid RB-3 C B E D A

It is confirmed from the results in Table 4 that according to the treatment liquid of the example (a treatment liquid containing an ether solvent as the solvent A-1 and an ester solvent as the solvent B-2), it is possible to form a film in the exposed portion with suppressed pattern collapse A pattern in which impairment is suppressed, and bridging defects are suppressed. In addition, it was confirmed that the treatment liquid of the example has a low electrical resistivity and is excellent in safety. In addition, it was confirmed from the results in Table 4 that when the content of the first organic solvent relative to the total content of the first organic solvent and the second organic solvent is 50% by mass or more (preferably, 80% by mass or more), a pattern can be formed A pattern in which collapse is further suppressed and film deterioration in the exposed portion is further suppressed, and the resistivity of the treatment liquid itself is also appropriate. Wherein, the second organic solvent is ethyl acetate, and when the content of the first organic solvent is 80% by mass or more relative to the total content of the first organic solvent and the second organic solvent, pattern collapse can be further suppressed and exposed to light The film loss of the part is further suppressed, the bridging defect is further suppressed, and the resistivity of the treatment liquid itself is also appropriate.

It was confirmed that the treatment liquid of the comparative example did not meet the desired requirements.

[Table 8] table 5 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid C-1 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment liquid C-2 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment liquid C-3 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 10 Treatment fluid C-4 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 15 Treatment liquid C-5 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-ethyl-1-hexanol 104-76-6 20.7 66.3 14.6 19.1 2.8 7 3 20 Treatment liquid C-6 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 15 Treatment fluid C-7 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 45 Treatment fluid C-8 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 75 Treatment fluid C-9 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 110 Treatment fluid C-10 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 15 Treatment fluid C-11 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30 Treatment fluid C-12 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 45 Treatment liquid C-13 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 75 Treatment fluid C-14 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 110 Treatment fluid C-15 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 25 Treatment fluid C-16 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid C-17 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 35 Treatment fluid C-18 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 40 Treatment fluid C-19 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 20 Treatment fluid C-20 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid C-21 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment fluid C-22 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid C-23 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 20 Treatment fluid C-24 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid C-25 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 30 Treatment fluid C-26 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 35 Treatment fluid C-27 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 9 1 20 Treatment fluid C-28 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 7 3 twenty four Treatment fluid C-29 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 5 5 28 Treatment fluid C-30 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 3 7 33

[Table 9] Continued Table 5 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid C-31 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 9 1 twenty two Treatment fluid C-32 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 7 3 27 Treatment fluid C-33 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 5 5 33 Treatment fluid C-34 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 3 7 39 Treatment fluid C-35 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 15 Treatment fluid C-36 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 45 Treatment fluid C-37 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 75 Treatment fluid C-38 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 110 Treatment fluid C-39 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 13 Treatment fluid C-40 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 40 Treatment fluid C-41 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 70 Treatment fluid C-42 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 95 Treatment fluid C-43 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 10 Treatment fluid C-44 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 40 Treatment fluid C-45 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 60 Treatment fluid C-46 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 80 Treatment fluid C-47 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 10 Treatment fluid C-48 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 40 Treatment fluid C-49 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 60 Treatment fluid C-50 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 80 Treatment fluid C-51 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 45 Treatment fluid C-52 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 45 Treatment fluid C-53 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 30 Treatment fluid C-54 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2-ethyl-1-hexanol 104-76-7 20.7 63.3 14.6 19.1 2.8 7 3 35 Treatment fluid C-55 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 20 Treatment fluid C-56 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 50 Treatment fluid C-57 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 80 Treatment fluid C-58 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 115 Treatment fluid C-59 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 15 Treatment fluid C-60 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30

[Table 10] Continued Table 5 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid C-61 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 45 Treatment fluid C-62 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 75 Treatment fluid C-63 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 110 Treatment fluid C-64 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 25 Treatment fluid C-65 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid C-66 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 35 Treatment fluid C-67 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 40 Treatment fluid C-68 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 20 Treatment fluid C-69 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid C-70 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment fluid C-71 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid C-72 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 20 Treatment fluid C-73 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid C-74 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 30 Treatment fluid C-75 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 35 Treatment fluid C-76 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 9 1 18 Treatment fluid C-77 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 7 3 twenty two Treatment fluid C-78 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 5 5 27 Treatment fluid C-79 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 3 7 32 Treatment fluid C-80 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 9 1 twenty two Treatment fluid C-81 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 7 3 27 Treatment fluid C-82 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 5 5 32 Treatment fluid C-83 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 3 7 38 Treatment fluid C-84 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 14 Treatment fluid C-85 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 35 Treatment fluid C-86 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 42 Treatment fluid C-87 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 70 Treatment fluid C-88 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 100 Treatment fluid C-89 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 20 Treatment fluid C-90 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 50

[Table 11] Continued Table 5 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid C-91 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 80 Treatment fluid C-92 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 115 Treatment fluid C-93 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 15 Treatment fluid C-94 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 45 Treatment fluid C-95 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 65 Treatment fluid C-96 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 85 Treatment fluid C-97 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 15 Treatment fluid C-98 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 45 Treatment fluid C-99 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 65 Treatment fluid C-100 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 85 Treatment fluid C-101 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 35 Treatment fluid C-102 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 35 Treatment fluid C-103 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 20 Treatment fluid C-104 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 25 Treatment fluid C-105 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 20 Treatment fluid C-106 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 50 Treatment fluid C-107 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 80 Treatment fluid C-108 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 115 Treatment fluid C-109 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 15 Treatment fluid C-110 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30 Treatment fluid C-111 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 45 Treatment fluid C-112 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 75 Treatment fluid C-113 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 110 Treatment fluid C-114 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 25 Treatment fluid C-115 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid C-116 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 35 Treatment fluid C-117 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 40 Treatment fluid C-118 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 20 Treatment fluid C-119 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid C-120 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30

[Table 12] Continued Table 5 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid C-121 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid C-122 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 20 Treatment fluid C-123 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid C-124 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 30 Treatment fluid C-125 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 35 Treatment fluid C-126 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 14 Treatment fluid C-127 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 42 Treatment fluid C-128 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 70 Treatment fluid C-129 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 100 Treatment fluid C-130 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 20 Treatment fluid C-131 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 50 Treatment fluid C-132 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 80 Treatment fluid C-133 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 115 Treatment fluid C-134 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 15 Treatment fluid C-135 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 45 Treatment fluid C-136 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 65 Treatment fluid C-137 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 85 Treatment fluid C-138 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 15 Treatment fluid C-139 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 45 Treatment fluid C-140 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 65 Treatment fluid C-141 1,5-Cyclooctadiene 111-78-4 14.3 67.8 12.9 19.2 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 85 Treatment fluid C-142 Undecane 1120-21-4 15.9 100.0 0.0 0.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 55 Treatment fluid C-143 Undecane 1120-21-4 15.9 100.0 0.0 0.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 55 Treatment fluid C-144 Undecane 1120-21-4 15.9 100.0 0.0 0.0 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid C-145 Undecane 1120-21-4 15.9 100.0 0.0 0.0 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid C-146 Undecane 1120-21-4 15.9 100.0 0.0 0.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid C-147 Undecane 1120-21-4 15.9 100.0 0.0 0.0 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 30 Treatment fluid C-148 Undecane 1120-21-4 15.9 100.0 0.0 0.0 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 35 Treatment fluid RC-1 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-butanol 78-92-2 20.7 43.9 15.8 40.3 0.6 9 1 15 Treatment fluid RC-2 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 MIBC 108-11-2 21.1 51.5 14.5 34.0 1.5 9 1 20 Treatment fluid RC-3 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Benzyl alcohol 100-51-6 21.1 47.9 16.4 35.7 1.1 9 1 25

[Table 13] Table 6 Type of treatment liquid Evaluation results Resolution Exposure film loss Bridging defect Resistivity Dense pattern DOT pattern Sparse pattern Example C-1 Treatment fluid C-1 A B A A A B Example C-2 Treatment liquid C-2 A B A A A B Example C-3 Treatment liquid C-3 A A A A A C Example C-4 Treatment fluid C-4 A B A A A A Example C-5 Treatment liquid C-5 A B A A B A Example C-6 Treatment liquid C-6 A B A A A B Example C-7 Treatment fluid C-7 A B A A A B Example C-8 Treatment fluid C-8 B B A A A B Example C-9 Treatment fluid C-9 B C A A A A Example C-10 Treatment fluid C-10 A B A A A B Example C-11 Treatment fluid C-11 A B A A A B Example C-12 Treatment fluid C-12 A B A A A B Example C-13 Treatment liquid C-13 A C A A A B Example C-14 Treatment fluid C-14 B C A A A A Example C-15 Treatment fluid C-15 A A A A A B Example C-16 Treatment fluid C-16 A A A A A A Example C-17 Treatment fluid C-17 A A A A A A Example C-18 Treatment fluid C-18 A B A A A A Example C-19 Treatment fluid C-19 A A A A A B Example C-20 Treatment fluid C-20 A A A A A A Example C-21 Treatment fluid C-21 A A A A A A Example C-22 Treatment fluid C-22 A A A A A A Example C-23 Treatment fluid C-23 A A A A A B Example C-24 Treatment fluid C-24 A A A A A A Example C-25 Treatment fluid C-25 A B A A A A Example C-26 Treatment fluid C-26 B B A A A A Example C-27 Treatment fluid C-27 A A A A A B Example C-28 Treatment fluid C-28 A A A A A A Example C-29 Treatment fluid C-29 A A A A A A Example C-30 Treatment fluid C-30 A A A A A A Example C-31 Treatment fluid C-31 A A A A A B Example C-32 Treatment fluid C-32 A A A A A A Example C-33 Treatment fluid C-33 A A A A A A Example C-34 Treatment fluid C-34 B B A A A A Example C-35 Treatment fluid C-35 A B A A A C Example C-36 Treatment fluid C-36 A B A A A C Example C-37 Treatment fluid C-37 A C A A A C Example C-38 Treatment fluid C-38 A C B A A C Example C-39 Treatment fluid C-39 A A A A A C Example C-40 Treatment fluid C-40 A A A A A C Example C-41 Treatment fluid C-41 A A A A A C Example C-42 Treatment fluid C-42 A A A A A C Example C-43 Treatment fluid C-43 A B A A A B Example C-44 Treatment fluid C-44 A B A A A A Example C-45 Treatment fluid C-45 A B A A A A

