WO2014192768A1

WO2014192768A1 - Pattern-forming method, actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, method for producing electronic device, and electronic device

Info

Publication number: WO2014192768A1
Application number: PCT/JP2014/064021
Authority: WO
Inventors: 創古谷; 研由後藤; 三千紘白川; 正洋吉留
Original assignee: 富士フイルム株式会社
Priority date: 2013-05-30
Filing date: 2014-05-27
Publication date: 2014-12-04
Also published as: JP2014235179A; TW201501177A

Abstract

　This pattern-forming method is characterized by including the following steps: a step in which an actinic ray-sensitive or radiation-sensitive resin composition containing a resin, the solvability of which in an organic solvent decreases as a result of the action of acid, a solvent, and a compound that generates a component that forms ionic bonds with polar groups in the resin, is applied onto a substrate to form an actinic ray-sensitive or radiation-sensitive film; a step in which the actinic ray-sensitive or radiation-sensitive film is exposed; and a step in which the exposed actinic ray-sensitive or radiation-sensitive film is developed using a developer including an organic solvent, to form a negative pattern.

Description

Pattern forming method, actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, method for producing electronic device, and electronic device

The present invention relates to a pattern forming method used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal and a thermal head, and other photofabrication lithography processes, and an activity sensitive used in the pattern forming method. The present invention relates to a light-sensitive or radiation-sensitive resin composition, an actinic light-sensitive or radiation-sensitive film, a method for producing an electronic device, and an electronic device. Particularly suitable for exposure with an ArF exposure apparatus and an immersion projection exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source, and actinic ray sensitivity or radiation sensitivity used in the pattern formation method The present invention relates to a resin composition, an actinic ray-sensitive or radiation-sensitive film, a method for producing an electronic device, and an electronic device.

Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. An example of a positive-type chemical amplification image forming method will be described. By exposure with an excimer laser, an electron beam, extreme ultraviolet light, or the like, an acid generator in an exposed area is decomposed to generate an acid, and a post-exposure baking (PEB) : Post Exposure Bake) using an acid generated as a reaction catalyst to change an alkali-insoluble group to an alkali-soluble group and removing an exposed portion with an alkali developer.

On the other hand, in recent years, a negative pattern forming method using a developer containing an organic solvent is being developed. For example, Patent Document 1 uses a developer obtained by adding a nitrogen-containing compound to an organic solvent as a developer. Thus, a method for forming a negative pattern is described.

Further, Patent Document 12 describes a double development technique as a double patterning technique for further increasing the resolution. By utilizing the fact that the polarity of the resin in the resist composition by exposure becomes high polarity in regions with high light intensity and low polarity in regions with low light intensity, By dissolving in a high-polarity developer and dissolving the low exposure area in a developer containing an organic solvent, the intermediate exposure area remains undissolved by development and has a line-and-half with an exposure mask half pitch. A space pattern is formed.

Japanese Patent No. 5056974 JP 2008-292975 A

In the formation of a negative pattern using a developer containing an organic solvent, film thickness, line width variation (LWR), which is presumed to be caused by a low dissolution contrast between the unexposed area and the exposed area, Further improvements in other performances are required. In addition, for pattern formation using a double development technique, it is required to suppress film slippage during development using a developer containing an organic solvent.

The present invention relates to a pattern forming method capable of forming a pattern with small line width variation (LWR) and reduced film slip, an actinic ray-sensitive or radiation-sensitive resin composition that can be suitably used in this method, and an activity It is an object to provide a light-sensitive or radiation-sensitive film. Another object of the present invention is to provide an electronic device manufacturing method and an electronic device including the pattern forming method.

In one aspect, the present invention is as follows.
[1] An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin whose solubility in an organic solvent is reduced by the action of an acid, a solvent, and a compound that generates a component that forms an ionic bond with a polar group in the resin A step of applying an object on a substrate to form an actinic ray-sensitive or radiation-sensitive film;
-Exposing the actinic ray-sensitive or radiation-sensitive film; and
A pattern forming method comprising: developing the actinic ray-sensitive or radiation-sensitive film exposed using a developer containing an organic solvent to form a negative pattern;

[2] The pattern forming method according to [1], further comprising a step of developing using an alkali developer to form a positive pattern.

[3] Steps including the steps included in the pattern forming method according to [1] in the order as described, and further developing with an alkaline developer to form a positive pattern are referred to as the exposure step. The pattern forming method according to [1] or [2], which is included during the developing step using a developer containing an organic solvent.

[4] The pattern forming method according to any one of [1] to [3], further including a step of decomposing the compound that generates a component that forms an ionic bond with a polar group.

[5] The step of including the steps included in the pattern forming method according to [1] in the order described, and further decomposing the compound that generates a component that forms an ionic bond with the polar group, The pattern forming method according to any one of [1] to [4], which is included between the step and the developing step using a developer containing an organic solvent.

[6] The pattern forming method according to [3] includes a component that forms an ionic bond with a polar group between the developing step using an alkali developer and the developing step using a developer containing an organic solvent. A pattern forming method, further comprising a step of decomposing the generated compound.

[7] The pattern forming method according to any one of [4] to [6], wherein the compound that generates a component that forms an ionic bond with a polar group is decomposed by heating.

[8] The pattern forming method according to [7], wherein the heating is performed at a temperature of 120 ° C. or higher.

[9] The pattern forming method according to any one of [1] to [8], wherein the exposure is performed through an immersion liquid.

[10] The pattern according to any one of [1] to [9], wherein the compound that generates a component that forms an ionic bond with a polar group is represented by the following general formula (1): Forming method.

Where
R ₁ and R ₂ each independently represents a hydrogen atom or a substituent.

R ₃ represents a substituent.

At least two of R ₁ , R ₂ and R ₃ may be connected to each other to form a ring.

[11] An actinic ray-sensitive or sensitive material comprising a resin whose solubility in an organic solvent is reduced by the action of an acid, a solvent, and a compound that generates a component that forms an ionic bond with a polar group in the resin. Radiation resin composition.

[12] The actinic ray-sensitive or radiation-sensitive resin composition according to [11], wherein the compound that generates a component that forms an ionic bond with a polar group is represented by the following general formula (1): object.

R ₃ represents a substituent.

[13] The content of the compound that generates a component that forms an ionic bond with a polar group is 2 to 10% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition as described in [11] or [12].

[14] An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive composition according to any one of [11] to [13].

[15] An electronic device manufacturing method including the pattern forming method according to any one of [1] to [10].

[16] An electronic device manufactured by the method for manufacturing an electronic device according to [14].

INDUSTRIAL APPLICABILITY According to the present invention, a pattern forming method capable of forming a pattern with small line width variation (LWR) and reduced film slip, an actinic ray-sensitive or radiation-sensitive resin composition that can be suitably used in this method, and activity sensitivity A light-sensitive or radiation-sensitive film can be provided. Further, according to the present invention, an electronic device manufacturing method and an electronic device including the pattern forming method can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have 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).

Here, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-ray, electron beam (EB), and the like. . In the present invention, light means actinic rays or radiation.

In addition, “exposure” here means not only exposure with far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light, etc. typified by mercury lamps and excimer lasers, but also particle beams such as electron beams and ion beams, unless otherwise specified. Include drawing in exposure.

