JPWO2019044668A1 - Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive resin film, pattern forming method, and electronic device manufacturing method - Google Patents

Abstract

(A) contains a repeating unit represented by the specific general formula, a repeating unit represented by the specific general formula, and a repeating unit represented by the specific general formula, and is represented by the general formula (1). A resin having a repeating unit content of 25 to 50 mol% with respect to all repeating units in the resin (A), (B) a compound which generates an acid upon irradiation with actinic rays or radiation, and (C). Provided are an actinic ray-sensitive or radiation-sensitive resin composition containing a solvent, an actinic ray-sensitive or radiation-sensitive resin film using the same, a pattern forming method, and an electronic device manufacturing method.

Description

  The present invention provides an actinic ray-sensitive or radiation-sensitive resin composition, which is suitably used in a semiconductor manufacturing process such as IC, a circuit board such as a liquid crystal and a thermal head, and other photolithography lithography process. The present invention relates to an actinic ray- or radiation-sensitive resin film, a pattern forming method, and an electronic device manufacturing method. In particular, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive resin film, a pattern forming method, and an electronic device manufacturing method, which are preferably used for exposure in a KrF exposure apparatus. Regarding

Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method of the resist in order to compensate the sensitivity decrease due to light absorption. A positive chemical amplification image forming method will be described as an example. When exposed to an excimer laser, an electron beam, or extreme ultraviolet light, the acid generator in the exposed portion decomposes to generate an acid, and the bake after exposure (PEB : Post Exposure Bake) is used to convert the alkali-insoluble group into an alkali-soluble group by using the generated acid as a reaction catalyst, and the exposed portion is removed by an alkali developing solution.
Due to the demands of fine processing technology, not only the current mainstream positive type, but also the development of fine pattern formation by negative images is being performed.

  For example, in Patent Document 1, a step of forming a resist film using an actinic ray-sensitive or radiation-sensitive composition containing a resin having a specific structure, a step of exposing the resist film, and an organic material containing an antioxidant A pattern forming method including a step of developing with a processing solution is disclosed. Here, in the embodiment of Patent Document 1, a 4-inch silicon wafer, a 6-inch silicon wafer, and an 8-inch silicon are used as the silicon wafer on which the resist film is formed.

International publication 2016/104565

Incidentally, the resist composition is applied to substrates of various sizes depending on the application, and there is also a form in which the resist composition is applied onto a substrate having a wide diameter (for example, 12 inches or more). However, in particular, it is difficult to obtain high film thickness uniformity for a film provided on such a wide-diameter substrate, and further improvement in film thickness uniformity has been demanded.
In view of the above problems, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin excellent in film thickness uniformity even when provided on the above-mentioned wide-diameter substrate (for example, a diameter of 12 inches or more). It is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a film, an actinic ray-sensitive or radiation-sensitive resin film using the same, a pattern forming method, and an electronic device manufacturing method. . In particular, an actinic ray-sensitive or radiation-sensitive resin composition suitable for KrF exposure and organic solvent development, an actinic ray-sensitive or radiation-sensitive resin film using the same, a pattern forming method, and a method for manufacturing an electronic device To provide.

  The present invention has the following constitutions, whereby the above object of the present invention is achieved.

[1]
(A) contains a repeating unit represented by the following general formula (1), a repeating unit represented by the following general formula (2), and a repeating unit represented by the following general formula (3),
A resin in which the content of the repeating unit represented by the general formula (1) is in the range of 25 to 50 mol% with respect to all the repeating units in the resin (A),
An actinic ray-sensitive or radiation-sensitive resin composition containing (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and (C) a solvent.

In the general formula (2), R ₁ represents a hydrogen atom or a methyl group. R ₂ and R ₃ each independently represent a hydrocarbon group having 1 to 4 carbon atoms. However, R ₂ and R ₃ may be bonded to each other to form a ring having 3 to 8 carbon atoms. R ₄ represents a polycyclic hydrocarbon group having 6 to 20 carbon atoms.
In the general formula (3), R ₅ is a hydrogen atom or a methyl group. R _{6, R 7} and _{R 8} each independently represents a linear or branched hydrocarbon group having 1 to 4 carbon atoms.

[2]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein in the repeating unit represented by the general formula (2), R ₄ is an adamantyl group, a norbornyl group, or a bicyclooctyl group.
[3]
The actinic ray according to [1] or [2], wherein the content of the repeating unit represented by the general formula (2) is 25 to 50 mol% with respect to all the repeating units in the resin (A). Or radiation-sensitive resin composition.
[4]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], which is for KrF exposure.
[5]
Actinic ray obtained by applying the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4] onto a substrate by spin coating at a maximum rotation speed of 2500 rpm or less. Or radiation-sensitive resin film.

[6]
(A) A step of forming a film from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], (B) a step of exposing the film, and (C) A pattern forming method comprising the step of developing the exposed film with a developing solution containing an organic solvent to form a negative pattern.
[7]
The pattern forming method according to [6], wherein the developing solution is butyl acetate.
[8]
A method for manufacturing an electronic device, including the pattern forming method according to [6] or [7]

  According to the present invention, even when provided on a substrate having a wide diameter (for example, a diameter of 12 inches or more), it is possible to form an actinic ray-sensitive or radiation-sensitive resin film excellent in film thickness uniformity. And a radiation-sensitive resin composition, and an actinic ray-sensitive or radiation-sensitive resin film using the same, a pattern forming method, and an electronic device manufacturing method can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
In the notation of a group (atom group) in the present specification, notation that does not indicate substituted or unsubstituted encompasses not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The term “actinic ray” or “radiation” as used herein means, for example, a bright line spectrum of a mercury lamp, deep ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB) and the like. To do. In the present invention, light means actinic rays or radiation.
Unless otherwise specified, the term “exposure” used in the present specification refers to not only exposure using deep ultraviolet rays such as mercury lamps and excimer lasers, extreme ultraviolet rays, X-rays and EUV rays, but also electron beams, ion beams, etc. Drawing with particle beam is also included in exposure.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention comprises (A) a repeating unit represented by the following general formula (1), a repeating unit represented by the following general formula (2), and the following general formula ( Containing a repeating unit represented by 3),
The content of the repeating unit represented by the general formula (1) is in the range of 25 to 50 mol% with respect to all the repeating units in the resin (A) (hereinafter, also referred to simply as “resin (A)”). Say),
An actinic ray-sensitive or radiation-sensitive resin composition containing (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and (C) a solvent.

In the general formula (2), R ₁ represents a hydrogen atom or a methyl group. R ₂ and R ₃ each independently represent a hydrocarbon group having 1 to 4 carbon atoms. However, R ₂ and R ₃ may be bonded to each other to form a ring having 3 to 9 carbon atoms. R ₄ represents a polycyclic hydrocarbon group having 6 to 20 carbon atoms.
In the general formula (3), R ₅ is a hydrogen atom or a methyl group. R _{6, R 7} and _{R 8} each independently represents a linear or branched hydrocarbon group having 1 to 4 carbon atoms.