[Table 14] Continued Table 6 Type of treatment liquid Evaluation results Resolution Exposure film loss Bridging defect Resistivity Dense pattern DOT pattern Sparse pattern Example C-46 Treatment fluid C-46 A B B A A A Example C-47 Treatment fluid C-47 A B A A B B Example C-48 Treatment fluid C-48 A B A A B A Example C-49 Treatment fluid C-49 A B A A A A Example C-50 Treatment fluid C-50 A C A A A A Example C-51 Treatment fluid C-51 A B A A A B Example C-52 Treatment fluid C-52 A B A A A B Example C-53 Treatment fluid C-53 A B A A A A Example C-54 Treatment fluid C-54 A B A A B A Example C-55 Treatment fluid C-55 A B A A A B Example C-56 Treatment fluid C-56 B B A A A B Example C-57 Treatment fluid C-57 C B A A A B Example C-58 Treatment fluid C-58 C B A A A A Example C-59 Treatment fluid C-59 A C A A A B Example C-60 Treatment fluid C-60 A B A A A B Example C-61 Treatment fluid C-61 A B A A A B Example C-62 Treatment fluid C-62 A C A A A A Example C-63 Treatment fluid C-63 B C A A A A Example C-64 Treatment fluid C-64 A A A A A B Example C-65 Treatment fluid C-65 A A A A A A Example C-66 Treatment fluid C-66 A A A A A A Example C-67 Treatment fluid C-67 A B A A A A Example C-68 Treatment fluid C-68 A A A A A B Example C-69 Treatment fluid C-69 A A A A A A Example C-70 Treatment fluid C-70 A A A A A A Example C-71 Treatment fluid C-71 A A A A A A Example C-72 Treatment fluid C-72 A A A A A B Example C-73 Treatment fluid C-73 A A A A A A Example C-74 Treatment fluid C-74 A B A A A A Example C-75 Treatment fluid C-75 B B A A A A Example C-76 Treatment fluid C-76 A A A A A B Example C-77 Treatment fluid C-77 A A A A A A Example C-78 Treatment fluid C-78 A A A A A A Example C-79 Treatment fluid C-79 A A A A A A Example C-80 Treatment fluid C-80 A A A A A B Example C-81 Treatment fluid C-81 A A A A A A Example C-82 Treatment fluid C-82 A A A A A A Example C-83 Treatment fluid C-83 B B A A A A Example C-84 Treatment fluid C-84 A A A A A B Example C-85 Treatment fluid C-85 A A A A A B Example C-86 Treatment fluid C-86 A A A A A B Example C-87 Treatment fluid C-87 A A A A A C Example C-88 Treatment fluid C-88 A A A A A C Example C-89 Treatment fluid C-89 A B A A A B Example C-90 Treatment fluid C-90 A B A A A B

[Table 15] Continued Table 6 Type of treatment liquid Evaluation results Resolution Exposure film loss Bridging defect Resistivity Dense pattern DOT pattern Sparse pattern Example C-91 Treatment fluid C-91 B C A A A B Example C-92 Treatment fluid C-92 B C B A A A Example C-93 Treatment fluid C-93 A B A A A B Example C-94 Treatment fluid C-94 A B A A A A Example C-95 Treatment fluid C-95 B C A A A A Example C-96 Treatment fluid C-96 B C B A A A Example C-97 Treatment fluid C-97 A B A A B B Example C-98 Treatment fluid C-98 A B A A B A Example C-99 Treatment fluid C-99 B C A A A A Example C-100 Treatment fluid C-100 C C A A A A Example C-101 Treatment fluid C-101 A B A A A B Example C-102 Treatment fluid C-102 A B A A A B Example C-103 Treatment fluid C-103 A B A A A A Example C-104 Treatment fluid C-104 A B A A B A Example C-105 Treatment fluid C-105 A B A A A B Example C-106 Treatment fluid C-106 A B A A A B Example C-107 Treatment fluid C-107 B B A A A B Example C-108 Treatment fluid C-108 B C A A A A Example C-109 Treatment fluid C-109 A B A A A B Example C-110 Treatment fluid C-110 A B A A A B Example C-111 Treatment fluid C-111 A B A A A B Example C-112 Treatment fluid C-112 A C A A A A Example C-113 Treatment fluid C-113 B C A A A A Example C-114 Treatment fluid C-114 A A A A A B Example C-115 Treatment fluid C-115 A A A A A A Example C-116 Treatment fluid C-116 A A A A A A Example C-117 Treatment fluid C-117 A B A A A A Example C-118 Treatment fluid C-118 A A A A A B Example C-119 Treatment fluid C-119 A A A A A A Example C-120 Treatment fluid C-120 A A A A A A Example C-121 Treatment fluid C-121 A A A A A A Example C-122 Treatment fluid C-122 A A A A A B Example C-123 Treatment fluid C-123 A A A A A A Example C-124 Treatment fluid C-124 A B A A A A Example C-125 Treatment fluid C-125 B B A A A A Example C-126 Treatment fluid C-126 A A A A A B Example C-127 Treatment fluid C-127 A A A A A B Example C-128 Treatment fluid C-128 A A A A A C Example C-129 Treatment fluid C-129 A A A A A C Example C-130 Treatment fluid C-130 A B A A A B Example C-131 Treatment fluid C-131 A B A A A B Example C-132 Treatment fluid C-132 A C A A A B Example C-133 Treatment fluid C-133 A C B A A A Example C-134 Treatment fluid C-134 A B A A A B Example C-135 Treatment fluid C-135 A B A A A A Example C-136 Treatment fluid C-136 A C A A A A

[Table 16] Continued Table 6 Type of treatment liquid Evaluation results Resolution Exposure film loss Bridging defect Resistivity Dense pattern DOT pattern Sparse pattern Example C-137 Treatment fluid C-137 A C B A A A Example C-138 Treatment fluid C-138 A B A A B B Example C-139 Treatment fluid C-139 A B A A B A Example C-140 Treatment fluid C-140 A C A A A A Example C-141 Treatment fluid C-141 A C A A A A Example C-142 Treatment fluid C-142 C B A A A B Example C-143 Treatment fluid C-143 C B A A A B Example C-144 Treatment fluid C-144 A A A A A A Example C-145 Treatment fluid C-145 A A A A A A Example C-146 Treatment fluid C-146 A A A A A A Example C-147 Treatment fluid C-147 B B A A A A Example C-148 Treatment fluid C-148 C B A A B A Comparative example RC-1 Treatment fluid RC-1 E E E E A A Comparative example RC-2 Treatment fluid RC-2 C D C E A A Comparative example RC-3 Treatment fluid RC-3 D E D E A A

It is confirmed from the results in Table 6 that according to the treatment liquid of the example (a treatment liquid containing a hydrocarbon solvent as the solvent A-1 and an alcohol solvent as the solvent B-1), it is possible to form a film in the exposed area with suppressed pattern collapse A pattern in which impairment is suppressed, and bridging defects are suppressed. Furthermore, it is confirmed from the results in Table 6 that the second organic solvent contains selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3 -When one or more of pentanol, 2,6-dimethyl-4-heptanol and 2-octanol, or any one of 2,6-dimethyl-4-heptanol and 3-octanol In the above case, or an acyclic alcohol solvent containing a triple bond in the molecule (preferably selected from 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1 -Heptyn-3-ol and 7-octyn-1-ol), the pattern collapse is further suppressed, the film loss of the exposed part is further suppressed, and the bridging defect is further suppressed. Wherein, when it is confirmed that the second organic solvent contains any one or more of 2,6-dimethyl-4-heptanol and 3-octanol or contains an acyclic alcohol solvent having a triple bond in the molecule (preferably selected From one or more of 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-heptyn-3-ol and 7-octyn-1-ol) Regardless of the type of the first organic solvent and the content ratio of the first organic solvent to the second organic solvent, pattern collapse is further suppressed, film deterioration of the exposed part is further suppressed, and bridging defects are further suppressed. Furthermore, it is confirmed from the results in Table 6 that the second organic solvent contains 3,7-dimethyl-3-octanol, and the content of the first organic solvent relative to the sum of the content of the first organic solvent and the second organic solvent is At 40 to 80% by mass (preferably at 60 to 80% by mass), it is possible to form a pattern in which pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridging defects are further suppressed. In addition, it was confirmed from the results in Table 6 that the second organic solvent contains one or more selected from 3,5,5-trimethyl-1-hexanol and 3-ethyl-3-pentanol, and the first organic solvent When the total content of the first organic solvent and the second organic solvent is 20 to 80% by mass (preferably 40 to 80% by mass), pattern formation can be further suppressed, and film loss in the exposed area can be further suppressed. A pattern that is suppressed, and bridging defects are further suppressed. In addition, it was confirmed from the results in Table 6 that the second organic solvent contains 2-octanol and the content of the first organic solvent is 20 to 80% by mass relative to the total content of the first organic solvent and the second organic solvent. A pattern is formed in which pattern collapse is further suppressed, film deterioration in the exposed portion is further suppressed, and bridging defects are further suppressed.