The pattern forming method of the present invention comprises a step of applying an actinic ray-sensitive or radiation-sensitive resin composition on a substrate to form an actinic ray-sensitive or radiation-sensitive film, the actinic ray-sensitive or radiation-sensitive film. And the step of developing the actinic ray-sensitive or radiation-sensitive film exposed using a developer containing an organic solvent to form a negative pattern, the actinic ray-sensitive or radiation-sensitive As a functional resin composition, a composition containing a resin that reduces the solubility in an organic solvent by the action of an acid, a solvent, and a compound that generates a component that forms an ionic bond with a polar group in the resin (hereinafter referred to as “the present invention”). Or the like ".

In the step of developing the chemically amplified resist film with a developer containing an organic solvent (hereinafter also referred to as “organic solvent developer”) to form a negative pattern, the exposed portion remains as a pattern and the unexposed portion is removed. However, the present inventors have improved the LWR of the pattern by adding a compound that generates a component that forms an ionic bond with a polar group into the actinic ray-sensitive or radiation-sensitive resin composition, and the film It has been found that the reduction is reduced. This is because the component that forms an ionic bond with the polar group generated from the compound (B) acts on the polar group generated by decomposition by the action of the acid in the resin in the exposed portion, thereby forming a salt. It is presumed that the insolubilization of the resist with respect to the organic solvent developer is increased, and the dissolution contrast between the unexposed portion and the exposed portion is increased.

Hereinafter, each step included in the pattern forming method of the present invention will be described in detail, and then the actinic ray-sensitive or radiation-sensitive resin composition suitably used for this pattern forming method will be described in detail.

As described above, the pattern forming method of the present invention includes:
A step of applying an actinic ray-sensitive or radiation-sensitive resin composition containing a compound that generates a component that forms an ionic bond with a polar group to form an actinic ray-sensitive or radiation-sensitive film;
-Exposing the actinic ray-sensitive or radiation-sensitive film; and
-Developing the actinic ray-sensitive or radiation-sensitive film exposed using an organic solvent-based developer to form a negative pattern.

[Decomposition step of a compound that generates a component that forms an ionic bond with a polar group]
In one embodiment, the pattern forming method of the present invention decomposes a compound that generates a component that forms an ionic bond with a polar group, contained in the composition of the present invention, and the solubility in an organic solvent is reduced by the action of an acid. A step of generating a component that forms an ionic bond with a polar group in the resin. Here, the “polar group in the resin” is a group (resin (A)) whose solubility in an organic solvent is reduced by the action of an acid described later (“resin (A)”), which decomposes by the action of an acid to generate a polar group ( Acid-decomposable group) means a polar group generated by the decomposition of the acid-decomposable group, and when the resin (A) has a polar group from the beginning, the polar group and the acid It means both polar groups generated by decomposing decomposable groups.

In the pattern forming method of the present invention, the step of decomposing a compound that generates a component that forms an ionic bond with a polar group is included, for example, between an exposure step and a development step using an organic solvent developer. When the pattern forming method of the present invention includes a post-exposure bake (PEB) step after the exposure step and before the development step as described later, a component that forms an ionic bond with the polar group is generated. Preferably, the step of decomposing the compound to be included is included between the PEB step and the development step using an organic developer. After the PEB step, by decomposing a compound that generates a component that forms an ionic bond with the polar group, after the deprotection of the acid-decomposable group in the resin proceeds by the PEB step, the compound is decomposed and generated. This is preferable because the formed component and the polar group generated by the above deprotection form a salt.

As means for decomposing a compound that generates a component that forms an ionic bond with a polar group, for example, irradiation with visible light / ultraviolet light, heating, or the like can be applied.

When decomposing a compound that generates a component that forms an ionic bond with a polar group by heating, the heating means is not particularly limited, and for example, means provided in a normal exposure / development machine may be used. However, a hot plate or the like may be used.
The heating temperature for decomposing the compound that generates a component that forms an ionic bond with the polar group is appropriately set depending on the compound. For example, the heating temperature is preferably 90 to 250 ° C., and preferably 120 to 200 ° C. It is more preferable to carry out at 120 to 170 ° C.
For example, the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 120 seconds.
The pattern forming method of the present invention may include a developing step a plurality of times, for example, a developing step of forming a negative pattern using an organic solvent developer, and a developing of forming a positive pattern using an alkali developer. And a process. In this case, it is preferable to first perform the first development using an alkali developer, and then to perform the second development using an organic solvent-based developer. In this case, the component that forms an ionic bond with the polar group is added. The decomposition step of the generated compound is preferably included between the first development step using an alkali developer and the second development step using an organic solvent developer. Thereby, the dissolution contrast of an unexposed part and an exposed part becomes still larger, and the effect of this invention increases.

[Film forming process]
The actinic ray-sensitive or radiation-sensitive resin composition can be applied to the substrate by a generally known method. For example, an actinic ray-sensitive or radiation-sensitive resin composition may be formed by applying an actinic ray-sensitive or radiation-sensitive resin composition on the substrate at the center of the wafer and then rotating the substrate with a spinner. Alternatively, an actinic ray-sensitive or radiation-sensitive film may be applied while rotating to form an actinic ray-sensitive or radiation-sensitive film.

[Heating process]
In one embodiment, the pattern forming method of the present invention may include a heating step. Here, the heating step is different from the above-described step of thermally decomposing a compound that generates a component that forms an ionic bond with the polar group, for example, to promote the reaction of the exposed portion and improve the sensitivity and pattern profile. Furthermore, it means heating at a temperature at which the above compound does not decompose.

The pattern forming method of the present invention preferably includes, for example, a preheating (PB) process after the film forming process and before the exposure process.
In another form, the pattern forming method of the present invention preferably includes a post-exposure heating (PEB) step after the exposure step and before the development step.

The heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. for both PB and PEB.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.

[Exposure process]
Although there is no restriction | limiting in the light source wavelength used for the exposure method of this invention, Infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, an electron beam, etc. can be mentioned, Preferably it is 250 nm or less. More preferably 220 nm or less, particularly preferably far ultraviolet light having a wavelength of 1 to 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, etc., KrF excimer laser, ArF excimer laser, EUV or electron beam are preferable, and ArF excimer laser is more preferable.

Also, an immersion exposure method can be applied in the exposure process of the present invention. The immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a modified illumination method.

When performing immersion exposure, (1) after forming the film on the substrate, before the exposure step and / or (2) after exposing the film via the immersion liquid, Prior to the heating step, a step of washing the surface of the membrane with an aqueous chemical may be performed.

The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the film. In the case of an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.

When water is used, an additive (liquid) that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist layer on the wafer and can ignore the influence on the optical coating on the lower surface of the lens element.
As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage is obtained that the refractive index change as a whole liquid can be made extremely small.

On the other hand, distilled water is preferable as the water to be used because it causes distortion of the optical image projected on the resist when an opaque material or impurities whose refractive index is significantly different from that of water are mixed with 193 nm light. Further, pure water filtered through an ion exchange filter or the like may be used.

The electrical resistance of the water used as the immersion liquid is preferably 18.3 MQcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed.

Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive that increases the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

The receding contact angle of the resist film formed by using the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is 70 ° or more at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%, and through the immersion medium. Suitable for exposure, preferably 75 ° or more, more preferably 75 to 85 °.
If the receding contact angle is too small, it cannot be suitably used for exposure through an immersion medium, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited. In order to achieve a preferable receding contact angle, it is preferable to include the hydrophobic resin (HR) in the actinic ray-sensitive or radiation-sensitive composition. Alternatively, the receding contact angle may be improved by forming a coating layer (so-called “topcoat”) of a hydrophobic resin composition on the resist film.

In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. In this case, the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

[Development process]
The development step in the pattern forming method of the present invention is performed using a developer (organic developer) containing an organic solvent. As a result, a negative pattern is formed.

As the organic developer, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

Examples of ester solvents 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. Examples include 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, and propyl lactate. be able to.

Examples of the alcohol solvents 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, methoxymethylbuta Glycol ether solvents such as Lumpur can be mentioned.

Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. 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.

In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents and ester solvents, and in particular, butyl acetate or ketone as the ester solvent. A developer containing methyl amyl ketone (2-heptanone) as a system solvent is preferred.

A plurality of solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. However, in order to fully exhibit 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 moisture.
That is, the amount of the organic solvent used in 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, with respect to the total amount of the developer.

The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting 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, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.

An appropriate amount of a surfactant can be added to the organic developer as required.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in the specifications of US Pat. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type 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 with respect to the total amount of the developer.

Further, if necessary, nitrogen-containing compounds described in JP-A-2013-11833, particularly [0021] to [0063] may be added to the organic developer.

As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.

When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is As an example, it is preferably 2 mL / sec / mm ² or less, more preferably 1.5 mL / sec / mm ² or less, and still more preferably 1 mL / sec / mm ² or less. There is no particular lower limit on the flow rate, but 0.2 mL / sec / mm ² or more is preferable in consideration of throughput. Details of this are described in JP 2010-232550 A, in particular paragraphs 0022 to 0029.

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

In addition, when the pattern forming method of the present invention includes a plurality of development steps, as described above, the step of developing using an alkaline developer and the step of developing using an organic developer may be combined. As a result, FIG. 1-FIG. 11 and the like, it can be expected that a pattern having a half of the spatial frequency of the optical image can be obtained.

When the pattern forming method of the present invention includes a step of developing using an alkali developer, the alkali developer that can be used is not particularly limited, but generally, it is 2.38% by mass of tetramethylammonium hydroxide. An aqueous solution is desirable. In addition, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
As a rinsing solution in the rinsing treatment performed after alkali development, pure water can be used, and an appropriate amount of a surfactant can be added.
[Rinse process]
After the step of developing using an organic developer, it is preferable to include a rinse step of washing using a rinse solution. The rinsing liquid is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. As the rinsing liquid, a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. It is preferable.

Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent and ether solvent are the same as those described in the developer containing an organic solvent.

In one embodiment of the present invention, after the development step, the step of washing with a rinse liquid containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents. More preferably, the step of washing with a rinsing solution containing an alcohol solvent or an ester solvent is performed, and the step of washing with a rinsing solution containing a monohydric alcohol is particularly preferred. Preferably, a 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. Specific examples include 1-hexanol, 2-hexanol, and 4-methyl-2-pen. Tanol, 1-pentanol, 3-methyl-1-butanol and the like can be used.
A plurality of these components may be mixed, or may be used by mixing with an organic solvent other than the above.

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. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

The vapor pressure of the rinsing solution 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, more preferably 0.1 kPa or more and 5 kPa or less at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

An appropriate amount of a surfactant can be added to the rinse solution.
In the rinsing step, the wafer that has been developed using the developer containing the organic solvent is washed using the rinse solution containing the organic solvent. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. can be applied. Among these, a cleaning process is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 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 rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. 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.

The organic developer, alkali developer, and / or rinse solution used in the present invention preferably have few impurities such as various fine particles and metal elements. In order to obtain such chemicals with few impurities, these chemicals are manufactured in a clean room, and filtered with various filters such as Teflon (registered trademark) filters, polyolefin filters, ion exchange filters, etc. It is preferable to reduce impurities. As for the metal element, the metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn are all preferably 10 ppm or less, and preferably 5 ppm or less. More preferred.

The storage container for the developer and the rinsing liquid is not particularly limited, and containers such as polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin that are used for electronic materials can be used as appropriate. In order to reduce impurities eluted from the container, it is also preferable to select a container having a small amount of components eluted from the inner wall of the container into the chemical solution. As such a container, a container whose inner wall is a perfluoro resin (for example, FluoroPure PFA composite drum (wetted inner surface; PFA resin lining) manufactured by Entegris), steel drum can (wetted inner surface; zinc phosphate coating) manufactured by JFE ).

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

The pattern obtained by the pattern forming method of the present invention is generally suitably used as an etching mask for a semiconductor device or the like, but can also be used for other purposes. Other uses include, for example, guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. JP-A-3-270227, JP-A-2013-164509, etc.).

<Actinic ray-sensitive or radiation-sensitive resin composition>
The composition of this invention contains the compound which generate | occur | produces the component which forms an ion bond with the resin in which the solubility with respect to an organic solvent reduces by the effect | action of an acid, a solvent, and the polar group in the said resin.
In one embodiment, the composition of the present invention may further contain at least one of a compound capable of generating an acid upon irradiation with actinic rays or radiation, a hydrophobic resin, a basic compound, and a surfactant.
Hereinafter, each of these components will be described.

[Compounds that generate components that form ionic bonds with polar groups]
The compound that generates a component that forms an ionic bond with the polar group contained in the composition of the present invention is decomposed by light irradiation, heating, etc., and the polar group in the resin whose solubility in an organic solvent is reduced by the action of an acid described later. And a compound that generates a component that forms an ionic bond.
A compound that generates a component that forms an ionic bond with a polar group has a predetermined stability against the action of an acid. Specifically, a compound that generates a component that forms an ionic bond with a polar group has the stability evaluated by the following stability test against the action of an acid.
Stability test: A compound capable of forming an ion bond with a polar group (5 mg) and trifluoromethanesulfonic acid (10 mg) are dissolved in CDCl ₃ (1.0 mL) and allowed to stand at 25 ° C. for 1 hour. . Thereafter, ¹ H-NMR of the mixture is measured, and a compound in which 90% or more of the compound remains is stabilized in an acid based on the peak intensity of the compound and its decomposition product.

In one embodiment of the present invention, the compound that generates a component that forms an ionic bond with a polar group is preferably a compound that decomposes by heat to generate a component that forms an ionic bond with a polar group. Here, as a component which forms an ionic bond with a polar group generated by decomposition of a compound, for example, a base can be mentioned. The base here should just be a thing which can form an ionic bond with a polar group. More specifically, the base has a pKa of the conjugate acid of usually 4 or more, preferably 6 or more, and more preferably 8 or more. The upper limit value of the pKa of the conjugate acid is not limited to obtaining, but is preferably 18 or less, more preferably 16 or less, and still more preferably 14 or less. The pKa value described here is a value obtained by calculation using ACD / ChemSketch (ACD / LabsLab8.00 Release Product Version: 8.08). The base is preferably an amine, and more preferably a secondary or tertiary amine.

The compound that generates a component that forms an ionic bond with the polar group is preferably, for example, a compound represented by the following general formula (1).