When such an actinic ray-sensitive or radiation-sensitive resin composition of the present invention is applied to a wide-diameter substrate, it is possible to form an actinic ray-sensitive or radiation-sensitive resin film having excellent film thickness uniformity. The reason for this is not clear, but it is estimated as follows.
In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the resin (A) is a repeating unit represented by the general formula (1), a repeating unit represented by the general formula (2), and It contains the repeating unit represented by the general formula (3), and the content of the repeating unit represented by the general formula (1) is 25 to 50 mol% with respect to all the repeating units in the resin (A). Has become. In particular, it is considered that the content of the repeating unit represented by the general formula (1) with respect to all the repeating units contributes to the improvement of the film thickness uniformity.
When the content of the repeating unit represented by the general formula (1) is 25 mol% or more based on all the repeating units in the resin (A), the interaction between the resins can be sufficiently obtained, An actinic ray-sensitive or radiation-sensitive resin obtained by suppressing the occurrence of unevenness on the film surface, which is likely to occur due to too weak interaction between resins during drying in forming an actinic ray-sensitive or radiation-sensitive resin film. It is estimated that the film thickness uniformity is excellent.
On the other hand, when the content of the repeating unit represented by the general formula (1) is 50 mol% or less with respect to all the repeating units in the resin (A), the interaction between the resins does not become too high. . Here, when the actinic ray-sensitive or radiation-sensitive resin composition is applied to a wafer having a large diameter such as a 12-inch wafer by the spin coating method, as compared with the case where a wafer having a small diameter is used. The coating film provided on the outer peripheral portion of the wafer is easily affected by the wind accompanying the rotation of the wafer. Specifically, the resulting actinic ray-sensitive or radiation-sensitive resin film, especially in the outer peripheral portion thereof, tends to suffer from the above-mentioned wind-induced unevenness, resulting in a decrease in film thickness uniformity. However, in the actinic ray-sensitive or radiation-sensitive resin film of the present invention, since the interaction between the resins does not become too high as described above, unevenness of the outer peripheral portion due to the wind is unlikely to occur, and It is presumed that the film thickness uniformity of the actinic ray-sensitive or radiation-sensitive resin film is excellent.
From the above, by setting the content of the repeating unit represented by the general formula (1) to 25 to 50 mol% with respect to all the repeating units in the resin (A), the resulting actinic ray-sensitive or light-sensitive It is presumed that the thickness of the radioactive resin film is excellent.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention will be described below.
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is a negative type developing agent (when exposed, its solubility in a developing solution decreases, the exposed portion remains as a pattern, and the unexposed portion is removed. It is preferably used for development. That is, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is an actinic ray-sensitive or radiation-sensitive resin composition for organic solvent development used for development using a developer containing an organic solvent. be able to. Here, the term “for organic solvent development” means an application provided for a step of developing using a developing solution containing at least an organic solvent.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is typically a resist composition, and preferably a negative resist composition (that is, a resist composition for organic solvent development). The composition according to the present invention is typically a chemically amplified resist composition.

[1] Resin (A)
The resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains the repeating unit represented by the general formula (1) and is represented by the general formula (1). The content of the repeating unit is 25 to 50 mol%, preferably 30 to 45 mol%, and more preferably 35 to 40 mol% based on all the repeating units in the resin (A).

  In the general formula (1), the hydroxyl group is preferably bonded to the benzene ring at the para position with respect to the main chain. Specifically, the general formula (1) preferably has a para-hydroxystyrene skeleton.

In the general formula (2), R ₁ represents a hydrogen atom or a methyl group.
R ₂ and R ₃ each independently represent a hydrocarbon group having 1 to 4 carbon atoms. As the hydrocarbon group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Alternatively, a tert-butyl group may be mentioned.

As the ring having 3 to 8 carbon atoms which R ₂ and R ₃ may be bonded to each other to form, a cycloalkyl group having 3 to 8 carbon atoms is preferable, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, Examples thereof include a cyclohexyl group and a cyclooctyl group.

R ₄ represents a polycyclic hydrocarbon group having 6 to 20 carbon atoms. As the polycyclic hydrocarbon group having 6 to 20 carbon atoms, a polycyclic cycloalkyl group having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, and a bicyclooctyl group. Group, α-pinel group, tricyclodecanyl group, tetracyclododecyl group, androstanyl group and the like. At least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
R ₄ is an adamantyl group, a norbornyl group, or a bicyclooctyl group (bicyclo [2.2.2] octyl group, bicyclo [3.3.0] octyl group, bicyclo [3.2.1] octyl group). preferable.

  Each of the above groups may have a substituent, and examples of the substituent include a hydroxyl group, a halogen atom (for example, a fluorine atom), an alkyl group (having 1 to 4 carbon atoms), a cycloalkyl group (having 3 carbon atoms). To 8), an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms), and the like, with 8 or less carbon atoms being preferable.

The content of the repeating unit represented by the general formula (2) is preferably 25 to 50 mol%, more preferably 30 to 47.5, based on all the repeating units in the resin (A). Mol%, and more preferably 35 to 45 mol%.
The content of the repeating unit represented by the general formula (2) is preferably 25 to 50 mol% with respect to all the repeating units in the resin (A), and is represented by the general formula (2). It is considered that the interaction between the repeating unit and the repeating unit represented by the general formula (1) can be weakened, and the film thickness uniformity of the actinic ray-sensitive or radiation-sensitive resin film is improved.

  The repeating unit represented by the above general formula (2) of the resin (A) may be one type, or two or more types may be used in combination.

Specific preferred examples of the repeating unit represented by the general formula (2) are shown below, but the invention is not limited thereto.
In the specific examples, Rx represents a hydrogen atom or a methyl group. Rxa and Rxb each independently represent a hydrocarbon group having 1 to 4 carbon atoms. Z represents a substituent, and when a plurality of Zs are present, the plurality of Zs may be the same as or different from each other. p represents 0 or a positive integer. Specific examples and preferable examples of Z are the same as the specific examples and preferable examples of the substituent that each group such as R _{1 to} R ₄ may have.

In the general formula (3), R ₅ is a hydrogen atom or a methyl group.
R _{6, R 7} and _{R 8} each independently represents a linear or branched hydrocarbon group having 1 to 4 carbon atoms. As the linear or branched hydrocarbon group having 1 to 4 carbon atoms, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and specifically, methyl group, ethyl group, n-propyl group , Isopropyl group, n-butyl group, isobutyl group, or tert-butyl group.

  Each of the above groups may have a substituent, and examples of the substituent include a hydroxyl group, a halogen atom (for example, a fluorine atom), an alkyl group (having 1 to 4 carbon atoms), a cycloalkyl group (having 3 carbon atoms). To 8), an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms), and the like, with 8 or less carbon atoms being preferable.

  The content of the repeating unit represented by the general formula (3) is preferably 10 to 35 mol%, more preferably 15 to 30 mol%, based on all the repeating units in the resin (A). , And more preferably 20 to 25 mol%.

  The repeating unit represented by the above general formula (3) of the resin (A) may be one type, or two or more types may be used in combination.

  Preferred specific examples of the repeating unit represented by the above general formula (3) are shown below, but the present invention is not limited thereto.

  The resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is a repeating unit represented by the general formula (1), a repeating unit represented by the general formula (2), And when containing only the repeating unit represented by the general formula (3), the content (mol%) of the repeating unit represented by the general formula (1) with respect to all the repeating units in the resin (A) and Content (mol%) of the repeating unit represented by the general formula (2) with respect to all repeating units in the resin (A) and all the repeating units represented by the general formula (3) in the resin (A). The total of the content (mol%) with respect to the unit is 100.

[Other repeating units]
The resin (A) may further have a repeating unit having a lactone structure. As the repeating unit having a lactone structure, a repeating unit represented by the following general formula (AII) is more preferable.

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group (preferably having 1 to 4 carbon atoms).
Preferred substituents which 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, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and a hydrogen atom or a methyl group is particularly preferable.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether bond, an ester bond, a carbonyl group, or a divalent linking group combining these. Ab is preferably a single _bond, -Ab 1 -CO ₂ - is a divalent linking group represented by.
Ab ₁ is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
V represents a group having a lactone structure.

  As the group having a lactone structure, any group having a lactone structure can be used, but it is preferably a 5- to 7-membered ring lactone structure, and a 5- to 7-membered ring lactone structure having a bicyclo structure or a spiro structure. It is preferable that the other ring structure is condensed in the formed form. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). Further, the lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-8), (LC1-13) and (LC1-14).

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a monovalent cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkoxycarbonyl group having 2 to 8 carbon atoms. , A carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, the plural substituents (Rb ₂ ) may be the same or different, and the plural substituents (Rb ₂ ) may be bonded to each other to form a ring. .

  The repeating unit having a lactone group usually has optical isomers, but any optical isomer may be used. Further, one optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one type of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.