In addition, it is confirmed from the results in Table 6 that the second organic solvent is 2-ethyl-1-hexanol, and the content of the first organic solvent is less than 40% by mass relative to the total content of the first organic solvent and the second organic solvent. At this time, it is possible to form a pattern in which pattern collapse is further suppressed, film deterioration of the exposed portion is further suppressed, and bridge defects are further suppressed. Wherein, it is confirmed that the first organic solvent contains 1,5-cyclooctadiene, the second organic solvent is 2-ethyl-1-hexanol, and the content of the first organic solvent is relative to the first organic solvent and the second organic solvent When the total content of is less than 40% by mass, it is possible to form a pattern in which pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridge defects are further suppressed.

It was confirmed that the treatment liquid of the comparative example did not meet the desired requirements.

[Table 17] Table 7 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid D-1 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Ethyl Acetate 141-97-9 20.7 51.4 22.7 25.9 0.3 7 3 30 Treatment fluid D-2 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 7 3 35 Treatment fluid D-3 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Methyl pyruvate 600-22-6 21.6 47.1 28.4 24.5 -0.37 9 1 20 Treatment fluid D-4 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Ethyl pyruvate 617-35-6 21.1 49.6 27.2 23.3 0.16 9 1 20 Treatment fluid D-5 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Diethyl oxalate 95-92-1 21.8 49.1 24.2 26.7 0.89 9 1 20 Treatment fluid D-6 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 9 1 25 Treatment fluid D-7 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 3 7 45 Treatment fluid D-8 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Ethyl Acetate 141-97-9 20.7 51.4 22.7 25.9 0.3 9 1 20 Treatment fluid D-9 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Ethyl Acetate 141-97-9 20.7 51.4 22.7 25.9 0.3 3 7 40 Treatment fluid D-10 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 Ethyl Acetate 141-97-9 20.7 51.4 22.7 25.9 0.3 7 3 30 Treatment fluid D-11 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 7 3 35 Treatment fluid D-12 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 Methyl pyruvate 600-22-6 21.6 47.1 28.4 24.5 -0.37 9 1 20 Treatment fluid D-13 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 Ethyl pyruvate 617-35-6 21.1 49.6 27.2 23.3 0.16 9 1 20 Treatment fluid D-14 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 Diethyl oxalate 95-92-1 21.8 49.1 24.2 26.7 0.89 9 1 20 Treatment fluid D-15 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 9 1 25 Treatment fluid D-16 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 Dimethyl malonate 108-59-8 20.6 49.8 21.0 29.1 0.07 3 7 45 Treatment fluid D-17 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 Ethyl Acetate 141-97-9 20.7 51.4 22.7 25.9 0.3 9 1 20 Treatment fluid D-18 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 Ethyl Acetate 141-97-9 20.7 51.4 22.7 25.9 0.3 3 7 40 Treatment fluid RD-1 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Propylene glycol-1-monomethyl ether-2-acetate 108-65-6 17.9 50.3 18.1 31.6 0.6 7 3 25.0 Treatment fluid RD-2 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 2-ethoxy ethyl acetate 111-15-9 18.2 58.0 20.3 21.7 0.7 7 3 25.0 Treatment fluid RD-3 Ethyl cyclohexane 1678-91-7 16.4 100.0 0.0 0.0 Methyl benzoate 93-58-3 21.1 59.4 25.8 14.8 2.11 7 3 40 Treatment fluid RD-4 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 Propylene glycol-1-monomethyl ether-2-acetate 108-65-6 17.9 50.3 18.1 31.6 0.6 7 3 25.0 Treatment fluid RD-5 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 2-ethoxy ethyl acetate 111-15-9 18.2 58.0 20.3 21.7 0.7 7 3 25.0 Treatment fluid RD-6 Symmetric Trimethylbenzene 108-67-8 18.6 93.8 3.1 3.1 Methyl benzoate 93-58-3 21.1 59.4 25.8 14.8 2.11 7 3 40

[Table 18] Table 8 Type of treatment liquid Evaluation results Resolution Exposure film loss Bridging defect Resistivity Dense pattern Sparse pattern Example D-1 Treatment fluid D-1 C B B A A Example D-2 Treatment fluid D-2 C B B A A Example D-3 Treatment fluid D-3 B B A B A Example D-4 Treatment fluid D-4 B B A B A Example D-5 Treatment fluid D-5 B B A B A Example D-6 Treatment fluid D-6 B B A B A Example D-7 Treatment fluid D-7 C B C A A Example D-8 Treatment fluid D-8 B B A A A Example D-9 Treatment fluid D-9 C B C A A Example D-10 Treatment fluid D-10 C B B A A Example D-11 Treatment fluid D-11 C B B A A Example D-12 Treatment fluid D-12 B B A B A Example D-13 Treatment fluid D-13 B B A B A Example D-14 Treatment fluid D-14 B B A B A Example D-15 Treatment fluid D-15 B B A B A Example D-16 Treatment fluid D-16 C B C A A Example D-17 Treatment fluid D-17 B B A A A Example D-18 Treatment fluid D-18 C B C A A Comparative example RD-1 Treatment fluid RD-1 E E E A A Comparative example RD-2 Treatment fluid RD-2 E E E D A Comparative example RD-3 Treatment fluid RD-3 C B D D A Comparative example RD-4 Treatment fluid RD-4 E E E A A Comparative example RD-5 Treatment fluid RD-5 E E E D A Comparative example RD-6 Treatment fluid RD-6 C B D D A

It is confirmed from the results in Table 8 that according to the treatment liquid of the example (a treatment liquid containing a hydrocarbon solvent as the solvent A-1 and an ester solvent as the solvent B-2), it is possible to form a film in the exposed area with suppressed pattern collapse A pattern in which impairment is suppressed, and bridging defects are suppressed. In addition, it was confirmed that the treatment liquid of the example has a low electrical resistivity and is excellent in safety. In addition, it was confirmed from the results in Table 8 that when the content of the first organic solvent relative to the total content of the first organic solvent and the second organic solvent is 50% by mass or more (preferably, 80% by mass or more), a pattern can be formed A pattern in which collapse is further suppressed, and film deterioration in the exposed portion is further suppressed, and the resistivity of the treatment liquid itself is also appropriate. In addition, when the second organic solvent is ethyl acetylacetate, and the content of the first organic solvent is 80% by mass or more with respect to the total content of the first organic solvent and the second organic solvent, pattern collapse can be further suppressed and exposed to light. The film loss of the part is further suppressed, the bridging defect is further suppressed, and the resistivity of the treatment liquid itself is also appropriate.

It was confirmed that the treatment liquid of the comparative example did not meet the desired requirements.