Where
R ₁ and R ₂ each independently represents a hydrogen atom or a substituent.
R ₃ represents a substituent.
At least two of R ₁ , R ₂ and R ₃ may be connected to each other to form a ring.

Examples of the substituent represented by R ₁ and R ₂ include an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 3 carbon atoms). 30), an aralkyl group (preferably having 7 to 30 carbon atoms), an alkylcarbonyl group (preferably having 2 to 30 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms), and the like.
These groups may further have a substituent. Examples of the substituent include a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group, an alkoxy group, and a halogen atom. Is mentioned.

In one embodiment of the present invention, R ₁ and R ₂ are preferably a hydrogen atom, an alkyl group, or a cycloalkyl group.

As described above, at least two of R ₁ , R ₂ and R ₃ may be connected to each other to form a ring. When R ₁ and R ₂ are bonded to each other to form a ring together with the nitrogen atom in the formula, a hetero atom may be further included in addition to the nitrogen atom in the formula, and the formed ring may be a single ring or a polycyclic ring. It may be a ring.

The ring formed by combining R ₁ and R ₂ together with the nitrogen atom in the formula preferably has 20 or less carbon atoms, such as pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2,5-diazabicyclo [2 2.1] heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, indole, in Groups derived from heterocyclic compounds such as phosphorus, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane, and groups derived from these heterocyclic compounds A group derived from a chain or branched alkane, a group derived from a cycloalkane, a group derived from an aromatic compound, a group derived from a heterocyclic compound, a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, Examples include a group substituted with one or more functional groups such as morpholino group and oxo group.

R ₃ represents a substituent as described above.
The substituent represented by R ₃ is preferably, for example, a hydroxyalkyl group, and examples of the hydroalkyl group include a group represented by the following general formula (1a).

In the general formula (1a), n represents an integer of 1 to 15. n is preferably 4 or 5.

In another embodiment, the substituent represented by R ₃ is preferably a group represented by the following general formula (1b).

In general formula (d-1),
X represents NH or O.
Each Ra is independently a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), an alkenyl group (preferably 2 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably Represents an aralkyl group (preferably 7 to 10 carbon atoms), or an alkoxyalkyl group (preferably 2 to 10 carbon atoms). These groups may further have a substituent, and examples of the substituent include the same specific examples as those exemplified above as the substituents which the substituent represented by R ₁ and R ₂ may have. Is mentioned.

Two Ras may be connected to each other to form a ring. One of the two Ras may be linked to R ₁ or R ₂ in the general formula (1) to form a ring.

In one embodiment of the present invention, Ra is preferably an alkyl group, a cycloalkyl group, or an alkoxyalkyl group.
Specific examples of the compound that generates a component that forms an ionic bond with the polar group include the following compounds.

In this invention, the compound which generate | occur | produces the component which forms an ion bond with a polar group may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the compound that generates a component that forms an ionic bond with the polar group in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention can be appropriately adjusted and used. The content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, still more preferably 1 to 10% by mass, and particularly preferably 2 to 10% by mass based on the total solid content of the resin composition. % By weight, particularly preferably 3 to 10% by weight.
[Resin whose solubility in organic solvents decreases due to the action of acid]
A resin whose solubility in an organic solvent is reduced by the action of an acid (hereinafter also referred to as “resin (A)”) is a resin whose polarity is changed by the action of an acid, and the solubility in an organic solvent developer by the action of an acid. And the solubility in an alkaline developer increases.

Resin (A) is a group (hereinafter also referred to as “acid-decomposable group”) that decomposes by the action of an acid to generate a polar group in the main chain or side chain of the resin, or both of the main chain and side chain. Have.

The acid-decomposable group preferably has a structure protected by a group capable of decomposing and leaving a polar group by the action of an acid.

The polar group is not particularly limited as long as it is a group that is hardly soluble or insoluble in a developer containing an organic solvent, but a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group. , Sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkyl Sulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group and other acidic groups (2.38 mass% tetramethylaure conventionally used as a resist developer) Group dissociates in mode onium hydroxide aqueous solution), or alcoholic hydroxyl group.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group). An aliphatic alcohol substituted with a functional group (for example, a fluorinated alcohol group (such as a hexafluoroisopropanol group)) is excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa of 12 or more and 20 or less.

Preferred polar groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.

A preferred group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.

Examples of the group leaving with an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), —C (R ₀₁ ) (R ₀₂ ). ) (OR ₃₉ ) and the like.

In the formula, R ₃₆ to R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The alkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl Group, octyl group and the like.

The cycloalkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. Those having 3 to 20 carbon atoms are preferred. The aryl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

The aralkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group and a naphthylmethyl group.

The alkenyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

The ring formed by combining R ₃₆ and R ₃₇ is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable, and a monocyclic cycloalkyl group having 5 carbon atoms is particularly preferable.

The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

[Repeating unit having acid-decomposable group]
The resin (A) preferably has a repeating unit having an acid-decomposable group.
In one embodiment, the resin (A) contains, as a repeating unit having an acid-decomposable group, a repeating unit (AI) that is decomposed by an acid to generate a carboxyl group (hereinafter also referred to as “repeating unit (AI)”). It is preferable to have a repeating unit represented by the following general formula (aI) or (aI ′).

In general formulas (aI) and (aI ′)
Xa ₁ represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
T represents a single bond or a divalent linking group.
Rx ₁ to Rx ₃ each independently represents an alkyl group or a cycloalkyl group. Two of Rx ₁ to Rx ₃ may combine to form a ring structure.

Examples of the divalent linking group of T include an alkylene group, —COO—Rt— group, —O—Rt— group, phenylene group and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.

T in the general formula (aI) is preferably a single bond or a —COO—Rt— group, more preferably a —COO—Rt— group, from the viewpoint of insolubilization of the resist in an organic solvent developer. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.
T in the general formula (aI ′) is preferably a single bond.

The alkyl group of _Xa1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).

The alkyl group for X _a1 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.

X _a1 is preferably a hydrogen atom or a methyl group.

The alkyl group of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl. And those having 1 to 4 carbon atoms such as t-butyl group are preferred.

Examples of the cycloalkyl group of Rx ₁ , Rx ₂ and Rx ₃ include polycyclic rings such as a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. Are preferred.

The ring structure formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ includes a monocyclic cycloalkane ring such as cyclopentyl ring and cyclohexyl ring, norbornane ring, tetracyclodecane ring, tetracyclododecane ring, adamantane ring A polycyclic cycloalkyl group such as is preferable. A monocyclic cycloalkane ring having 5 or 6 carbon atoms is particularly preferable.

Rx ₁ , Rx ₂ and Rx ₃ are preferably each independently an alkyl group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a cycloalkyl group (3 to 8 carbon atoms), a halogen atom, an alkoxy group (carbon 1 to 4), a carboxyl group, an alkoxycarbonyl group (2 to 6 carbon atoms), and the like, and 8 or less carbon atoms are preferable. Among these, from the viewpoint of further improving the dissolution contrast with respect to a developer containing an organic solvent before and after acid decomposition, a substituent having no hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom is more preferable ( For example, it is more preferable that it is not an alkyl group substituted with a hydroxyl group, etc.), a group consisting of only a hydrogen atom and a carbon atom is more preferable, and a linear or branched alkyl group or a cycloalkyl group is particularly preferable. preferable.