The resin (A) may or may not contain a repeating unit having a lactone structure, but when it contains a repeating unit having a lactone structure, the content of the repeating unit in the resin (A) is It is preferably in the range of 0.5 to 50 mol%, more preferably in the range of 1 to 40 mol%, and still more preferably in the range of 3 to 30 mol%, based on the repeating units. The repeating unit may be of one type or a combination of two or more types. By using the specific lactone structure, the resolution of the pattern is improved and the rectangular profile is improved.
Specific examples of the repeating unit having a lactone structure in the resin (A) are shown below, but the invention is not limited thereto. In the formula, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

The resin (A) may have a repeating unit having an acid group. Examples of the acid group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol in which the α-position is substituted with an electron-withdrawing group (eg, hexafluoroisopropanol group), which has a carboxyl group. It is more preferable to have a repeating unit. By containing the repeating unit having an acid group, the resolution in contact hole applications is increased. As the repeating unit having an acid group, a repeating unit in which an acid group is directly bonded to the resin main chain such as a repeating unit of acrylic acid or methacrylic acid, or an acid group in the resin main chain through a linking group is used. Repeating units are bonded, further introduced into the end of the polymer chain by using a polymerization initiator or a chain transfer agent having an acid group at the time of polymerization, both are preferable, the linking group is a monocyclic or polycyclic hydrocarbon structure. May have. Particularly preferred are repeating units of acrylic acid and methacrylic acid.
Specific examples of the repeating unit having an acid group are shown below, but the present invention is not limited thereto.
In the specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The resin (A) may or may not contain a repeating unit having an acid group, but when the resin (A) contains a repeating unit having an acid group, the content of the repeating unit is It is preferably 1 to 25 mol%, more preferably 1 to 20 mol%, and further preferably 3 to 15 mol% with respect to all the repeating units in ().

The resin (A) is a repeating unit other than the above-mentioned repeating unit and may further have a repeating unit having a hydroxyl group or a cyano group. This makes it possible to improve substrate adhesion and developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group. In the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, the alicyclic hydrocarbon structure is preferably an adamantyl group, a diamantyl group or a norbornane group, more preferably an adamantyl group. Further, it is preferably substituted with a hydroxyl group, and more preferably contains a repeating unit having an adamantyl group substituted with at least one hydroxyl group.
In particular, the resin (A) most preferably contains a repeating unit having a hydroxyadamantyl group or a dihydroxyadamantyl group from the viewpoint of suppressing the diffusion of the generated acid. As the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, a partial structure represented by the following general formulas (VIIa) to (VIId) is preferable, and a partial structure represented by the following general formula (VIIa) is more preferable. .

In the general formulas (VIIa) to (VIIc),
R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are hydroxyl groups and the rest are hydrogen atoms. In formula (VIIa), it is more preferable that _two members out of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom.

  Examples of the repeating units having the partial structures represented by the general formulas (VIIa) to (VIId) include the repeating units represented by the following general formulas (AIIa) to (AIId).

In the general formulas (AIIa) to (AIId),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
R ₂ c to R ₄ c are in the general formula (VIIa) ~ _(VIIc), same meanings as R 2 c~R ₄ c.
Specific examples of the repeating unit having a hydroxyl group or a cyano group are shown below, but the present invention is not limited thereto.

  The resin (A) may or may not contain a repeating unit having a hydroxyl group or a cyano group, but when the resin (A) contains a repeating unit having a hydroxyl group or a cyano group, the above repeating unit is used. The content of the unit is preferably 1 to 40 mol%, more preferably 3 to 35 mol%, and further preferably 5 to 30 mol% with respect to all the repeating units in the resin (A).

  The resin (A) in the present invention may further have a repeating unit having an alicyclic hydrocarbon structure having no polar group (for example, the above-mentioned acid group, hydroxyl group or cyano group) and not exhibiting acid decomposability. This makes it possible to appropriately adjust the solubility of the resin during development using a developing solution containing an organic solvent. Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

In formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.
Ra represents a hydrogen atom, an alkyl group or _-CH 2 -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

The cyclic structure contained in R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group, and cycloalkenyl group having 3 to 12 carbon atoms such as cyclohexenyl group. Groups. The preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, more preferably a cyclopentyl group or a cyclohexyl group.

The polycyclic hydrocarbon group includes a ring-assembled hydrocarbon group and a crosslinked cyclic hydrocarbon group, and examples of the ring-assembled hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, a bicyclic type such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon ring, tricyclic hydrocarbon ring such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [ 4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, perhydro-1,4-methano-5,8-methanonaphthalene ring, and other tetracyclic hydrocarbon rings. Further, the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydro. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.

Examples of preferable crosslinked cyclic hydrocarbon rings include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable crosslinked cyclic hydrocarbon rings include a norbornyl group and an adamantyl group.

  These alicyclic hydrocarbon groups may have a substituent, and preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. To be Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The above alkyl group may further have a substituent, and as the substituent which may further have a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, an amino group substituted with a hydrogen atom. A group can be mentioned.

  Examples of the substituent of the hydrogen atom include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group and an aralkyloxycarbonyl group. The preferred alkyl group is an alkyl group having 1 to 4 carbon atoms, the preferred substituted methyl group is methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl group, and the preferred substituted ethyl group is , 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferred acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl groups, and the like, aliphatic acyl groups having 1 to 6 carbon atoms, and alkoxycarbonyl. Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

The resin (A) has an alicyclic hydrocarbon structure having no polar group and may or may not contain a repeating unit which does not exhibit acid decomposability, but the resin (A) does not have a polar group. When it contains a repeating unit which has a cyclic hydrocarbon structure and does not exhibit acid-decomposability, the content of the repeating unit is preferably 1 to 40 mol% based on all the repeating units in the resin (A), It is preferably 1 to 20 mol%.
Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The resin (A) used in the composition of the present invention is, in addition to the above repeating structural unit, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and actinic ray-sensitive or radiation-sensitive resin composition. It is possible to have various repeating structural units for the purpose of adjusting the resolving power, heat resistance, sensitivity, etc.

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.
Thereby, the performance required for the resin used in the composition of the present invention, in particular,
(1) Solubility in coating solvent,
(2) Film-forming property (glass transition point),
(3) Alkali developability,
(4) Membrane slippage (hydrophobicity / alkali-soluble group selection),
(5) Adhesion of the unexposed area to the substrate,
(6) It is possible to finely adjust the dry etching resistance and the like.

Examples of such a monomer include addition-polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters, and the like. The compound etc. which have one unsaturated bond can be mentioned.
In addition, any addition-polymerizable unsaturated compound that is copolymerizable with the monomers corresponding to the above various repeating structural units may be copolymerized.

In the resin (A) used in the composition of the present invention, the content molar ratio of each repeating structural unit is such that the dry etching resistance of the actinic ray-sensitive or radiation-sensitive resin composition, standard developer suitability, substrate adhesion, resist The profile is appropriately set to adjust the resolution, heat resistance, sensitivity, etc., which are generally required performances of the resist.
The form of the resin (A) in the present invention may be any of random type, block type, comb type and star type. The resin (A) can be synthesized, for example, by radical, cation, or anionic polymerization of an unsaturated monomer corresponding to each structure. It is also possible to obtain the target resin by polymerizing after using an unsaturated monomer corresponding to the precursor of each structure.

  The resin (A) in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a batch polymerization method in which a monomer species and an initiator are dissolved in a solvent and polymerized by heating, and a solution of the monomer species and the initiator is dropped into a heating solvent over 1 to 10 hours. A dropping polymerization method and the like may be mentioned, and the dropping polymerization method is preferable. Examples of the reaction solvent include tetrahydrofuran, 1,4-dioxane, ethers such as diisopropyl ether and methyl ethyl ketone, ketones such as methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Further, a solvent which dissolves the composition of the present invention, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone described later, can be mentioned. More preferably, polymerization is performed using the same solvent as that used for the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. As a result, generation of particles during storage can be suppressed.

  The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon. As the polymerization initiator, a commercially available radical initiator (azo type initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo type initiator is preferable, and an azo type initiator having an ester group, a cyano group or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, the reaction mixture is put into a solvent to recover the desired polymer by a method such as powder or solid recovery. The reaction concentration is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is generally 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60 to 100 ° C.

  After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification is carried out by washing with water or combining appropriate solvents to remove residual monomer and oligomer components, liquid-liquid extraction method, ultrafiltration method to extract and remove only those having a specific molecular weight or less, and a purification method in a solution state. , Solid state purification such as reprecipitation method that removes residual monomers by coagulating the resin in the poor solvent by dropping the resin solution into the poor solvent or washing the filtered resin slurry with the poor solvent A usual method such as a method can be applied. For example, a solvent in which the resin is hardly soluble or insoluble (a poor solvent) is brought into contact with the reaction solution in a volume amount of 10 times or less, preferably 10 to 5 times, to precipitate the resin as a solid.

  The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of the polymer. It can be appropriately selected from compounds, ethers, ketones, esters, carbonates, alcohols, carboxylic acids, water, mixed solvents containing these solvents, and the like.