[Table 19] Table 9 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid E-1 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment fluid E-2 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment fluid E-3 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 15 Treatment fluid E-4 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 20 Treatment fluid E-5 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 15 Treatment fluid E-6 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 45 Treatment fluid E-7 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 75 Treatment fluid E-8 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 110 Treatment fluid E-9 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 15 Treatment fluid E-10 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30 Treatment fluid E-11 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 40 Treatment fluid E-12 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 65 Treatment fluid E-13 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 90 Treatment fluid E-14 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 25 Treatment fluid E-15 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid E-16 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 35 Treatment fluid E-17 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 40 Treatment fluid E-18 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 1 9 45 Treatment fluid E-19 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 20 Treatment fluid E-20 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid E-21 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment fluid E-22 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid E-23 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 1 9 40 Treatment fluid E-24 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 20 Treatment fluid E-25 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid E-26 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 30 Treatment fluid E-27 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 35 Treatment fluid E-28 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 1 9 40 Treatment fluid E-29 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 9 1 18 Treatment fluid E-30 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 7 3 twenty two Treatment fluid E-31 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 5 5 28 Treatment fluid E-32 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 3 7 31 Treatment fluid E-33 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 1 9 35

[Table 20] Continued Table 9 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid E-34 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 9 1 twenty two Treatment fluid E-35 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 7 3 28 Treatment fluid E-36 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 5 5 34 Treatment fluid E-37 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 3 7 40 Treatment fluid E-38 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 1 9 46 Treatment fluid E-39 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 15 Treatment fluid E-40 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 30 Treatment fluid E-41 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 40 Treatment fluid E-42 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 60 Treatment fluid E-43 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 85 Treatment fluid E-44 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 15 Treatment fluid E-45 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 45 Treatment fluid E-46 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 75 Treatment fluid E-47 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 110 Treatment fluid E-48 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 10 Treatment fluid E-49 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 40 Treatment fluid E-50 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 60 Treatment fluid E-51 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 80 Treatment fluid E-52 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 10 Treatment fluid E-53 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 40 Treatment fluid E-54 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 60 Treatment fluid E-55 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 80 Treatment fluid E-56 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment fluid E-57 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment fluid E-58 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 15 Treatment fluid E-59 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 20 Treatment fluid E-60 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 15 Treatment fluid E-61 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 45 Treatment fluid E-62 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 75 Treatment fluid E-63 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 110 Treatment fluid E-64 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 15 Treatment fluid E-65 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30 Treatment fluid E-66 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 40 Treatment fluid E-67 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 65 Treatment fluid E-68 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 90

[Table 21] Continued Table 9 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid E-69 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 25 Treatment fluid E-70 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid E-71 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 35 Treatment fluid E-72 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 40 Treatment fluid E-73 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 1 9 45 Treatment fluid E-74 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 20 Treatment fluid E-75 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid E-76 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment fluid E-77 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid E-78 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 1 9 40 Treatment fluid E-79 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 20 Treatment fluid E-80 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid E-81 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 30 Treatment fluid E-82 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 35 Treatment fluid E-83 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 1 9 40 Treatment fluid E-84 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 9 1 19 Treatment fluid E-85 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 7 3 twenty three Treatment fluid E-86 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 5 5 30 Treatment fluid E-87 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 3 7 35 Treatment fluid E-88 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 1 9 41 Treatment fluid E-89 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 9 1 twenty four Treatment fluid E-90 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 7 3 30 Treatment fluid E-91 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 5 5 35 Treatment fluid E-92 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 3 7 40 Treatment fluid E-93 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 1 9 45 Treatment fluid E-94 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 15 Treatment fluid E-95 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 30 Treatment fluid E-96 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 40 Treatment fluid E-97 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 60 Treatment fluid E-98 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 85 Treatment fluid E-99 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 15 Treatment fluid E-100 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 45 Treatment fluid E-101 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 75 Treatment fluid E-102 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 110

[Table 22] Continued Table 9 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid E-103 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 10 Treatment fluid E-104 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 40 Treatment fluid E-105 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 60 Treatment fluid E-106 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 80 Treatment fluid E-107 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 10 Treatment fluid E-108 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 40 Treatment fluid E-109 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 60 Treatment fluid E-110 Butyl Butyrate 109-21-7 17.8 64.7 12.0 23.2 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 80 Treatment fluid E-111 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment fluid E-112 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment fluid E-113 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 15 Treatment fluid E-114 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 20 Treatment fluid E-115 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 15 Treatment fluid E-116 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 45 Treatment fluid E-117 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 75 Treatment fluid E-118 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 110 Treatment fluid E-119 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 15 Treatment fluid E-120 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30 Treatment fluid E-121 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 40 Treatment fluid E-122 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 65 Treatment fluid E-123 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 90 Treatment fluid E-124 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 25 Treatment fluid E-125 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid E-126 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 35 Treatment fluid E-127 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 40 Treatment fluid E-128 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 1 9 45 Treatment fluid E-129 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 20 Treatment fluid E-130 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid E-131 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment fluid E-132 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid E-133 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 1 9 40 Treatment fluid E-134 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 20 Treatment fluid E-135 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid E-136 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 30 Treatment fluid E-137 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 35 Treatment fluid E-138 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 1 9 40

[Table 23] Continued Table 9 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid E-139 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 15 Treatment fluid E-140 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 30 Treatment fluid E-141 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 40 Treatment fluid E-142 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 60 Treatment fluid E-143 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 85 Treatment fluid E-144 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 15 Treatment fluid E-145 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 45 Treatment fluid E-146 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 75 Treatment fluid E-147 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 110 Treatment fluid E-148 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 10 Treatment fluid E-149 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 40 Treatment fluid E-150 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 60 Treatment fluid E-151 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 80 Treatment fluid E-152 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 10 Treatment fluid E-153 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 40 Treatment fluid E-154 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 60 Treatment fluid E-155 Ethyl 2-methylvalerate 39255-32-8 17.4 66.2 14.8 19.0 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 80 Treatment fluid E-156 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 3,7-Dimethyl-3-octanol 78-69-6 19.7 65.7 10.3 24.0 3.5 7 3 55 Treatment fluid E-157 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30 Treatment fluid E-158 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 30 Treatment fluid E-159 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid E-160 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 25 Treatment fluid E-161 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 35 Treatment fluid E-162 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 55 Treatment fluid E-163 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 30 Treatment fluid E-164 Hexyl acetate 142-92-7 17.8 64.2 11.8 24.0 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 35 Treatment fluid RE-1 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 2-butanol 78-92-2 20.7 43.9 15.8 40.3 0.6 9 1 15 Treatment fluid RE-2 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 4-methyl-2-pentanol 108-11-2 21.1 51.5 14.5 34.0 1.5 9 1 20 Treatment fluid RE-3 Isobutyl isobutyrate 97-85-8 17.1 68.0 14.2 17.8 Benzyl alcohol 100-51-6 21.1 47.9 16.4 35.7 1.1 9 1 25 Treatment fluid RE-4 Butyl crotonate 7299-91-4 19.9 63.4 15.2 21.4 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 13.0 24.0 3.5 7 3 55 Treatment fluid RE-5 Butyl crotonate 7299-91-4 19.9 63.4 15.2 21.4 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 30

[Table 24] Table 10 Type of treatment liquid Evaluation results Resolution Exposure film loss Bridging defect Resistivity Dense pattern DOT pattern Sparse pattern Example E-1 Treatment fluid E-1 B C B A A A Example E-2 Treatment fluid E-2 B C B A A A Example E-3 Treatment fluid E-3 B C B A A A Example E-4 Treatment fluid E-4 B C B A B A Example E-5 Treatment fluid E-5 B B B A A A Example E-6 Treatment fluid E-6 B C B A A A Example E-7 Treatment fluid E-7 C C B A A A Example E-8 Treatment fluid E-8 C C B A A A Example E-9 Treatment fluid E-9 A B A A A A Example E-10 Treatment fluid E-10 A B A A A A Example E-11 Treatment fluid E-11 A B A A A A Example E-12 Treatment fluid E-12 A C A A A A Example E-13 Treatment fluid E-13 A C A A A A Example E-14 Treatment fluid E-14 A A A A A A Example E-15 Treatment fluid E-15 A A A A A A Example E-16 Treatment fluid E-16 A A A A A A Example E-17 Treatment fluid E-17 A A A A A A Example E-18 Treatment fluid E-18 B A A A A A Example E-19 Treatment fluid E-19 A B A A A A Example E-20 Treatment fluid E-20 A A A A A A Example E-21 Treatment fluid E-21 A A A A A A Example E-22 Treatment fluid E-22 A A A A A A Example E-23 Treatment fluid E-23 A A A A A A Example E-24 Treatment fluid E-24 A A A A A A Example E-25 Treatment fluid E-25 A A A A A A Example E-26 Treatment fluid E-26 A B A A A A Example E-27 Treatment fluid E-27 A B A A A A Example E-28 Treatment fluid E-28 A B A A A A Example E-29 Treatment fluid E-29 A A A A A A Example E-30 Treatment fluid E-30 A A A A A A Example E-31 Treatment fluid E-31 A A A A A A Example E-32 Treatment fluid E-32 A A A A A A Example E-33 Treatment fluid E-33 A A A A A A Example E-34 Treatment fluid E-34 A A A A A A Example E-35 Treatment fluid E-35 A A A A A A Example E-36 Treatment fluid E-36 A B A A A A Example E-37 Treatment fluid E-37 A B A A A A Example E-38 Treatment fluid E-38 A B A A A A Example E-39 Treatment fluid E-39 A A A A A B Example E-40 Treatment fluid E-40 A A A A A B Example E-41 Treatment fluid E-41 A A A A A B Example E-42 Treatment fluid E-42 A A A A A B Example E-43 Treatment fluid E-43 A A A A A B Example E-44 Treatment fluid E-44 B B B A A A Example E-45 Treatment fluid E-45 B B B A A A