Specific examples of the repeating unit represented by the general formula (aI) or (aI ′) are given below, but the present invention is not limited to these specific examples.

In specific examples, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. 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 preferred examples of Z are the same as specific examples and preferred examples of the substituent that each group such as Rx ₁ to Rx ₃ may have.

In the following specific examples, Xa represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.

In one embodiment, the resin (A) preferably contains, as a repeating unit having an acid-decomposable group, a repeating unit having a total of 4 to 9 carbon atoms at the site decomposed by the acid. More preferably, in the above general formula (aI), the —C (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) moiety has 4 to 9 carbon atoms.

More preferably, in the general formula (aI), all of Rx ₁ , Rx ₂ and Rx ₃ are methyl groups or ethyl groups, or an aspect represented by the following general formula (aII).

In general formula (aII),
R ₃₁ represents a hydrogen atom or an alkyl group.
R ₃₂ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group.
R ₃₃ represents an atomic group necessary for forming a monocyclic alicyclic hydrocarbon structure together with the carbon atom to which R ₃₂ is bonded. In the alicyclic hydrocarbon structure, a part of carbon atoms constituting the ring may be substituted with a hetero atom or a group having a hetero atom.

Here, the total number of carbon atoms of R ₃₂ and R ₃₃ is 8 or less.

The alkyl group for R ₃₁ may have a substituent, and examples of the substituent include a fluorine atom and a hydroxyl group.
R ₃₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₃₂ is preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and more preferably a methyl group or an ethyl group.

The monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring.

In the monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom, examples of the hetero atom that can form the ring include an oxygen atom and a sulfur atom. Examples of the group having a hetero atom include a carbonyl group and the like. Can be mentioned. However, the group having a hetero atom is preferably not an ester group (ester bond).

The monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom is preferably formed only from the carbon atom and the hydrogen atom.

Further, in another form, the resin (A) is a repeating unit having an acid-decomposable group, the repeating unit having an acid-decomposing site containing 10 to 20 carbon atoms and a polycyclic structure. Unit (aIII) may be included.

As the repeating unit (aIII) having 10 to 20 carbon atoms in the acid decomposition site and containing a polycyclic structure in the acid decomposition site, Rx ₁ , Rx ₂ and Rx in the above general formula (aI) can be used. _In an embodiment in which one of ₃ is a group having an adamantane skeleton and the remaining two are linear or branched alkyl groups, or in general formula (aI), _{two of} Rx ₁ , Rx ₂ and Rx ₃ are bonded An embodiment in which an adamantane structure is formed and the remaining one is a linear or branched alkyl group is preferred.

Moreover, resin (A) may have a repeating unit which decomposes | disassembles by the effect | action of an acid and produces an alcoholic hydroxyl group as represented below as a repeating unit which has an acid-decomposable group.
In the following specific examples, Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

One type of repeating unit having an acid-decomposable group that can be contained in the resin (A) may be used, or two or more types may be used in combination.
When the resin (A) contains a repeating unit having two or more kinds of acid-decomposable groups, for example, in the above general formula (aI), all of Rx ₁ , Rx ₂ and Rx ₃ are methyl groups or ethyl groups The embodiment or the repeating unit of the embodiment represented by the general formula (aII) and the above-described repeating unit having 10 to 20 carbon atoms in the acid decomposition site and containing a polycyclic structure in the acid decomposition site ( A combination with a repeating unit represented by aIII) is preferred.

Preferred specific combinations in the case where the resin (A) contains two types of repeating units having an acid-decomposable group include the following.

The total amount of repeating units having an acid-decomposable group is preferably from 30 to 80 mol%, more preferably from 40 to 75 mol%, particularly preferably from 45 to 70 mol%, based on all repeating units constituting the resin (A). 50 to 70 mol% is most preferable.

The content of the repeating unit represented by the general formula (aI) is preferably from 30 to 80 mol%, more preferably from 40 to 75 mol%, more preferably from 45 to 70 mol% based on all repeating units constituting the resin (A). % Is particularly preferable, and 50 to 70 mol% is most preferable.

Further, the ratio of the repeating unit (aIII) to all repeating units having an acid-decomposable group is preferably 3 to 50 mol%, more preferably 5 to 40 mol%, and most preferably 5 to 30 mol%.

[Repeating unit having lactone structure or sultone structure]
The resin (A) may contain a repeating unit having a lactone structure or a sultone structure.

Any lactone structure or sultone structure can be used as long as it has a lactone structure or sultone structure, but a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable. Other ring structures are condensed in a form that forms a bicyclo structure or spiro structure in a membered lactone structure, or other rings that form a bicyclo structure or a spiro structure in a 5- to 7-membered ring sultone structure Those having a condensed ring structure are more preferable. A lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3), More preferably, it has a repeating unit having A lactone structure or a sultone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), especially A preferred lactone structure is (LC1-4). By using such a specific lactone structure, LER and development defects are improved.

The lactone structure portion or the sultone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, and carboxyl groups. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferred are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different. A plurality of substituents (Rb ₂ ) may be bonded to form a ring.

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

The repeating unit having a lactone structure or a sultone structure is preferably a repeating unit represented by the following general formula (III).

In the general formula (III),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).

R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof independently when there are a plurality of R ₀ .

Z is independently a single bond, an ether bond, an ester bond, an amide bond, or a urethane bond when there are a plurality of Zs.

Or urea bond

Represents. Here, each R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.

n is the number of repetitions of the structure represented by —R ₀ —Z—, and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, —R ₀ —Z— does not exist and becomes a single bond.

R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

The alkylene group and cycloalkylene group represented by R ₀ may have a substituent.

Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

The alkyl group for R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

The alkylene group of R ₀ , the cycloalkylene group, and the alkyl group in R ₇ may each be substituted. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a mercapto group, a hydroxyl group, Examples thereof include alkoxy groups such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group and benzyloxy group, and acyloxy groups such as acetyloxy group and propionyloxy group.

R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

The preferred chain alkylene group for R ₀ is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. A preferred cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group. In order to exhibit the effect of the present invention, a chain alkylene group is more preferable, and a methylene group is particularly preferable.

The monovalent organic group having a lactone structure or a sultone structure represented by R ₈ is not limited as long as it has a lactone structure or a sultone structure. Specific examples include those represented by the general formulas (LC1-1) to ( LC1-21) and a lactone structure or a sultone structure represented by any of (SL1-1) to (SL1-3), among which the structure represented by (LC1-4) is particularly preferable. Further, n ₂ in (LC1-1) to (LC1-21) is more preferably 2 or less.

R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or sultone structure, or a monovalent organic group having a lactone structure or sultone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. A monovalent organic group having a lactone structure (cyanolactone) having a cyano group as a substituent is more preferable.

Specific examples of the repeating unit having a group having a lactone structure or a sultone structure are shown below, but the present invention is not limited thereto.

In order to enhance the effect of the present invention, it is also possible to use a repeating unit having two or more lactone structures or sultone structures in combination.

When the resin (A) contains a repeating unit having a lactone structure or a sultone structure, the content of the repeating unit having a lactone structure or a sultone structure is 5 to 60 mol% with respect to all the repeating units in the resin (A). It is preferably 5 to 55 mol%, more preferably 10 to 50 mol%.