The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, etc., but is generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass, relative to 100 parts by mass of the polymer solution. More preferably, it is 300 to 1000 parts by mass.
The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C, preferably around room temperature (for example, about 20 to 35 ° C). The precipitation or reprecipitation operation can be performed by a known method such as a batch system or a continuous system using a commonly used mixing container such as a stirring tank.
The precipitated or reprecipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, dried and then used. The filtration is carried out using a solvent resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).
Note that the resin may be once precipitated, separated, and then dissolved in a solvent again, and brought into contact with a solvent in which the resin is sparingly soluble or insoluble. That is, after the completion of the radical polymerization reaction, a solvent in which the polymer is sparingly soluble or insoluble is brought into contact with the resin to precipitate the resin (step a), the resin is separated from the solution (step b), and the resin solution A is dissolved again. Is prepared (step c), and then a solvent in which the resin is sparingly soluble or insoluble is brought into contact with the resin solution A in a volume amount of less than 10 times that of the resin solution A (preferably 5 times or less). Thus, a method including depositing a resin solid (step d) and separating the deposited resin (step e) may be used.

In order to prevent the resin from aggregating after the composition is prepared, for example, as described in JP 2009-037108 A, the synthesized resin is dissolved in a solvent to form a solution, and the solution is You may add the process of heating at about 30 to 90 degreeC for about 30 minutes to 4 hours.
The weight average molecular weight of the resin (A) used in the composition of the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and more preferably 2,000 to 100,000 in terms of polystyrene by GPC method. It is more preferably 3,000 to 70,000, and particularly preferably 5,000 to 50,000. By setting the weight average molecular weight to 1,000 to 200,000, heat resistance and dry etching resistance can be prevented from being deteriorated, and developability is deteriorated or viscosity is increased to deteriorate film formability. Can be prevented.

The dispersity (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.2 to 2.4, and particularly preferably 1.4 to 2.2. Those in the range of are used. When the molecular weight distribution satisfies the above range, the resolution and the resist shape are excellent, the side wall of the resist pattern is smooth, and the roughness is excellent.
In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the content of the resin (A) in the entire composition is preferably 30 to 99% by mass, more preferably 60 to 95% by mass, based on the total solid content. Is.
In the present invention, the resin (A) may be used alone or in combination of two or more.

[3] Compound (B) which generates an acid upon irradiation with actinic rays or radiation
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains (B) a compound that generates an acid upon irradiation with actinic ray or radiation (hereinafter, also referred to as “acid generator (B)”).
The acid generator (B) is not particularly limited, but is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation.
The compound (B) that generates an acid upon irradiation with actinic rays or radiation may be in the form of a low molecular weight compound, or may be in the form of being incorporated in a part of the polymer. Further, the form of the low molecular weight compound and the form of being incorporated in a part of the polymer may be used in combination.
When the compound (B) which generates an acid upon irradiation with actinic rays or radiation is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and 1000 or less. Is more preferable.
When the compound (B) that generates an acid upon irradiation with actinic rays or radiation is in the form of being incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above. ) May be incorporated in a resin different from the above.

  Examples thereof include a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imidosulfonate, an oxime sulfonate, a diazodisulfone, a disulfone and an o-nitrobenzyl sulfonate, and the acid generator (B) contains a sulfonium salt or an iodonium salt. It is preferable.

  Further, a group in which an acid-generating group or a compound is introduced into the main chain or side chain of a polymer by irradiation with these actinic rays or radiation, for example, US Pat. No. 3,849,137, German Patent 3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, The compounds described in JP-A-62-153853, JP-A-63-146029 and the like can be used.

  Further, compounds capable of generating an acid by light described in US Pat. No. 3,779,778 and European Patent 126,712 can also be used.

  Compounds represented by the following general formulas (ZI), (ZII), and (ZIII) are preferable as the acid generator (B), which is a compound that decomposes upon irradiation with actinic rays or radiation to generate an acid. Can be mentioned.

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
Z ⁻ represents a non-nucleophilic anion, and preferably, a sulfonic acid anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^{− and the} like can be mentioned. Is an organic anion containing a carbon atom. Examples of preferable organic anions include organic anions represented by the following formulas AN1 to AN3.

In formulas AN1 to AN3, Rc _{1 to} Rc ₃ each independently represents an organic group. Examples of the organic group in Rc _{1 to} Rc ₃ include those having 1 to 30 carbon atoms, preferably an optionally substituted alkyl group, a monocyclic or polycyclic cycloalkyl group, a hetero atom-containing cyclic group, and an aryl group. , Or a plurality of them are linked by a linking group such as a single bond, —O—, —CO ₂ —, —S—, —SO ₃ —, —SO ₂ —, —SO ₂ N (Rd ₁ ) —. A group can be mentioned. Further, it may form a ring structure with other bonded alkyl group or aryl group.
Rd ₁ represents a hydrogen atom or an alkyl group, and may form a ring structure with a bonded alkyl group or aryl group.
The organic group of Rc _{1 to} Rc ₃ may be an alkyl group whose 1-position is substituted with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved.

The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Two of R _{201 to} R ₂₀₃ may be bonded to each other to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group.
Examples of the group formed by combining two members out of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).
Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the corresponding groups in the compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described later. be able to.

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of _R 201 _{to R 203} of a compound represented by (ZI) is, at least one bond with structure of _R 201 _{to R 203} of another compound represented by formula (ZI) The compound may have.

  As more preferable component (Z1), the compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below can be mentioned.

The compound (ZI-1) is an arylsulfonium compound in which at least one of R _{201 to} R _{203 in} formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.
Arylsulfonium _compound, all of R 201 _{to R 203} may be an aryl group _{or a} part of R 201 _{to R 203} may be an aryl group with the remaining being an alkyl group.
Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, and an aryldialkylsulfonium compound.
The aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group, a naphthyl group and a fluorene group, and a heteroaryl group such as an indole residue and a pyrrole residue, more preferably a phenyl group and an indole residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group which the arylsulfonium compound optionally has is preferably a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group and sec. -Butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group and the like can be mentioned.
The aryl group and alkyl group as R _{201 to} R ₂₀₃ include an alkyl group (for example, 1 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, It may have a hydroxyl group or a phenylthio group as a substituent. Preferred substituents are linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, and most preferably alkyl groups having 1 to 4 carbon atoms, It is an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted on any one of the three R _{201 to} R ₂₀₃ , or may be substituted on all three. Further, when R _{201 to} R ₂₀₃ are aryl groups, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (ZI-2) will be described.
The compound (ZI-2) is a compound when R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an aromatic ring-free organic group. Here, the aromatic ring also includes an aromatic ring containing a hetero atom.
The aromatic ring-free organic group as R _{201 to} R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylmethyl group, an allyl group or a vinyl group, and more preferably a direct group. It is a chain or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkoxycarbonylmethyl group, and most preferably a linear or branched 2-oxoalkyl group.
The alkyl group and cycloalkyl group as R _{201 to} R ₂₀₃ are preferably linear or branched alkyl groups having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), Examples thereof include a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).
The 2-oxoalkyl group as R _{201 to} R ₂₀₃ may be linear or branched and is preferably a group having> C═O at the 2-position of the above alkyl group.
The 2-oxocycloalkyl group as R _{201 to} R ₂₀₃ is preferably a group having> C═O at the 2-position of the above cycloalkyl group.
The alkoxy group in the alkoxycarbonylmethyl group as R _{201 to} R ₂₀₃ is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
Two of R _{201 to} R ₂₀₃ may be bonded to each other to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group. Examples of the group formed by combining two members out of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).

Next, the compound (ZI-3) will be described.
The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

In the general formula (ZI-3),
R _{1c to} R _5c are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group. Represents a nitro group, an alkylthio group or an arylthio group.
R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

Any two or more of R _{1c to} R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to each other to form a ring structure. Well, this ring structure may contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, or a polycyclic condensed ring formed by combining two or more of these rings. Examples of the ring structure include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

Examples of the group formed by combining any two or more _members out of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
The group formed by combining R _5c and R _6c or R _5c and R _x is preferably a single bond or an alkylene group, and the alkylene group includes a methylene group, an ethylene group and the like. .
Zc ^- represents a non-nucleophilic anion, preferably Z ^- represents, in particular, as described above.