[Table 25] Continued Table 10 Type of treatment liquid Evaluation results Resolution Exposure film loss Bridging defect Resistivity Dense pattern DOT pattern Sparse pattern Example E-46 Treatment fluid E-46 B B B A A A Example E-47 Treatment fluid E-47 B C C A A A Example E-48 Treatment fluid E-48 B B B A A A Example E-49 Treatment fluid E-49 B B B A A A Example E-50 Treatment fluid E-50 B C B A A A Example E-51 Treatment fluid E-51 B C C A A A Example E-52 Treatment fluid E-52 B B B A B A Example E-53 Treatment fluid E-53 B B B A B A Example E-54 Treatment fluid E-54 B C B A A A Example E-55 Treatment fluid E-55 B C B A A A Example E-56 Treatment fluid E-56 B B B A A A Example E-57 Treatment fluid E-57 B B B A A A Example E-58 Treatment fluid E-58 B B B A A A Example E-59 Treatment fluid E-59 B B B A B A Example E-60 Treatment fluid E-60 B B B A A A Example E-61 Treatment fluid E-61 B B B A A A Example E-62 Treatment fluid E-62 C C B A A A Example E-63 Treatment fluid E-63 C C B A A A Example E-64 Treatment fluid E-64 A B A A A A Example E-65 Treatment fluid E-65 A B A A A A Example E-66 Treatment fluid E-66 A B A A A A Example E-67 Treatment fluid E-67 A C A A A A Example E-68 Treatment fluid E-68 A C A A A A Example E-69 Treatment fluid E-69 A A A A A A Example E-70 Treatment fluid E-70 A A A A A A Example E-71 Treatment fluid E-71 A A A A A A Example E-72 Treatment fluid E-72 A A A A A A Example E-73 Treatment fluid E-73 A B A A A A Example E-74 Treatment fluid E-74 A A A A A A Example E-75 Treatment fluid E-75 A A A A A A Example E-76 Treatment fluid E-76 A A A A A A Example E-77 Treatment fluid E-77 A A A A A A Example E-78 Treatment fluid E-78 A A A A A A Example E-79 Treatment fluid E-79 A A A A A A Example E-80 Treatment fluid E-80 A A A A A A Example E-81 Treatment fluid E-81 A A A A A A Example E-82 Treatment fluid E-82 A B A A A A Example E-83 Treatment fluid E-83 A B A A A A Example E-84 Treatment fluid E-84 A A A A A A Example E-85 Treatment fluid E-85 A A A A A A Example E-86 Treatment fluid E-86 A A A A A A Example E-87 Treatment fluid E-87 A A A A A A Example E-88 Treatment fluid E-88 A A A A A A Example E-89 Treatment fluid E-89 A A A A A A Example E-90 Treatment fluid E-90 A A A A A A Example E-91 Treatment fluid E-91 A A A A A A Example E-92 Treatment fluid E-92 A B A A A A

[Table 26] Continued Table 10 Type of treatment liquid Evaluation results Resolution Exposure film loss Bridging defect Resistivity Dense pattern DOT pattern Sparse pattern Example E-93 Treatment fluid E-93 A B A A A A Example E-94 Treatment fluid E-94 A A A A A B Example E-95 Treatment fluid E-95 A A A A A B Example E-96 Treatment fluid E-96 A A A A A B Example E-97 Treatment fluid E-97 A A A A A B Example E-98 Treatment fluid E-98 A A A A A B Example E-99 Treatment fluid E-99 B B B A A A Example E-100 Treatment fluid E-100 B B B A A A Example E-101 Treatment fluid E-101 B C B A A A Example E-102 Treatment fluid E-102 B C C A A A Example E-103 Treatment fluid E-103 B B B A A A Example E-104 Treatment fluid E-104 B B B A A A Example E-105 Treatment fluid E-105 B C B A A A Example E-106 Treatment fluid E-106 B C C A A A Example E-107 Treatment fluid E-107 B B B A B A Example E-108 Treatment fluid E-108 B B B A B A Example E-109 Treatment fluid E-109 B C B A A A Example E-110 Treatment fluid E-110 B C B A A A Example E-111 Treatment fluid E-111 B C B A A A Example E-112 Treatment fluid E-112 B C B A A A Example E-113 Treatment fluid E-113 B C B A A A Example E-114 Treatment fluid E-114 B C B A B A Example E-115 Treatment fluid E-115 B C B A A A Example E-116 Treatment fluid E-116 B C B A A A Example E-117 Treatment fluid E-117 C C B A A A Example E-118 Treatment fluid E-118 C C B A A A Example E-119 Treatment fluid E-119 A C A A A A Example E-120 Treatment fluid E-120 A C A A A A Example E-121 Treatment fluid E-121 A C A A A A Example E-122 Treatment fluid E-122 A C A A A A Example E-123 Treatment fluid E-123 A C A A A A Example E-124 Treatment fluid E-124 A B A A A A Example E-125 Treatment fluid E-125 A B A A A A Example E-126 Treatment fluid E-126 A B A A A A Example E-127 Treatment fluid E-127 A B A A A A Example E-128 Treatment fluid E-128 A C A A A A Example E-129 Treatment fluid E-129 A B A A A A Example E-130 Treatment fluid E-130 A B A A A A Example E-131 Treatment fluid E-131 A B A A A A Example E-132 Treatment fluid E-132 A B A A A A Example E-133 Treatment fluid E-133 A C A A A A Example E-134 Treatment fluid E-134 A B A A A A Example E-135 Treatment fluid E-135 A B A A A A Example E-136 Treatment fluid E-136 A C A A A A Example E-137 Treatment fluid E-137 A C A A A A Example E-138 Treatment fluid E-138 A C A A A A

[Table 27] Continued Table 10 Type of treatment liquid Evaluation results Resolution Exposure film loss Bridging defect Resistivity Dense pattern DOT pattern Sparse pattern Example E-139 Treatment fluid E-139 A A A A A B Example E-140 Treatment fluid E-140 A A A A A B Example E-141 Treatment fluid E-141 A B A A A B Example E-142 Treatment fluid E-142 A B A A A B Example E-143 Treatment fluid E-143 A B A A A B Example E-144 Treatment fluid E-144 B C B A A A Example E-145 Treatment fluid E-145 B C B A A A Example E-146 Treatment fluid E-146 B C B A A A Example E-147 Treatment fluid E-147 B C C A A A Example E-148 Treatment fluid E-148 B C B A A A Example E-149 Treatment fluid E-149 B C B A A A Example E-150 Treatment fluid E-150 B C B A A A Example E-151 Treatment fluid E-151 B C C A A A Example E-152 Treatment fluid E-152 B C B A B A Example E-153 Treatment fluid E-153 B C B A B A Example E-154 Treatment fluid E-154 B C B A A A Example E-155 Treatment fluid E-155 B C B A A A Example E-156 Treatment fluid E-156 C C B A A A Example E-157 Treatment fluid E-157 B C B A A A Example E-158 Treatment fluid E-158 A B A A A A Example E-159 Treatment fluid E-159 A B A A A A Example E-160 Treatment fluid E-160 B B B A A A Example E-161 Treatment fluid E-161 B B A A A C Example E-162 Treatment fluid E-162 C C B A A A Example E-163 Treatment fluid E-163 C C B A A A Example E-164 Treatment fluid E-164 C C B A B A Comparative Example RE-1 Treatment fluid RE-1 E E E E A A Comparative Example RE-2 Treatment fluid RE-2 D D D E A A Comparative Example RE-3 Treatment fluid RE-3 D E D E A A Comparative Example RE-4 Treatment fluid RE-4 E E E A A A Comparative Example RE-5 Treatment fluid RE-5 E E E A A A

It is confirmed from the results in Table 10 that according to the treatment liquid of the example (a treatment liquid containing an ester solvent as the solvent A-1 and an alcohol solvent as the solvent B-1), it is possible to form a film in the exposed area with suppressed pattern collapse A pattern in which impairment is suppressed, and bridging defects are suppressed. In addition, it was confirmed that the treatment liquid of the example has a low electrical resistivity and is excellent in safety. Furthermore, it is confirmed from the results in Table 10 that the second organic solvent contains selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3 -When one or more of pentanol and 2-octanol, or when any one or more of 2,6-dimethyl-4-heptanol and 3-octanol is included, or when it includes an acyclic ring having a triple bond in the molecule Alcohol solvent (preferably selected from 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-heptyn-3-ol and 7-octyne- In the case of one or more of 1-alcohols), pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridging defects are further suppressed. In addition, it was confirmed that the resistivity of the treatment liquid was low and the safety was also excellent. In addition, when it is confirmed that the second organic solvent contains 2-octanol, when it contains any one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or when it contains an acyclic ring having a triple bond in the molecule The alcohol solvent (preferably selected from 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-heptyn-3-ol and 7-octyne-1 -In the case of one or more of alcohols), pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridge defects are further suppressed. Furthermore, when it is confirmed that the second organic solvent contains any one or more of 2,6-dimethyl-4-heptanol and 3-octanol, or contains an acyclic alcohol solvent having a triple bond in the molecule (preferably One or more selected from 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-heptyn-3-ol and 7-octyn-1-ol) When the content of the first organic solvent is 60% by mass or more relative to the total content of the first organic solvent and the second organic solvent, pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridging defects are further suppressed. Be suppressed.