[Repeating unit having a cyclic carbonate structure]
Moreover, the resin (A) may have a repeating unit having a cyclic carbonate structure.
The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).

In general formula (A-1),
R _A ¹ represents a hydrogen atom or an alkyl group.
R _A ² each independently represents a substituent when n is 2 or more.
A represents a single bond or a divalent linking group.
Z represents an atomic group that forms a monocyclic or polycyclic structure together with a group represented by —O—C (═O) —O— in the formula.
n represents an integer of 0 or more.

The general formula (A-1) will be described in detail.
The alkyl group represented by R _A ¹ may have a substituent such as a fluorine atom. R _A ¹ preferably represents a hydrogen atom, a methyl group or a trifluoromethyl group, and more preferably represents a methyl group.

The substituent represented by R _A ² is, for example, an alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, an amino group, or an alkoxycarbonylamino group. Preferred are alkyl groups having 1 to 5 carbon atoms, such as linear alkyl groups having 1 to 5 carbon atoms; branched alkyl groups having 3 to 5 carbon atoms. The alkyl group may have a substituent such as a hydroxyl group.

N is an integer of 0 or more representing the number of substituents. n is, for example, preferably 0 to 4, more preferably 0.

Examples of the divalent linking group represented by A include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond, or a combination thereof. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 5 carbon atoms is more preferable.

In one embodiment of the present invention, A is preferably a single bond or an alkylene group.

As the monocycle containing —O—C (═O) —O— represented by Z, for example, in the cyclic carbonate represented by the following general formula (a), n _A = 2 to 4 5 To 7-membered ring, preferably 5-membered ring or 6-membered ring (n _A = 2 or 3), more preferably 5-membered ring (n _A = 2).

Examples of the polycycle containing —O—C (═O) —O— represented by Z include, for example, a cyclic carbonate represented by the following general formula (a) together with one or more other ring structures: Examples include a structure forming a condensed ring and a structure forming a spiro ring. The “other ring structure” that can form a condensed ring or a spiro ring may be an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring. .

The resin (A) may contain one of repeating units represented by the general formula (A-1) alone, or may contain two or more kinds.

In the resin (A), the content of the repeating unit having a cyclic carbonate structure (preferably, the repeating unit represented by the general formula (A-1)) is based on the total repeating units constituting the resin (A). It is preferably 3 to 80 mol%, more preferably 3 to 60 mol%, particularly preferably 3 to 30 mol%, and most preferably 10 to 15 mol%. By setting it as such a content rate, the developability as a resist, low defect property, low LWR, low PEB temperature dependence, a profile, etc. can be improved.

Specific examples of the repeating unit represented by formula (A-1) are shown below, but the present invention is not limited thereto.
Incidentally, _R ^{A 1} in the following specific examples are the same meaning as _R ^{A 1} in the general formula (A-1).

[Repeating unit having a hydroxyl group, a cyano group or a carbonyl group]
The resin (A) may have a repeating unit having a hydroxyl group, a cyano group, or a carbonyl group. This improves the substrate adhesion and developer compatibility.
However, the repeating unit represented by the following general formula (3) is preferably not contained in the resin (A) from the viewpoint of the effect of the present invention. For example, the content of the repeating unit represented by the general formula (3) is preferably 0 to 5 mol%, preferably 0 to 3 mol% with respect to all the repeating units constituting the resin (A). Is more preferable and 0 mol% is particularly preferable.

In the formula, m represents an integer of 1 to 3, and R represents a hydrogen atom or an alkyl group.
The alkyl group as R may have a substituent, which is a hydroxyl group, an alkylcosyl group, a carboxyl group, an alkoxycarbonyl group, an aminocarbonyl group, a sulfonyl group, a sulfoxyl group, a nitrile group, a nitro group, a sulfone group. It is an acid group.

The repeating unit having a hydroxyl group, a cyano group or a carbonyl group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group, a cyano group or a carbonyl group, and preferably has no acid-decomposable group. .

Further, the repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group, a cyano group or a carbonyl group is preferably different from the repeating unit having an acid-decomposable group (that is, a repeating unit which is stable with respect to an acid). Preferably).

As the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group, a cyano group or a carbonyl group, an adamantyl group, a diadamantyl group and a norbornane group are preferable.

More preferred examples include repeating units represented by any of the following general formulas (AIIa) to (AIIc). However, the repeating unit represented by the general formula (3) is excluded.

In the formula, R _X represents a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group.

Ab represents a single bond or a divalent linking group.

Examples of the divalent linking group represented by Ab include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond, or a combination thereof. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group.

In one embodiment of the present invention, Ab is preferably a single bond or an alkylene group.

Rp represents a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group. A plurality of Rp may be the same or different, but at least one of the plurality of Rp represents a hydroxyl group or a hydroxyalkyl group.

The resin (A) may or may not contain a repeating unit having a hydroxyl group, a cyano group or a carbonyl group, but the resin (A) contains a repeating unit having a hydroxyl group, a cyano group or a carbonyl group. When it contains, the content rate of the repeating unit which has a hydroxyl group, a cyano group, or a carbonyl group (except for the repeating unit represented by the general formula (3) above) is based on all repeating units in the resin (A). The amount is preferably 1 to 40 mol%, more preferably 3 to 30 mol%, still more preferably 5 to 25 mol%.

Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.

More preferably, the repeating unit which has a carbonyl group represented by the following general formula (AIIIa) or (AIIIb) can be mentioned.

In the above general formulas (AIIIa) and (AIIIb), Ac represents a single bond or a divalent linking group, and preferred examples are the repeating units represented by any one of the above general formulas (AIIa) to (AIIc) It is the same as that of Ab in the unit.

Specific examples of the repeating unit represented by the general formula (AIIIa) or (AIIIb) are shown below, but the present invention is not limited thereto.

In addition, monomers described in [0011] and thereafter of International Publication No. 2011-122336, or corresponding repeating units can be used as appropriate.

[Repeating unit having acid group]
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, a naphthol structure, and an aliphatic alcohol group (for example, hexafluoroisopropanol group) in which the α-position is substituted with an electron withdrawing group. It is more preferable to have a repeating unit having a carboxyl group. By containing the repeating unit having an acid group, the resolution in the contact hole application is increased. The repeating unit having an acid group includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an acid group in the main chain of the resin through a linking group. Either a repeating unit that is bonded, or a polymerization initiator or chain transfer agent having an acid group, is introduced at the end of the polymer chain during polymerization, and the linking group is a monocyclic or polycyclic cyclic hydrocarbon structure. You may have. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

The resin (A) may or may not contain a repeating unit having an acid group, but when it is contained, the content of the repeating unit having an acid group is relative to all the repeating units in the resin (A). It is preferably 25 mol% or less, and more preferably 20 mol% or less. When resin (A) contains the repeating unit which has an acid group, content of the repeating unit which has an acid group in resin (A) is 1 mol% or more normally.

Specific examples of the repeating unit having an acid group are shown below, but the present invention is not limited thereto.
In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

[Repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability]
The resin (A) in the present invention can further have a repeating unit that has an alicyclic hydrocarbon structure that does not have a polar group (for example, the acid group, hydroxyl group, cyano group) and does not exhibit acid decomposability. . As a result, the elution of low molecular components from the resist film to the immersion liquid during immersion exposure can be reduced, and the solubility of the resin can be appropriately adjusted during development using a developer containing an organic solvent. . Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

In general 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 a —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, particularly preferably a hydrogen atom or a methyl group.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include cycloalkenyl having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like, and cycloalkyl groups having 3 to 12 carbon atoms and cyclohexenyl group. Groups. A preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, and more preferred examples include a cyclopentyl group and a cyclohexyl group.