Specific examples of the alkoxy group in the alkoxycarbonyl group as R _{1c to} R _{5c are the same} as the specific examples of the alkoxy group as R _{201 to} R ₂₀₃ .
Specific examples of the alkyl group in the alkylcarbonyloxy group and the alkylthio group as R _{1c to} R _{5c are the same} as the specific examples of the alkyl group as R _{201 to} R ₂₀₃ .
Specific examples of the cycloalkyl group in the cycloalkylcarbonyloxy group as R _{1c to} R _{5c are the same} as the specific examples of the cycloalkyl group as R _{201 to} R ₂₀₃ above.
Specific examples of the aryl group in the aryloxy group and the arylthio group as R _{1c to} R _{5c are the same} as the specific examples of the aryl group as R _{201 to} R ₂₀₃ .

  Examples of the cation in the compound (ZI-2) or (ZI-3) in the present invention include the cations described in paragraph [0036] and subsequent paragraphs of US Patent Application Publication No. 2012/0076996.

Next, the compound (ZI-4) will be described.
The compound (ZI-4) is represented by the following general formula (ZI-4).

In the general formula (ZI-4),
R ₁₃ represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group. These groups may have a substituent.
When a plurality of R _14's are present, each independently has a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. Represents These groups may have a substituent.
Each R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. Two R _15's may combine with each other to form a ring. When two R _{15 s} are bonded to each other to form a ring, the ring skeleton may contain a hetero atom such as an oxygen atom or a nitrogen atom. In one aspect, it is preferable that two R _15's are alkylene groups and are bonded to each other to form a ring structure.
l represents an integer of 0 to 2.
r represents an integer of 0 to 8.
Zc ^- represents a non-nucleophilic anion, preferably Z ^- represents, in particular, as described above.

In the general formula (ZI-4), the alkyl group for R ₁₃ , R ₁₄ and R ₁₅ is linear or branched and is preferably a group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group or n. -Butyl group, t-butyl group and the like are preferable.
Examples of the cation of the compound represented by the general formula (ZI-4) in the present invention include paragraphs [0121], [0123], [0124] of JP2010-256842A, and JP2011-76056A. The cations described in paragraphs [0127], [0129], [0130], etc. can be mentioned.

Next, general formulas (ZII) and (ZIII) will be described.
In formula _{(ZII), (ZIII),} R 204 ~R 207 each independently an optionally substituted aryl group, which may have a substituent alkyl group, or have a substituent Represents an optionally substituted cycloalkyl group.
Specific examples and preferable examples of the aryl group of R _{204 to} R ₂₀₇ are the same as those described as the aryl group of R _{201 to} R ₂₀₃ in the compound (ZI-1).
Specific examples of the alkyl group and cycloalkyl group of R _{204 to} R ₂₀₇ , suitable examples thereof include those described as the linear, branched or cyclic alkyl group as R _{201 to} R ₂₀₃ in the compound (ZI-2). It is the same.
Z ⁻ has the same meaning as Z ^{− in} formula (ZI).

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation as the acid generator (B), preferred compounds further include compounds represented by the following general formulas (ZIV), (ZV) and (ZVI). Can be mentioned.

In the general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted aryl group.
R ₂₀₈ independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group in the general formulas (ZV) and (ZVI). From the viewpoint of increasing the strength of the generated acid, R ₂₀₈ is preferably substituted with a fluorine atom.
_R209 and _R210 each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, an alkylthio group or an electron-withdrawing group.
In addition, R ₂₀₉ and R ₂₁₀ may combine to form a ring structure. These ring structures may contain an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group, an arylene group, or the like.
R ₂₀₉ is preferably a substituted or unsubstituted aryl group. R ₂₁₀ is preferably an electron-withdrawing group, more preferably a cyano group or a fluoroalkyl group.
A represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group.

Specific examples of the aryl group of Ar ₃ , Ar ₄ , R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as the specific examples of the aryl group of R _{201 to} R ₂₀₃ in the general formula (ZI-1). be able to.
Specific examples of the alkyl group and the cycloalkyl group of R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as the specific examples of the alkyl group and the cycloalkyl group as R _{201 to} R ₂₀₃ in the general formula (ZI-2), respectively. You can list the following.
Examples of the alkyl moiety of the alkylthio group for R ₂₀₉ and R ₂₁₀ include the same as the specific examples of the alkyl group for R _{201 to} R ₂₀₃ in the general formula (ZI-2).
The alkylene group of A is an alkylene group having 1 to 12 carbon atoms (for example, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group), and the cycloalkylene group of A is a carbon number. A 3-12 monocyclic or polycyclic cycloalkylene group (for example, a cyclohexylene group, a norbornylene group, an adamantylene group, etc.) can be used as the alkenylene group for A as an alkenylene group having 2 to 12 carbon atoms (for example, an ethenylene group). , A propenylene group, a butenylene group, etc.), and the arylene group of A includes an arylene group having 6 to 10 carbon atoms (eg, a phenylene group, a tolylene group, a naphthylene group).

A compound having a plurality of structures represented by formula (ZVI) is also preferable in the present invention. For example, either R ₂₀₉ or R ₂₁₀ of the compound represented by the general formula (ZVI) has a structure in which it is bonded to either R ₂₀₉ or R ₂₁₀ of the other compound represented by the general formula (ZVI). It may be a compound.

Among the compounds that decompose as an acid generator (B) by irradiation with actinic rays or radiation to generate an acid, more preferably, the compound has good solubility in a developing solution containing an organic solvent in an unexposed area and has a development defect. From the viewpoint that is unlikely to occur, it is preferable that the compounds are represented by the above general formulas (ZIII) to (ZVI), that is, so-called nonionic compounds. Among them, the compound represented by the general formula (ZV) or (ZVI) is more preferable.
From the viewpoint of improving the acid generation efficiency and acid strength, the acid generator (B) preferably has a structure for generating an acid containing a fluorine atom.
Specific examples of the acid generator (B) are shown below, but the acid generator (B) is not limited thereto.

The acid generator (B) may be used alone or in combination of two or more. When using two or more kinds in combination, it is preferable to combine two or more kinds of organic acid-generating compounds except for the total number of atoms excluding hydrogen atoms.
For example, from the viewpoint of improving the acid generation efficiency and the acid strength, a mode in which a compound having a structure that generates an acid containing a fluorine atom and a compound not having such a structure are used in combination can be mentioned.
The content of the acid generator (B) in the composition is preferably 0.1 to 20% by mass, more preferably 0.5, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. -15% by mass, more preferably 1-10% by mass.

[4] Solvent (C)
Examples of the solvent that can be used when preparing the actinic ray-sensitive or radiation-sensitive resin composition in the present invention include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactate alkyl ester, and alkoxypropion. Examples of the organic solvent include acid alkyls, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds that may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates. be able to.
Specific examples of these solvents include those described in US Patent Application Publication No. 2008/0187860 [0441] to [0455].

In the present invention, a mixed solvent obtained by mixing a solvent containing a hydroxyl group in the structure with a solvent not containing a hydroxyl group may be used as the organic solvent.
The above-exemplified compounds can be appropriately selected as the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether ( PGME, also known as 1-methoxy-2-propanol) and ethyl lactate are more preferred. As the solvent containing no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether. Acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethylethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate are particularly preferable, and propylene glycol monomethyl ether acetate, ethylethoxypropionate, 2 -Heptanone is most preferred.
The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group is particularly preferable from the viewpoint of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

[5] Basic compound (E)
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may contain a basic compound (E) in order to reduce the performance change with time from exposure to heating.
As the basic compound, preferably, a compound having a structure represented by the following formulas (A) to (E) can be mentioned.

In the general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each is a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (having a carbon number of). 6 to 20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ^{206, which} may be the same or different, each represents an alkyl group having 1 to 20 carbon atoms.
Regarding the above-mentioned alkyl group, the alkyl group having a substituent is preferably 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.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

  Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate. Examples thereof include compounds having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole and benzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4,4]. 0] Undeca 7-ene and the like. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide and tris (t-butylphenyl). Examples thereof include sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. The compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion portion is a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the compound having an aniline structure include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline and N, N-dihexylaniline. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine and tris (methoxyethoxyethyl) amine. Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

Preferable basic compounds further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.
The amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonate ester group and the ammonium salt compound having a sulfonate ester group have at least one alkyl group bonded to a nitrogen atom. Is preferred. Further, it is preferable that the alkyl chain has an oxygen atom to form an oxyalkylene group. The number of oxyalkylene groups is 1 or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. _-CH 2 _CH 2 O Among the oxyalkylene group _{-, - CH (CH 3)} CH 2 O- or _-CH 2 _CH 2 _CH 2 O- structure is preferred.
Specific examples of the amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonic acid ester group and the ammonium salt compound having a sulfonic acid ester group include US Patent Application Publication No. 2007/0224539. Compounds (C1-1) to (C3-3) exemplified in [0066] in (6) are mentioned, but the invention is not limited thereto.