In addition, it was confirmed from the results in Table 10 that the first organic solvent contains an organic solvent with an SP value of 18.7 MPa ^1/2 or less, and a ΔP of 15.0 or less and a ΔD of 64.5 or more, and the second organic solvent contains 3,7-dimethyl When the content of the first organic solvent is 40 to 80% by mass relative to the total content of the first organic solvent and the second organic solvent, the pattern collapse can be further suppressed, and the film loss of the exposed part can be further suppressed. The pattern is further suppressed, and bridge defects are further suppressed. In addition, it was confirmed from the results in Table 10 that the first organic solvent contains an organic solvent having an SP value of 18.7 MPa ^1/2 or less, a ΔP of 15.0 or less and a ΔD of 64.5 or more, and the second organic solvent contains an organic solvent selected from 3, 5, and 5 -One or more of trimethyl-1-hexanol and 3-ethyl-3-pentanol, and the content of the first organic solvent relative to the total content of the first organic solvent and the second organic solvent is 20 to 80 At mass %, it is possible to form a pattern in which pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridge defects are further suppressed.

In addition, it was confirmed from the results in Table 10 that the first organic solvent contains an organic solvent with an SP value of 18.7 MPa ^1/2 or less, and a ΔP of 15.0 or less and a ΔD of 64.5 or more, and the second organic solvent contains an organic solvent selected from 2-octanol When there is more than one type of 2,6-dimethyl-4-heptanol, it is possible to form a pattern in which pattern collapse is further suppressed, film loss in the exposed part is further suppressed, and bridge defects are further suppressed.

In addition, it was confirmed from the results in Table 8 that the first organic solvent contained an organic solvent having an SP value of 18.7 MPa ^1/2 or less, a ΔP of 15.0 or less and a ΔD of 64.5 or more, and the second organic solvent was 2-ethyl-1- When the content of the first organic solvent is less than 40% by mass with respect to the total content of the first organic solvent and the second organic solvent, the formation pattern collapse is further suppressed, the film loss of the exposed part is further suppressed, and the bridge A pattern in which defects are further suppressed.

In addition, it was confirmed from the results in Table 10 that when the first organic solvent is an organic solvent having a ΔD of 64.5 or more, the collapse of the formed pattern is further suppressed. For example, it is inferred that the hexyl acetate of an organic solvent with a ΔD of less than 64.5, the functional group of the ester that is structurally easy to interact with the polymer is located at the end of the molecule, so compared with the butyl butyrate of the same molecular formula, the dispersion of the polymer High performance and easy to swell the resist.

It was confirmed that the treatment liquid of the comparative example did not meet the desired requirements.

[Table 28] Table 11 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid F-1 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment fluid F-2 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment fluid F-3 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 15 Treatment fluid F-4 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 20 Treatment fluid F-5 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 15 Treatment fluid F-6 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 20 Treatment fluid F-7 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 9 1 12 Treatment fluid F-8 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 5 5 35 Treatment fluid F-9 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 3 7 55 Treatment fluid F-10 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 1 9 85 Treatment fluid F-11 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 9 1 15 Treatment fluid F-12 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 5 5 30 Treatment fluid F-13 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 3 7 60 Treatment fluid F-14 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 1 9 90 Treatment fluid F-15 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 10 Treatment fluid F-16 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 25 Treatment fluid F-17 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 30 Treatment fluid F-18 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 35 Treatment fluid F-19 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 1 9 40 Treatment fluid F-20 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 10 Treatment fluid F-21 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid F-22 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment fluid F-23 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid F-24 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 1 9 40 Treatment fluid F-25 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 8 Treatment fluid F-26 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 twenty three Treatment fluid F-27 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 28 Treatment fluid F-28 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 33 Treatment fluid F-29 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 1 9 38

[Table 29] Continued Table 11 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid F-30 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 9 1 9 Treatment fluid F-31 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 7 3 twenty three Treatment fluid F-32 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 5 5 28 Treatment fluid F-33 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 3 7 34 Treatment fluid F-34 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 1-heptyn-3-ol 7383-19-9 20.5 49.8 17.0 33.1 1.6 1 9 39 Treatment fluid F-35 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 9 1 11 Treatment fluid F-36 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 7 3 27 Treatment fluid F-37 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 5 5 32 Treatment fluid F-38 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 3 7 38 Treatment fluid F-39 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 7-octyn-1-ol 871-91-0 20.3 50.6 17.8 31.6 1.6 1 9 44 Treatment fluid F-40 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 15 Treatment fluid F-41 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 45 Treatment fluid F-42 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 75 Treatment fluid F-43 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 110 Treatment fluid F-44 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 15 Treatment fluid F-45 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 45 Treatment fluid F-46 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 75 Treatment fluid F-47 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 110 Treatment fluid F-48 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 10 Treatment fluid F-49 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 40 Treatment fluid F-50 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 60 Treatment fluid F-51 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 80 Treatment fluid F-52 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 10 Treatment fluid F-53 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 40 Treatment fluid F-54 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 60 Treatment fluid F-55 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 80 Treatment fluid F-56 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment fluid F-57 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment fluid F-58 3-octanone 106-68-3 17.5 65.3 18.1 16.5 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 15

[Table 30] Continued Table 11 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid F-59 3-octanone 106-68-3 17.5 65.3 18.1 16.5 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 20 Treatment fluid F-60 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 9 1 10 Treatment fluid F-61 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 7 3 25 Treatment fluid F-62 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 5 5 30 Treatment fluid F-63 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 3 7 35 Treatment fluid F-64 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3-octanol 589-98-0 20.7 55.6 14.6 29.9 2.7 1 9 40 Treatment fluid F-65 3-octanone 106-68-3 17.5 65.3 18.1 16.5 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 9 1 10 Treatment fluid F-66 3-octanone 106-68-3 17.5 65.3 18.1 16.5 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 7 3 25 Treatment fluid F-67 3-octanone 106-68-3 17.5 65.3 18.1 16.5 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 5 5 30 Treatment fluid F-68 3-octanone 106-68-3 17.5 65.3 18.1 16.5 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 3 7 35 Treatment fluid F-69 3-octanone 106-68-3 17.5 65.3 18.1 16.5 1-octyn-3-ol 818-72-4 26.9 51.7 16.4 31.9 2.1 1 9 40 Treatment fluid F-70 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 9 1 8 Treatment fluid F-71 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 7 3 twenty three Treatment fluid F-72 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 5 5 28 Treatment fluid F-73 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 3 7 33 Treatment fluid F-74 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3,5-Dimethyl-1-hexyn-3-ol 107-54-0 26.1 60.0 13.0 27.0 1.8 1 9 38 Treatment fluid F-75 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 15 Treatment fluid F-76 3-octanone 106-68-3 17.5 65.3 18.1 16.5 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 20 Treatment fluid F-77 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 9 1 15 Treatment fluid F-78 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 5 5 45 Treatment fluid F-79 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 3 7 75 Treatment fluid F-80 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 1 9 110 Treatment fluid F-81 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 9 1 15 Treatment fluid F-82 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 5 5 45 Treatment fluid F-83 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 3 7 75 Treatment fluid F-84 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 1 9 110

[Table 31] Continued Table 11 Treatment liquid Drying time (seconds) First organic solvent Second organic solvent Ratio (mass ratio) species CAS SP value ΔD ΔP ΔH species CAS SP value ΔD ΔP ΔH ClogP First organic solvent Second organic solvent Treatment fluid F-85 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 9 1 10 Treatment fluid F-86 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 5 5 40 Treatment fluid F-87 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 3 7 60 Treatment fluid F-88 3-octanone 106-68-3 17.5 65.3 18.1 16.5 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 1 9 80 Treatment fluid F-89 3-octanone 106-68-3 17.5 65.3 18.1 16.5 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 9 1 10 Treatment fluid F-90 3-octanone 106-68-3 17.5 65.3 18.1 16.5 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 5 5 40 Treatment fluid F-91 3-octanone 106-68-3 17.5 65.3 18.1 16.5 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 3 7 60 Treatment fluid F-92 3-octanone 106-68-3 17.5 65.3 18.1 16.5 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 1 9 80 Treatment fluid RF-1 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 2-butanol 78-92-2 20.7 43.9 15.8 40.3 0.6 9 1 15 Treatment fluid RF-2 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 4-methyl-2-pentanol 108-11-2 21.1 51.5 14.5 34.0 1.5 9 1 20 Treatment fluid RF-3 Diisobutyl ketone 108-83-8 17.4 69.7 18.6 11.8 Benzyl alcohol 100-51-6 21.1 47.9 16.4 35.7 1.1 9 1 25 Treatment fluid RF-4 2-heptanone 110-43-0 18.1 61.9 21.9 16.2 3,7-Dimethyl-3-octanol 78-69-3 19.7 65.7 10.3 24.0 3.5 7 3 30 Treatment fluid RF-5 2-heptanone 110-43-0 18.1 61.9 21.9 16.2 3,5,5-Trimethyl-1-hexanol 3452-97-9 20.5 58.1 12.8 29.1 3.1 7 3 30 Treatment fluid RF-6 2-heptanone 110-43-0 18.1 61.9 21.9 16.2 2,6-Dimethyl-4-heptanol 108-82-7 19.9 51.7 10.8 37.5 3.0 7 3 15 Treatment fluid RF-7 2-heptanone 110-43-0 18.1 61.9 21.9 16.2 2-octanol 123-96-6 20.7 50.3 15.3 34.4 2.7 7 3 20 Treatment fluid RF-8 2-heptanone 110-43-0 18.1 61.9 21.9 16.2 3-ethyl-3-pentanol 597-49-9 20.8 58.7 13.3 28.0 2.1 7 3 15 Treatment fluid RF-9 2-heptanone 110-43-0 18.1 61.9 21.9 16.2 2-ethyl-1-hexanol 104-76-7 20.7 66.3 14.6 19.1 2.8 7 3 20