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings 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, tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring, and the like. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring is also included.

Preferred examples of the bridged cyclic hydrocarbon ring 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 examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

These alicyclic hydrocarbon groups may have a substituent. 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. It is done.

The resin (A) has an alicyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability. The content is preferably 1 to 50 mol%, more preferably 5 to 50 mol%, still more preferably 5 to 25 mol%, based on all repeating units in the resin (A).

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 .

[Repeating unit having an aromatic ring]
In the case where the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, or high-energy light (for example, EUV) having a wavelength of 50 nm or less, the resin (A) is represented by a hydroxystyrene repeating unit. It is preferable to have a unit having an aromatic ring.

The following can be illustrated as a specific example of resin (A) containing the repeating unit which has an aromatic ring, for example.

Resin (A) may be in an embodiment in which a structure corresponding to an acid generator described later is supported. Specifically, as such an embodiment, a structure described in JP2011-248019A (particularly, a structure described in paragraphs 0164 to 0191, a structure included in the resin described in the example in paragraph 0555). Etc. Even if the resin (A) has a structure corresponding to the acid generator, the composition of the present invention further includes an acid generator that is not supported on the resin (A) (that is, a compound described later). (B)) may be included.

Examples of the repeating unit having a structure corresponding to the acid generator include the following repeating units, but are not limited thereto.

The resin (A) used in the composition of the present invention includes, in addition to the above repeating structural units, 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 resolving power, heat resistance, sensitivity, and the like, which are general necessary characteristics.

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

Thereby, performance required for the resin used in the composition according to the present invention, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Fine adjustment such as dry etching resistance can be performed.

As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

In addition, any addition-polymerizable unsaturated compound that can be copolymerized with 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 molar ratio of each repeating structural unit is the dry etching resistance, standard developer suitability, substrate adhesion, resist profile of the actinic ray-sensitive or radiation-sensitive resin composition. Furthermore, it is appropriately set for adjusting the resolving power, heat resistance, sensitivity, etc., which are general required performances of the actinic ray-sensitive or radiation-sensitive resin composition.

When the composition of the present invention is for ArF exposure, the resin (A) used in the composition of the present invention has substantially no aromatic ring from the viewpoint of transparency to ArF light (specifically, The ratio of the repeating unit having an aromatic group in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, ideally 0 mol%, that is, no aromatic group). The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

The form of the resin (A) in the present invention may be any of random type, block type, comb type, and star type. Resin (A) is compoundable by the radical, cation, or anion polymerization of the unsaturated monomer corresponding to each structure, for example. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.

When the composition of the present invention contains a hydrophobic resin (HR) described later, the resin (A) does not contain a fluorine atom or a silicon atom from the viewpoint of compatibility with the hydrophobic resin (HR) ( Specifically, the ratio of the repeating unit having a fluorine atom or a silicon atom in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally 0 mol%.

The resin (A) used in the composition of the present invention is preferably such that all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.

The resin (A) in the present invention can be synthesized according to a conventional method (for example, by a method commonly used in the field of polymer synthesis such as radical polymerization, living radical polymerization, anion polymerization, and cation polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the photosensitive composition of the present invention. Thereby, the generation of particles during storage can be suppressed.

The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo 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, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.

After the reaction is complete, cool to room temperature and purify. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied.

For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times the volume of the reaction solution.

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 a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of polymer. A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.

The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally, 100 to 10,000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300 to 1000 parts by mass.

The temperature at the time of 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 method or a continuous method using a conventional mixing vessel such as a stirring tank.

Precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed 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).

It should be noted that once the resin is precipitated and separated, it may be dissolved again in a solvent, and the resin may be contacted with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is contacted to precipitate a resin (step a), the resin is separated from the solution (step b), and dissolved again in the solvent to obtain a resin solution A. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).

In order to prevent the resin from agglomerating after the preparation of the composition, for example, as described in JP-A-2009-037108, the synthesized resin is dissolved in a solvent to form a solution. A step of heating at about 30 ° C. to 90 ° C. for about 30 minutes to 4 hours may be added.

It is preferable to reduce unreacted low molecular components (monomers and oligomers) as much as possible by these purification steps.

The weight average molecular weight of the resin (A) in the present invention is preferably from 6000 to 50000, more preferably from 8000 to 30000, and most preferably from 10000 to 25000, in terms of polystyrene by GPC method. By setting this molecular weight range, it can be expected that the solubility in an organic developer becomes an appropriate numerical value.

The degree of dispersion (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0. Those in the range are used. The smaller the molecular weight distribution, the better the resolution and the resist shape, the smoother the sidewall of the resist pattern, and the better the roughness.

In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the blending ratio of the resin (A) in the entire composition is preferably 30 to 99% by mass, more preferably 60 to 95% by mass in the total solid content. It is.
In the present invention, the resin (A) may be used alone or in combination.
Although the specific example of resin (A) is shown below, it is not limited to these.

[Compound that generates acid upon irradiation with actinic ray or radiation]
The composition of the present invention may contain a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as “compound (B)” or “acid generator”).

In one embodiment of the present invention, examples of the acid generator include compounds represented by the following general formula (ZI), (ZII), or (ZIII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.

The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

Two of R ₂₀₁ to R ₂₀₃ may be bonded 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).

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by the general formula (ZI) is a single bond or at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by the general formula (ZI) It may be a compound having a structure bonded through a linking group.

Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).
Examples of Z ⁻ include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkyl carboxylate anion). Etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

The aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. Examples include 3 to 30 cycloalkyl groups.

The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 2 to 15 carbon atoms), an aryloxysulfonyl group (preferably a carbon atom) Number 6 to 20), alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. . The aryl group and ring structure of each group may further have an alkyl group (preferably having 1 to 15 carbon atoms) as a substituent. The aralkyl group in the aralkyl carboxylate anion is preferably 7 to 7 carbon atoms. 12 aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group and the like can be exemplified.

Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.

Examples of other Z ⁻ include fluorinated phosphorus (for example, PF ₆ ⁻ ), fluorinated boron (for example, BF ₄ ⁻ ), fluorinated antimony (for example, SbF ₆ ⁻ ), and the like.

Z ⁻ represents an aliphatic sulfonate anion substituted with a fluorine atom at least in the α-position of the sulfonic acid, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group substituted with a fluorine atom. Bis (alkylsulfonyl) imide anions and tris (alkylsulfonyl) methide anions in which the alkyl group is substituted with a fluorine atom are preferred.

In one embodiment of the present invention, the number of fluorine atoms contained in the anion as Z ⁻ is preferably 2 or 3.

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

_Examples of the organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group (preferably having 6 to 15 carbon atoms), a linear or branched alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (having 3 carbon atoms). To 15 are preferred).

Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used.

These aryl groups, alkyl groups and cycloalkyl groups as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may further have a substituent. Examples of the substituent include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.