  The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not contain a basic compound, but in the case of containing it, the amount of the basic compound used is as much as actinic ray-sensitive or radiation-sensitive. It is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the resin composition.

  The ratio of the acid generator and the basic compound used in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the deterioration of resolution due to the thickening of the resist pattern over time after exposure and heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

[6] Surfactant (F)
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not further contain a surfactant. It is more preferable to contain any one of a silicon-based surfactant and a surfactant having both a fluorine atom and a silicon atom, or two or more kinds.

Since the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less is used, good sensitivity and resolution are obtained, and adhesion and development defects It is possible to give a small resist pattern.
Examples of the fluorine-based and / or silicon-based surfactants include the surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. For example, Ftop EF301, EF303, (Shin-Akita Kasei Co., Ltd. )), Florard FC430, 431, 4430 (Sumitomo 3M Limited), Megafac F171, F173, F176, F189, F113, F110, F177, F120, R08, R41 (DIC Limited), Surflon S. -382, SC101, 102, 103, 104, 105, 106, KH-20 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (Toa Gosei Kagaku). Co., Ltd.), Surflon S-393 (Seimi Chemical Co., Ltd.), F-top EF12 , EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco Co., Ltd.), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), 2TX-18G, 208G, 208G, 208G. , 204D, 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (produced by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

Further, as the surfactant, in addition to the known ones described above, a fluoroaliphatic compound produced by a telomerization method (also called telomer method) or an oligomerization method (also called oligomer method) is used. It is possible to use a surfactant using a polymer having a fluoroaliphatic group formed therein. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
As the surfactant corresponding to the above, (manufactured by DIC _(Ltd.)) Megafac F178, F-470, F- 473, F-475, F-476, F-472, acrylates having a C _{6 F 13} group (or A copolymer of (meth) acrylate and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₃ F ₇ group, and (poly (oxyethylene)) acrylate (or methacrylate) and (poly ( (Oxypropylene)) acrylate (or methacrylate) and the like.

  Further, in the present invention, a surfactant other than the fluorine-based and / or silicon-based surfactant described in [0280] of US Patent Application Publication No. 2008/0248425 may be used.

  These surfactants may be used alone or in some combinations.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a surfactant, but the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant. In this case, the amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). %.

[7] Other additives (G)
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not contain a carboxylic acid onium salt. Examples of such carboxylic acid onium salts include those described in US Patent Application Publication No. 2008/0187860 [0605] to [0606].

  These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

When the actinic ray-sensitive or radiation-sensitive resin composition contains a carboxylic acid onium salt, the content thereof is generally 0.1 to 20% by mass, preferably 0, based on the total solid content of the composition. 0.5 to 10% by mass, more preferably 1 to 7% by mass.
If necessary, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may further have a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor and a solubility in a developer. A compound that accelerates the reaction (for example, a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound) can be contained.

Such a phenol compound having a molecular weight of 1000 or less can be obtained by referring to, for example, the methods described in JP-A-4-122938, JP-A-2-28531, U.S. Pat. No. 4,916,210, and European Patent 219294. It can be easily synthesized by those skilled in the art.
Specific examples of the alicyclic or aliphatic compound having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, and lithocholic acid, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acid, cyclohexanecarboxylic acid, and cyclohexane. Examples thereof include, but are not limited to, dicarboxylic acids.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably used in a film thickness of 30 to 250 nm, more preferably 30 to 200 nm, from the viewpoint of improving resolution. preferable. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range so as to have an appropriate viscosity and improving the coatability and film-forming property.
The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is usually 1.0 to 15% by mass, preferably 2.5 to 13% by mass, more preferably 3.0 to 12%. It is% by mass. By setting the solid content concentration in the above range, the resist solution can be uniformly applied onto the substrate, and further, a resist pattern having a high resolution and a rectangular profile and having excellent etching resistance is formed. It will be possible. Although the reason for this is not clear, it is likely that the solid content concentration of 10% by mass or less, preferably 5.7% by mass or less suppresses the aggregation of the material in the resist solution, particularly the photo-acid generator. As a result, it is considered that a uniform resist film could be formed.
The solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the actinic ray-sensitive or radiation-sensitive resin composition.

  The actinic ray-sensitive or radiation-sensitive resin composition in the present invention is prepared by dissolving the above-mentioned components in a predetermined organic solvent, preferably the mixed solvent, filtering the solution, and coating the solution on a predetermined support (substrate). To use. The pore size of the filter used for filter filtration is 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene or nylon. In the filter filtration, for example, as in JP-A-2002-62667, cyclic filtration may be performed, or a plurality of types of filters may be connected in series or in parallel to perform filtration. Also, the composition may be filtered multiple times. Further, the composition may be subjected to deaeration treatment before and after the filtration with a filter.

[8] Pattern Forming Method The pattern forming method (negative pattern forming method) of the present invention is
(A) a step of forming a film (actinic ray-sensitive or radiation-sensitive resin composition film) from the actinic ray-sensitive or radiation-sensitive resin composition,
(A) exposing the film, and (c) developing the exposed film with a developer containing an organic solvent to form a negative pattern.
At least.

The exposure in the step (a) may be immersion exposure.
The pattern forming method of the present invention preferably has (d) a heating step after (a) the exposure step.
The pattern forming method of the present invention may further include the step of (e) developing with an alkali developing solution.
The pattern forming method of the present invention can include (a) the exposure step a plurality of times.
The pattern forming method of the present invention may include (e) the heating step a plurality of times.

  The actinic ray-sensitive or radiation-sensitive resin film is preferably a resist film.

The actinic ray-sensitive or radiation-sensitive resin film of the present invention is a film formed by the above actinic ray-sensitive or radiation-sensitive resin composition, and for example, the substrate may have an actinic ray-sensitive or radiation-sensitive resin composition. It is a film formed by applying an object.
Specifically, the actinic ray-sensitive or radiation-sensitive resin film of the present invention is an actinic ray-sensitive resin obtained by applying the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition onto a substrate by spin coating. Alternatively, a radiation sensitive resin film is preferable.
The maximum rotation speed of the spin coating method is not particularly limited, but preferably 2500 rpm or less, more preferably 2250 rpm or less, and further preferably 2000 rpm or less.

  The resist film is formed from the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention described above, and more specifically, it is preferably formed on a substrate. In the pattern forming method of the present invention, the steps of forming a film of a actinic ray-sensitive or radiation-sensitive resin composition on a substrate, exposing the film, and developing are generally known methods. Can be done by.

It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the exposure step.
Further, it is also preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step.
The heating temperature for both PB and PEB is preferably 70 to 130 ° C, more preferably 80 to 120 ° C.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, further preferably 30 to 90 seconds.
The heating can be performed by a means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The bake accelerates the reaction in the exposed area and improves the sensitivity and pattern profile.

  Examples of the light source wavelength used in the exposure apparatus of the present invention include KrF excimer laser (248 nm), EUV (13 nm), and electron beam. KrF excimer laser is preferable.