[Table 32] Table 12 Type of treatment liquid Evaluation results Resolution Exposure film loss Bridging defect Resistivity Dense pattern DOT pattern Sparse pattern Example F-1 Treatment fluid F-1 B B B A A A Example F-2 Treatment fluid F-2 B B B A A A Example F-3 Treatment fluid F-3 B B B A A A Example F-4 Treatment fluid F-4 B B B A B A Example F-5 Treatment fluid F-5 A A A A A C Example F-6 Treatment fluid F-6 A B A A B A Example F-7 Treatment fluid F-7 A A A A A C Example F-8 Treatment fluid F-8 A A A A A C Example F-9 Treatment fluid F-9 A A A A A C Example F-10 Treatment fluid F-10 A A A A A C Example F-11 Treatment fluid F-11 A B A A A A Example F-12 Treatment fluid F-12 A B A A A A Example F-13 Treatment fluid F-13 A B A A A A Example F-14 Treatment fluid F-14 B C B A A A Example F-15 Treatment fluid F-15 A A A A A A Example F-16 Treatment fluid F-16 A A A A A A Example F-17 Treatment fluid F-17 A A A A A A Example F-18 Treatment fluid F-18 A B A A A A Example F-19 Treatment fluid F-19 B B A A A A Example F-20 Treatment fluid F-20 A A A A A A Example F-21 Treatment fluid F-21 A A A A A A Example F-22 Treatment fluid F-22 A A A A A A Example F-23 Treatment fluid F-23 A A A A A A Example F-24 Treatment fluid F-24 A A A A A A Example F-25 Treatment fluid F-25 A A A A A A Example F-26 Treatment fluid F-26 A A A A A A Example F-27 Treatment fluid F-27 A B A A A A Example F-28 Treatment fluid F-28 A B A A A A Example F-29 Treatment fluid F-29 B B A A A A Example F-30 Treatment fluid F-30 A A A A A A Example F-31 Treatment fluid F-31 A A A A A A Example F-32 Treatment fluid F-32 A A A A A A Example F-33 Treatment fluid F-33 A A A A A A Example F-34 Treatment fluid F-34 A A A A A A Example F-35 Treatment fluid F-35 A A A A A A Example F-36 Treatment fluid F-36 A A A A A A Example F-37 Treatment fluid F-37 A A A A A A Example F-38 Treatment fluid F-38 A B A A A A Example F-39 Treatment fluid F-39 B B A A A A Example F-40 Treatment fluid F-40 B B B A A A

[Table 33] Continued Table 12 Type of treatment liquid Evaluation results Resolution Exposure film loss Bridging defect Resistivity Dense pattern DOT pattern Sparse pattern Example F-41 Treatment fluid F-41 B B B A A A Example F-42 Treatment fluid F-42 C C B A A A Example F-43 Treatment fluid F-43 C C B A A A Example F-44 Treatment fluid F-44 B B B A A A Example F-45 Treatment fluid F-45 B C B A A A Example F-46 Treatment fluid F-46 B C B A A A Example F-47 Treatment fluid F-47 B C C A A A Example F-48 Treatment fluid F-48 B B B A A A Example F-49 Treatment fluid F-49 B B B A A A Example F-50 Treatment fluid F-50 B C B A A A Example F-51 Treatment fluid F-51 B C C A A A Example F-52 Treatment fluid F-52 B B B A B A Example F-53 Treatment fluid F-53 B B B A B A Example F-54 Treatment fluid F-54 B C B A A A Example F-55 Treatment fluid F-55 B C B A A A Example F-56 Treatment fluid F-56 B B B A A A Example F-57 Treatment fluid F-57 B B B A A A Example F-58 Treatment fluid F-58 A A A B A A Example F-59 Treatment fluid F-59 A B A A B A Example F-60 Treatment fluid F-60 A B A A A A Example F-61 Treatment fluid F-61 A B A A A A Example F-62 Treatment fluid F-62 A A A A A A Example F-63 Treatment fluid F-63 A A A A A A Example F-64 Treatment fluid F-64 B A A A A A Example F-65 Treatment fluid F-65 A B A A A A Example F-66 Treatment fluid F-66 A B A A A A Example F-67 Treatment fluid F-67 A A A A A A Example F-68 Treatment fluid F-68 A A A A A A Example F-69 Treatment fluid F-69 A A A A A A Example F-70 Treatment fluid F-70 A A A A A A Example F-71 Treatment fluid F-71 A A A A A A Example F-72 Treatment fluid F-72 A A A A A A Example F-73 Treatment fluid F-73 A A A A A A Example F-74 Treatment fluid F-74 B A A A A A Example F-75 Treatment fluid F-75 B B B A A A Example F-76 Treatment fluid F-76 B B B A B A Example F-77 Treatment fluid F-77 B B B A A A Example F-78 Treatment fluid F-78 B B B A A A Example F-79 Treatment fluid F-79 C C B A A A Example F-80 Treatment fluid F-80 C C B A A A

[Table 34] Continued Table 12 Type of treatment liquid Evaluation results Resolution Exposure film loss Bridging defect Resistivity Dense pattern DOT pattern Sparse pattern Example F-81 Treatment fluid F-81 B B B A A A Example F-82 Treatment fluid F-82 B B B A A A Example F-83 Treatment fluid F-83 B B B A A A Example F-84 Treatment fluid F-84 B C C A A A Example F-85 Treatment fluid F-85 B B B A A A Example F-86 Treatment fluid F-86 B C B A A A Example F-87 Treatment fluid F-87 B C B A A A Example F-88 Treatment fluid F-88 B C C A A A Example F-89 Treatment fluid F-89 B B B A B A Example F-90 Treatment fluid F-90 B B B A B A Example F-91 Treatment fluid F-91 B C B A A A Example F-92 Treatment fluid F-92 B C B A A A Comparative example F-1 Treatment fluid RF-1 E E E E A A Comparative example F-2 Treatment fluid RF-2 D E D E A A Comparative example F-3 Treatment fluid RF-3 D E D E A A Comparative example F-4 Treatment fluid RF-4 E E D B A B Comparative example F-5 Treatment fluid RF-5 E E D B A B Comparative example F-6 Treatment fluid RF-6 D D D B A A Comparative example F-7 Treatment fluid RF-7 D E D B B A Comparative example F-8 Treatment fluid RF-8 D E D B A A Comparative example F-9 Treatment fluid RF-9 D E D B B A

It is confirmed from the results in Table 12 that according to the treatment liquid of the example (a treatment liquid containing a ketone-based solvent as solvent A-2 and an alcohol-based solvent as solvent B-1), it is possible to form a film in the exposed portion with suppressed pattern collapse A pattern in which impairment is suppressed, and bridging defects are suppressed. In addition, it was confirmed that the treatment liquid of the example has a low electrical resistivity and is excellent in safety. In addition, it is confirmed from the results in Table 12 that the second organic solvent contains selected from 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, and 3-ethyl-3 -When one or more of pentanol, 2-octanol and 2,6-dimethyl-4-heptanol is included, any one or more of 2,6-dimethyl-4-heptanol and 3-octanol is included , Or containing an acyclic alcohol solvent with a triple bond in the molecule (preferably selected from 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1- In the case of one or more of heptyn-3-ol and 7-octyn-1-ol), the suppression of pattern collapse and the suppression of bridging defects are more excellent. Among them, it was confirmed from the results in Table 12 that when 2-octanol is included, when any one or more of 2,6-dimethyl-4-heptanol and 3-octanol is included, or when a non-intramolecular triple bond is included Cyclic alcohol solvent (preferably selected from 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-heptyn-3-ol and 7-octyne In the case of -1-ol), regardless of the type of the first organic solvent and the mixing ratio of the first organic solvent and the second organic solvent, the suppression of pattern collapse and the suppression of bridging defects are still excellent. Furthermore, it is confirmed from the results in Table 12 that the second organic solvent contains 3,7-dimethyl-3-octanol, and the content of the first organic solvent relative to the sum of the content of the first organic solvent and the second organic solvent is At 40 to 80% by mass, it is possible to form a pattern in which pattern collapse is further suppressed, film loss in the exposed portion is further suppressed, and bridging defects are further suppressed. In addition, it was confirmed from the results in Table 12 that the second organic solvent contains one or more selected from 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol and 2-octanol, And when the content of the first organic solvent is 20 to 80% by mass relative to the total content of the first organic solvent and the second organic solvent, pattern collapse can be further suppressed, film loss in the exposed portion is further suppressed, and defects are bridged. Further suppressed patterns.

In addition, it is confirmed from the results in Table 12 that the second organic solvent is 2-ethyl-1-hexanol, and the content of the first organic solvent is less than 40% by mass relative to the total content of the first organic solvent and the second organic solvent. At this time, it is possible to form a pattern in which pattern collapse is further suppressed, film deterioration of the exposed portion is further suppressed, and bridge defects are further suppressed.

Also, from the results of Table 2, Table 4, Table 6, Table 8, Table 10, and Table 12, it is confirmed that solvent A is solvent A-1 selected from hydrocarbon solvents and ether solvents, and solvent B is solvent B-1 In the case of (alcohol solvent), it is possible to form a pattern in which pattern collapse is further suppressed.

[Pattern formation (EUV exposure, negative development) and evaluation 2] In the pattern formation of Example A-1, the pattern formation was performed in the same manner except that the butyl acetate as the developer was changed to the treatment liquid A-1 shown in Table 1.

[Pattern formation (EUV exposure, negative development) and evaluation 3] In the pattern formation of Example A-2, the pattern formation was performed in the same manner except that the butyl acetate as the developer was changed to the treatment liquid A-2 shown in Table 1.

[Pattern formation (EUV exposure, negative development) and evaluation 4] In the pattern formation of Example A-3, the pattern formation was performed in the same manner except that the butyl acetate as the developer was changed to the treatment liquid A-3 shown in Table 1.

[Pattern formation (EUV exposure, negative development) and evaluation 5] In the pattern formation of Example E-1, the pattern formation was performed in the same manner except that isobutyl isobutyrate of the treatment liquid E-1 was changed to isobutyl butyrate.

[Pattern formation (EUV exposure, negative development) and evaluation 6] In the treatment solution E-1 (Example E-1) shown in Table 9, except for changing the isobutyl isobutyrate as the first organic solvent to isobutyl butyrate or butyl isobutyrate, the same The treatment liquid E-1-1 and the treatment liquid E-1-2 were produced in the same manner as the treatment liquid E-1, and the result was the same as the treatment liquid E-1 (Example E-1) result.

[Pattern formation (EUV exposure, negative development) and evaluation 7] (Example A-1’) The resist composition 2 was prepared by the same method as the resist composition 1 except that the resin (A-2) shown below was used instead of the resin (A-1).

[Chemical formula 70]

The composition ratio (molar ratio) of each repeating unit in the resin (A-2) is 60/40 from left to right. The above-mentioned molar ratio ^{is calculated by 1} H-NMR measurement. In addition, the weight average molecular weight (Mw) of standard polystyrene converted by gel permeation chromatography (GPC) (solvent: THF) of resin (A-2) is 11,000, and the molecular weight dispersion (Mw/Mn) is 1.60.

Except that the resist composition 2 was used in place of the resist composition 1, the pattern was formed and evaluated in the same procedure as in Example A-1. As a result, the pattern collapse was evaluated as follows: dense pattern is C, DOT The pattern is C, the sparse pattern is C, the evaluation of the film loss in the exposed part is A, and the evaluation of the bridge defect is A. From the comparison between Example A-1 and Example A-1', it was confirmed that when the resin contains the repeating unit (hydroxystyrene-based repeating unit) represented by the above general formula (1), the effect of the present invention can be further exhibited.

no.

no

no.

Claims (20)

A treatment liquid used for at least one of developing and cleaning a resist film obtained from a sensitizing ray or a radiation-sensitive composition, and containing an organic solvent for resist film patterning, the The treatment liquid contains: a first organic solvent that satisfies the following condition A and a second organic solvent that satisfies the following condition B, condition A: SP value is 18.7MPa ^1/2 or less and ΔP expressed by the following formula (1) is Hydrocarbon solvents, ether solvents or ester solvents of 15.0 or less, or ketone solvents with an SP value of 18.7MPa ^1/2 or less and ΔP expressed by the following formula (1) of 20.0 or less, condition B: SP value Alcohol solvents with 19.0 MPa ^1/2 or more and ClogP of 1.6 or more, or those with SP value of 19.0 MPa ^{1 1/2} or more and ΔH represented by the following formula (2) of 20.0 or more, and containing two or more carbonyl groups Ester solvent, formula (1): ΔP =δp/(δd+δp+δh)×100 Formula (2): ΔH =δh/(δd+δp+δh)×100 In formulas (1) and (2) , Δd represents the dispersion term of the Hansen solubility parameter, δp represents the polarity term of the Hansen solubility parameter, and δh represents the hydrogen bond term of the Hansen solubility parameter. The treatment liquid described in claim 1, wherein In the aforementioned condition B, the alcohol-based solvent includes an acyclic alcohol-based solvent, and the ester-based solvent includes an acyclic ester-based solvent. The treatment liquid described in claim 2, wherein The aforementioned acyclic ester-based solvent includes one or more selected from ethyl acetate, dimethyl malonate, pyruvate, and diethyl oxalate. The treatment liquid described in claim 2, wherein The aforementioned acyclic alcohol-based solvents include 3,7-dimethyl-3-octanol, 3,5,5-trimethyl-1-hexanol, 3-ethyl-3-pentanol, 2 One or more of 6-dimethyl-4-heptanol, 2-ethyl-1-hexanol, 1-heptanol, 2-octanol, 1-octanol, and 1-hexanol. The treatment liquid described in claim 2, wherein The aforementioned acyclic alcohol-based solvent contains any one or more of 2,6-dimethyl-4-heptanol and 3-octanol. The treatment liquid described in claim 2, wherein The aforementioned acyclic alcohol-based solvent has a triple bond in the molecule. The treatment liquid according to claim 6, wherein The aforementioned acyclic alcohol-based solvents include those selected from the group consisting of 1-octyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-heptyn-3-ol and 7-octyne One or more of -1-ols. The treatment liquid according to any one of claim 1 to claim 7, wherein In the first organic solvent, the hydrocarbon solvent includes a hydrocarbon solvent having 7 or more carbon atoms. The treatment liquid according to any one of claim 1 to claim 7, wherein In the aforementioned first organic solvent, the aforementioned hydrocarbon-based solvent contains at least one selected from ethylcyclohexane, symmetric trimethylbenzene, 1,5-cyclooctadiene, undecane, and decane. The treatment liquid according to any one of claim 1 to claim 7, wherein In the first organic solvent, the ether-based solvent includes at least one selected from the group consisting of pentyl ethers, butyl ethers, and diisopropyl ether. The treatment liquid according to any one of claim 1 to claim 7, wherein In the first organic solvent, the ether-based solvent includes at least one of diisoamyl ether and diisobutyl ether. The treatment liquid according to any one of claim 1 to claim 7, wherein In the aforementioned first organic solvent, the aforementioned ester-based solvent includes selected from the group consisting of isobutyl isobutyrate, butyl butyrate, ethyl 2-methyl-valerate, hexyl acetate, isobutyl butyrate, and butyl isobutyrate. At least one of esters. The treatment liquid according to any one of claim 1 to claim 7, wherein In the first organic solvent, the ketone solvent includes at least one of diisobutyl ketone and 3-octanone. The treatment liquid according to any one of claim 1 to claim 7, wherein The aforementioned treatment liquid is a rinsing liquid. The treatment liquid according to any one of claim 1 to claim 7, wherein the aforementioned sensitizing radiation or radiation-sensitive composition contains a resin having a repeating unit represented by the following general formula (1),

In the formula, A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group, R represents a substituent, a represents an integer from 1 to 3, b represents an integer from 0 to (5-a), and there are plural In the case of R, they may be the same as or different from each other, and plural R may be bonded to each other to form a ring. A pattern forming method, which includes: In the resist film forming step, the resist film is formed by using sensitizing rays or a radiation-sensitive composition; Exposure step, exposing the aforementioned resist film; and In the processing step, the exposed resist film is processed by the processing liquid described in any one of claim 1 to 14. A pattern forming method, which includes: In the resist film forming step, the resist film is formed by using sensitizing rays or a radiation-sensitive composition; Exposure step, exposing the aforementioned resist film; and The processing step is to process the exposed resist film, The aforementioned processing steps include: In the developing step, developing with a developing solution; and The rinsing step, washing with rinsing liquid, The aforementioned rinsing liquid is the treatment liquid described in any one of claim 1 to 14. The pattern forming method according to claim 17, wherein The aforementioned developer contains an ester solvent. The pattern forming method according to claim 18, wherein The aforementioned ester-based solvent includes selected from the group consisting of butyl acetate, pentyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, One or more of heptyl propionate, butyl butyrate, butyl isobutyrate, and isobutyl isobutyrate. The pattern forming method according to any one of claim 16 to claim 19, wherein the aforementioned sensitizing ray or radiation-sensitive composition includes a resin having a repeating unit represented by the following general formula (1),

In the formula, A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group, R represents a substituent, a represents an integer from 1 to 3, b represents an integer from 0 to (5-a), and there are plural In the case of R, they may be the same as or different from each other, and plural R may be bonded to each other to form a ring.