In the present invention, the substrate on which the film is formed is not particularly limited, and is an inorganic substrate such as silicon, SiN, SiO ₂ or SiN, a coating type inorganic substrate such as SOG, a semiconductor manufacturing process such as IC, a liquid crystal, a thermal head. A substrate generally used in the manufacturing process of a circuit board such as the above and other lithography process of photofabrication can be used.
In the pattern forming method of the present invention, a stepped substrate can be used as the substrate in microfabrication such as for ion implantation.
The step substrate is a substrate having at least one step shape formed on the substrate.
The film thickness of the laminated film formed on the stepped substrate means the height from the bottom surface of the stepped substrate to the upper surface of the resist film formed.
The height from the bottom surface of the step substrate to the top surface of the step shape is preferably smaller than the film thickness of the resist film, and is, for example, less than 200 nm.
For example, in the case of fine processing such as for ion implantation, a substrate in which fins and gates are patterned on a flat substrate can be used as the step substrate. The actinic ray-sensitive or radiation-sensitive resin composition is applied onto the stepped substrate on which the fins and gates are patterned as described above, and the film thickness of the resist film formed means the thickness of the resist film formed from the upper surface of the fins or gates. It means the height from the bottom surface on the stepped substrate to the upper surface of the resist film formed as described above, not the height to the upper surface of the resist film.
The sizes of fins and gates (width, length, height, etc.), intervals, structures, configurations, etc. are described in, for example, the Institute of Electronics, Information and Communication Engineers Vol. 91, No. 1, 2008 25-29 "Advanced FinFET process / integration technology" and Jpn. J. Appl. Phys. Vol. 42 (2003) pp. 4142-4146 Part 1, No. 6B, June 2003 “Fin-Type Double-Gate Metal-Oxide-Semiconductor Field-Effect Transistors Fabricated by Orientation-Dependent Alignment-Electrifying Alignment and Dependent Ejection and Ejection and Ejection and Ejection and Ejection”.
The pattern forming method of the present invention does not require an antireflection film from the viewpoint of achieving the effects of the present invention, but an organic antireflection film may be formed between the film and the substrate if necessary.
For example, an antireflection film may be provided under the resist. As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon and amorphous silicon and an organic film type composed of a light absorber and a polymer material can be used. The former requires equipment such as a vacuum vapor deposition apparatus, a CVD apparatus, and a sputtering apparatus for forming a film. Examples of the organic antireflection film include a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in Japanese Patent Publication No. 7-69611, an alkali-soluble resin, and a light absorber, and a maleic anhydride copolymerization described in US Pat. No. 5,294,680. A reaction product of a combination of a diamine type light absorber, a resin binder described in JP-A-6-118631 and a methylol melamine-based thermal crosslinking agent, a carboxylic acid group, an epoxy group and a light-absorbing group described in JP-A-6-118656. Acrylic resin type antireflection film having the same molecule, consisting of methylol melamine and benzophenone-based light absorber described in JP-A-8-87115, and low-molecular-weight absorber added to polyvinyl alcohol resin described in JP-A-8-179509. The thing etc. are mentioned.
Further, as the organic antireflection film, a commercially available organic antireflection film such as DUV30 series manufactured by Brewer Science Co., DUV-40 series, AR-2, AR-3, AR-5 manufactured by Shipley Co. may be used. it can.
If necessary, an antireflection film can be used as an upper layer of the resist.
Examples of the antireflection film include AQUATAR-II, AQUATAR-III, and AQUATAR-VII manufactured by AZ Electronic Materials Co., Ltd.

The pattern forming method of the present invention, as the developer in the step of developing with a developer containing an organic solvent (hereinafter, also referred to as an organic developer), a ketone solvent, an ester solvent, an alcohol solvent, A polar solvent such as an amide solvent and an ether solvent, and a hydrocarbon solvent can be used.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples thereof include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone and propylene carbonate.
Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl acetate. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. Butyl acetate is particularly preferred.
Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, Alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butano It can be mentioned glycol ether solvents such as Le.
Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of the amide-based solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
A plurality of the above solvents may be mixed, or a solvent other than the above and water may be mixed and used. However, in order to fully exert the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of water.
That is, the amount of the organic solvent used with respect to the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developing solution.
In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent. .

The vapor pressure of the organic developer at 20 ° C. is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. By adjusting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is achieved. The quality is improved.
Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, butyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl acetate Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, formic acid Ester, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc., n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, alcohol solvents such as n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, Propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymeth Glycol ether solvent such as rubutanol, ether solvent such as tetrahydrofuran, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, amide solvent of N, N-dimethylformamide, aromatic carbonization such as toluene and xylene Examples thereof include hydrogen-based solvents and aliphatic hydrocarbon-based solvents such as octane and decane.
Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone. , Ketone solvents such as phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3- Ester solvents such as methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate, n-butyl alcohol, ec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, and other alcohol solvents, ethylene glycol, diethylene glycol, triethylene glycol, and other glycol solvents. And glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether and methoxymethyl butanol, N-methyl-2 -Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide amide solvent, Aromatic hydrocarbon solvents such as cyclohexylene, octane, aliphatic hydrocarbon solvents decane.

If necessary, a surfactant can be added to the organic developing solution in an appropriate amount.
The surfactant is not particularly limited, but, for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant can be used. Examples of these fluorine and / or silicon surfactants include JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A-62-170950. JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, and US Pat. No. 5,405,720. Examples thereof include the surfactants described in Nos. 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511 and 5,824,451. , Preferably nonionic surfactants. The nonionic surfactant is not particularly limited, but it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant.
The amount of the surfactant used 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, based on the total amount of the developer.

Examples of the developing method include a method of dipping the substrate in a tank filled with the developing solution for a certain period of time (dip method), and a method of raising the developing solution on the surface of the substrate by surface tension and standing for a certain period of time (paddle method). Method), a method of spraying the developing solution on the substrate surface (spray method), a method of continuously discharging the developing solution on the substrate rotating at a constant speed while scanning the developing solution discharge nozzle at a constant speed (dynamic dispensing method) Etc. can be applied.
When the above various developing methods include a step of ejecting the developing solution from the developing nozzle of the developing device toward the resist film, the ejection pressure of the ejected developing solution (flow rate per unit area of the ejected developing solution) is It is preferably 2 mL / sec / mm ² or less, more preferably 1.5 mL / sec / mm ² or less, and further preferably 1 mL / sec / mm ² or less. Although there is no particular lower limit of the flow rate, 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.
By setting the discharge pressure of the discharged developing solution within the above range, it is possible to significantly reduce the pattern defects derived from the resist residue after development.
Although the details of this mechanism are not clear, it is likely that by setting the discharge pressure within the above range, the pressure applied by the developing solution to the resist film becomes small, and the resist film / resist pattern is inadvertently scraped or broken. Is considered to be suppressed.
The discharge pressure (mL / sec / mm ² ) of the developing solution is a value at the outlet of the developing nozzle in the developing device.

  Examples of the method of adjusting the discharge pressure of the developing solution include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure with supply from a pressure tank.

  Further, after the step of developing using a developing solution containing an organic solvent, a step of stopping the development may be carried out while substituting with another solvent.

  After the step of developing with a developing solution containing an organic solvent, it is preferable to include a step of washing with a rinse solution.

The rinse solution used in the rinse step after the step of developing with a developer containing an organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. . As the rinse liquid, a rinse liquid containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent is used. It is preferable.
Specific examples of the hydrocarbon-based solvent, the ketone-based solvent, the ester-based solvent, the alcohol-based solvent, the amide-based solvent, and the ether-based solvent may be the same as those described for the developer containing an organic solvent.
After the step of developing with a developer containing an organic solvent, more preferably, at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent and an amide solvent is contained. The step of washing with a rinse liquid is performed, more preferably the step of washing with a rinse liquid containing an alcohol solvent or an ester solvent is performed, and particularly preferably a rinse liquid containing a monohydric alcohol is used. The cleaning step is performed, and most preferably, the cleaning step is performed using a rinse liquid containing a monohydric alcohol having 5 or more carbon atoms.
Here, examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols, and specifically, 1-butanol, 2-butanol, and 3-methyl-1-butanol. , Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferred monohydric alcohols having 5 or more carbon atoms are 1-hexanol, 2-hexanol and 4-methyl-. Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. It can be.

  A plurality of each of the above components may be mixed, or an organic solvent other than the above may be mixed and used.

  The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. When the water content is 10% by mass or less, good developing characteristics can be obtained.

The vapor pressure of the rinse liquid used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C., more preferably 0.1 kPa or more and 5 kPa or less, and 0.1. Most preferably, it is 12 kPa or more and 3 kPa or less. By setting the vapor pressure of the rinse liquid to be not less than 0.05 kPa and not more than 5 kPa, the temperature uniformity in the wafer surface is improved, and the swelling caused by the penetration of the rinse liquid is suppressed, and the dimensional uniformity in the wafer surface is suppressed. Will improve.
An appropriate amount of a surfactant may be added to the rinse liquid before use.

  In the rinsing step, the wafer that has been developed with the developing solution containing the organic solvent is washed with the rinsing solution containing the organic solvent. The method of cleaning treatment is not particularly limited, but for example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (spin coating method), or immersing the substrate in a bath filled with the rinse liquid for a certain period of time. The method (dip method), the method of spraying the rinse liquid on the substrate surface (spray method), etc. can be applied. Among them, the cleaning treatment is performed by the spin coating method, and after the cleaning, the substrate is rotated at 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinse step. By the baking, the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed. The heating step after the rinsing step is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

When the pattern forming method of the present invention further has a step of developing with an alkali developing solution, examples of the alkali developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia. Inorganic alkalis such as water, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine and triamine. Alkaline aqueous solutions of alcohol amines such as ethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pyrelidine can be used.
Furthermore, alcohols and surfactants may be added in appropriate amounts to the alkaline aqueous solution before use.
The alkali concentration of the alkali developer is usually 0.1 to 20% by mass.
The pH of the alkaline developer is usually 10.0 to 15.0.
In particular, a 2.38% mass aqueous solution of tetramethylammonium hydroxide is desirable.

As the rinse liquid in the rinse treatment performed after the alkali development, pure water may be used and an appropriate amount of a surfactant may be added and used.
In addition, after the developing treatment or the rinsing treatment, a treatment of removing the developing solution or the rinsing fluid adhering to the pattern with a supercritical fluid can be performed.

The present invention also relates to a method for manufacturing an electronic device, including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.
The electronic device of the present invention is preferably mounted on electric and electronic equipment (home appliances, OA / media-related equipment, optical equipment, communication equipment, etc.).

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Synthesis Example 1 Synthesis of Resin (Pol-1) 600 g of cyclohexanone was placed in a 2 L flask, and nitrogen substitution was performed at a flow rate of 100 mL / min for 1 hour. Thereafter, 4.60 g (0.02 mol) of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the internal temperature was raised to 80 ° C. Next, the following monomers and 4.60 g (0.02 mol) of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 200 g of cyclohexanone to prepare a monomer solution. The monomer solution was added dropwise to the above flask heated to 80 ° C. over 6 hours. After the dropping was completed, the reaction was further performed at 80 ° C. for 2 hours.
4-acetoxystyrene 40.55 g (0.25 mol)
Monomer corresponding to Unit 2-1 104.96 g (0.40 mol)
Monomer corresponding to Unit 3-1 49.77 g (0.35 mol)
The reaction solution was cooled to room temperature and dropped into 3 L of hexane to precipitate a polymer. The filtered solid is dissolved in 500 mL of acetone, dropped again in 3 L of hexane, the filtered solid is dried under reduced pressure, and a copolymer of 4-acetoxystyrene / a monomer corresponding to Unit2-1 / a monomer corresponding to Unit3-1. 172 g were obtained.

10 g of the polymer obtained above, 40 mL of methanol, 200 mL of 1-methoxy-2-propanol, and 1.5 mL of concentrated hydrochloric acid were added to a reaction vessel, and the mixture was heated to 80 ° C. and stirred for 5 hours. The reaction solution was allowed to cool to room temperature and added dropwise to 3 L of distilled water. The filtered solid was dissolved in 200 mL of acetone, again dropped into 3 L of distilled water, and the filtered solid was dried under reduced pressure to obtain 8.1 parts by mass of resin (Pol-1). The obtained resin (Pol-1) had a weight average molecular weight of 13,000, a dispersity (Mw / Mn) of 1.5, and a composition ratio measured by ¹³ C-NMR of 25/40/35. there were.

The same operations as in Synthesis Example 1 were performed to synthesize resins (Pol-2) to (Pol-13) and resins (Pol-C1) to (Pol-C2).
In Table 1 below, for the resins (Pol-2) to (Pol-13) and the resins (Pol-C1) to (Pol-C2), repeating units (units), composition ratios (molar ratios), weight average molecular weights, Indicates the dispersity.

  The components and abbreviations in Table 1 above are as follows.

[Examples 1 to 14 and Comparative Examples 1 to 2]
[Preparation of actinic ray-sensitive or radiation-sensitive resin composition]
The components shown in Table 2 below are dissolved in a solvent to prepare a resist solution for each, and the resist solution is filtered through a nylon filter having a pore size of 0.03 μm to obtain an actinic ray-sensitive material having a solid content concentration of 3.5% by mass or A radiation-sensitive resin composition (resist composition) was prepared.

  The components and abbreviations in Table 2 above are as follows. [Acid generator]

[Basic compound]

[Surfactant]
W-1: Megafac R41 (manufactured by DIC Corporation)

[solvent]
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether (PGME)

The prepared actinic ray-sensitive or radiation-sensitive resin composition was evaluated by the following methods.
[Film thickness uniformity]
12-inch silicon wafer (diameter: 300 mm, thickness: 775 μm, material: single crystal silicon 12-inch silicon wafer, manufactured by MEMC Electronic Co., Ltd.), the resist composition shown in the above table was spin-coated (CLEAN TRACK LITHIUS Pro manufactured by Tokyo Electron). Was applied at a maximum rotation speed of 2000 rpm and baked at 100 ° C. for 60 seconds (Pre Bake; PB) to form a resist film having a film thickness of 400 nm.
The film thickness of the resist film was measured at 25 points with an F50 automatic mapping film thickness measurement system (manufactured by FILMETRICS), and the film thickness uniformity was evaluated as 3σ. The smaller the value, the better the film thickness uniformity. If it is 35 or less, there is no practical problem.
The results are shown in Table 3 below.

[Pattern formation]
An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film of 78 nm. Using a spin coater (CLEAN TRACK LITHIUS Pro manufactured by Tokyo Electron Ltd.), the resist composition (Res-1) prepared thereon was applied at a maximum rotation speed of 2000 rpm, and baked at 100 ° C. for 60 seconds to give a film thickness. A 400 nm resist film was formed. The obtained wafer was pattern-exposed using a KrF excimer laser scanner (PAS5500 / 850, manufactured by ASML) (NA0.75). After heating at 100 ° C. for 60 seconds, development with butyl acetate for 60 seconds and rinsing with pure water for 30 seconds gave a good hole pattern with a pitch of 400 nm and a hole diameter of 200 nm.

  As is clear from Table 3, when the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is used, the resulting resist film has excellent film thickness uniformity.

  According to the present invention, even when provided on a substrate having a wide diameter (for example, a diameter of 12 inches or more), it is possible to form an actinic ray-sensitive or radiation-sensitive resin film excellent in film thickness uniformity. And a radiation-sensitive resin composition, and an actinic ray-sensitive or radiation-sensitive resin film using the same, a pattern forming method, and an electronic device manufacturing method can be provided.

Although the present invention has been described in detail and with reference to particular embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on the Japanese patent application filed on Aug. 31, 2017 (Japanese Patent Application No. 2017-167851), the contents of which are incorporated herein by reference.

Claims (8)

(A) contains a repeating unit represented by the following general formula (1), a repeating unit represented by the following general formula (2), and a repeating unit represented by the following general formula (3),
A resin in which the content of the repeating unit represented by the general formula (1) is in the range of 25 to 50 mol% with respect to all the repeating units in the resin (A),
An actinic ray-sensitive or radiation-sensitive resin composition containing (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and (C) a solvent.

In the general formula (2), R ₁ represents a hydrogen atom or a methyl group. R ₂ and R ₃ each independently represent a hydrocarbon group having 1 to 4 carbon atoms. However, R ₂ and R ₃ may be bonded to each other to form a ring having 3 to 8 carbon atoms. R ₄ represents a polycyclic hydrocarbon group having 6 to 20 carbon atoms.
In the general formula (3), R ₅ is a hydrogen atom or a methyl group. R _{6, R 7} and _{R 8} each independently represents a linear or branched hydrocarbon group having 1 to 4 carbon atoms. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein in the repeating unit represented by the general formula (2), R ₄ is an adamantyl group, a norbornyl group, or a bicyclooctyl group.   The actinic ray-sensitive property according to claim 1 or 2, wherein the content of the repeating unit represented by the general formula (2) is 25 to 50 mol% with respect to all the repeating units in the resin (A). Radiation-sensitive resin composition.   The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, which is for KrF exposure.   The actinic ray-sensitive or actinic ray-sensitive resin obtained by applying the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4 onto a substrate by a spin coating method at a maximum rotation speed of 2500 rpm or less. Radiation-sensitive resin film.   (A) a step of forming a film from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, (a) a step of exposing the film, and (c) an exposure A pattern forming method including a step of developing the formed film with a developing solution containing an organic solvent to form a negative pattern.   The pattern forming method according to claim 6, wherein the developing solution is butyl acetate. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 6.