Two selected from R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded via a single bond or a linking group. Examples of the linking group include an alkylene group (preferably having 1 to 3 carbon atoms), —O—, —S—, —CO—, —SO ₂ — and the like, but are not limited thereto.

Preferred structures when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group include paragraphs 0046 and 0047 of JP-A-2004-233661, paragraphs 0040 to 0046 of JP-A-2003-35948, US Compounds exemplified as Formulas (I-1) to (I-70) in Patent Application Publication No. 2003 / 0224288A1, and Formulas (IA-1) to (I) in US Patent Application Publication No. 2003 / 0077540A1 And cation structures such as compounds exemplified as formulas (IA-54) and formulas (IB-1) to (IB-24).

More preferred examples of the compound represented by the general formula (ZI) include compounds represented by the following general formula (ZI-3) or (ZI-4). First, the compound represented by general formula (ZI-3) is demonstrated.

In the general formula (ZI-3),
R ₁ represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or an alkenyl group,
R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R ₂ and R ₃ may be linked to each other to form a ring,
R ₁ and R ₂ may combine with each other to form a ring,
R _X and R _y each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, or an alkoxycarbonylcycloalkyl group, R _X and R _y may be connected to each other to form a ring, and this ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or an amide bond.
Z ⁻ represents a non-nucleophilic anion.

The alkyl group as R ₁ is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. Specific examples include branched alkyl groups. The alkyl group of R ₁ may have a substituent.

The cycloalkyl group as R ₁ is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom or a sulfur atom in the ring. The cycloalkyl group of R ₁ may have a substituent.

The alkoxy group as R ₁ is preferably an alkoxy group having 1 to 20 carbon atoms. The alkoxy group of R ₁ may have a substituent.

The cycloalkoxy group as R ₁ is preferably a cycloalkoxy group having 3 to 20 carbon atoms. The cycloalkoxy group for R ₁ may have a substituent.

The aryl group as R ₁ is preferably an aryl group having 6 to 14 carbon atoms. The aryl group for R ₁ may have a substituent.
Examples of the alkenyl group as R ₁ include a vinyl group and an allyl group.

R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ₂ and R ₃ may be connected to each other to form a ring. However, at least one of R ₂ and R ₃ represents an alkyl group, a cycloalkyl group, or an aryl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R ₂ and R ₃ include those similar to the specific examples and preferred examples described above for R ₁ . When R ₂ and R ₃ are connected to each other to form a ring, the total number of carbon atoms that contribute to the formation of the ring contained in R ₂ and R ₃ is preferably 4 to 7, and is preferably 4 or 5 It is particularly preferred that

R ₁ and R ₂ may be connected to each other to form a ring. When R ₁ and R ₂ are connected to each other to form a ring, R ₁ is an aryl group (preferably a phenyl group or a naphthyl group which may have a substituent), and R ₂ has 1 to 4 carbon atoms. An alkylene group (preferably a methylene group or an ethylene group) is preferable, and examples of the preferable substituent include the same substituents that the aryl group as R ₁ may have. As another form in the case where R ₁ and R ₂ are connected to each other to form a ring, it is also preferable that R ₁ is a vinyl group and R ₂ is an alkylene group having 1 to 4 carbon atoms.

The alkyl group represented by R _X and R _y is preferably an alkyl group having 1 to 15 carbon atoms.

The cycloalkyl group represented by R _X and R _y is preferably a cycloalkyl group having 3 to 20 carbon atoms.

The alkenyl group represented by R _X and R _y is preferably 2 to 30 alkenyl groups such as a vinyl group, an allyl group, and a styryl group.

The aryl group represented by R _X and R _y is, for example, an aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

The alkyl group moiety of the 2-oxoalkyl group and alkoxycarbonylalkyl group represented by R _X and R _y, for example, those previously listed as R _X and R _y.

Examples of the cycloalkyl group part of the 2-oxocycloalkyl group and alkoxycarbonylcycloalkyl group represented by R _X and R _y include those enumerated above as R _X and Ry.

Z ^- is, for example, Z in the above general formula (ZI) ^- include those listed as.

The compound represented by the general formula (ZI-3) is preferably a compound represented by the following general formulas (ZI-3a) and (ZI-3b).

In the general formulas (ZI-3a) and (ZI-3b), R ₁ , R ₂ and R ₃ are as defined in the general formula (ZI-3).

Y represents an oxygen atom, a sulfur atom or a nitrogen atom, and is preferably an oxygen atom or a nitrogen atom. m, n, p and q represent integers, preferably 0 to 3, more preferably 1 to 2, and particularly preferably 1. The alkylene group connecting S ⁺ and Y may have a substituent, and preferred examples of the substituent include an alkyl group.

R ₅ represents a monovalent organic group when Y is a nitrogen atom, and is absent when Y is an oxygen atom or a sulfur atom. R ₅ is preferably a group containing an electron withdrawing group, and particularly preferably a group represented by the following general formulas (ZI-3a-1) to (ZI-3a-4).

In the above (ZI-3a-1) to (ZI-3a-3), R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, preferably an alkyl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R include those similar to the specific examples and preferred examples described above for R ₁ in formula (ZI-3).

In the above (ZI-3a-1) to (ZI-3a-4), * represents a bond connected to a nitrogen atom as Y in the compound represented by the general formula (ZI-3a).

When Y is a nitrogen atom, R ₅ is particularly preferably a group represented by —SO ₂ —R ₄ . R ₄ represents an alkyl group, a cycloalkyl group or an aryl group, preferably an alkyl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R ₄ include those similar to the specific examples and preferred examples described above for R ₁ .

The compound represented by the general formula (ZI-3) is particularly preferably a compound represented by the following general formulas (ZI-3a ′) and (ZI-3b ′).

In the general formulas (ZI-3a ′) and (ZI-3b ′), R ₁ , R ₂ , R ₃ , Y and R ₅ are as defined in the general formulas (ZI-3a) and (ZI-3b). It is.
Z ^- is, for example, Z in the above general formula (ZI) ^- include those listed as.
Specific examples of the cation moiety of the compound represented by the general formula (ZI-3) are given below.

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

In 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 there are a plurality of R _{14 s,} each independently represents a group having 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. To express. These groups may have a substituent.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring, and the atoms constituting the ring may include heteroatoms such as an oxygen atom, a sulfur atom and a nitrogen atom. These groups may have a substituent.

l represents an integer of 0-2.
r represents an integer of 0 to 8.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ^{− in} formula (ZI).

In the general formula (ZI-4), the alkyl groups of R ₁₃ , R ₁₄ and R ₁₅ are linear or branched and preferably have 1 to 10 carbon atoms.

Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include a monocyclic or polycyclic cycloalkyl group.

The alkoxy group for R ₁₃ and R ₁₄ is preferably linear or branched and has 1 to 10 carbon atoms.

The alkoxycarbonyl group for R ₁₃ and R ₁₄ is preferably linear or branched and has 2 to 11 carbon atoms.

Examples of the group having a cycloalkyl group of R ₁₃ and R ₁₄ include a group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.

The alkyl group of the alkyl group of R _14, include the same specific examples and the alkyl group as R _{13 ~} R ₁₅ described above.

The alkylsulfonyl group and cycloalkylsulfonyl group for R ₁₄ are linear, branched, or cyclic and preferably have 1 to 10 carbon atoms.

Examples of the substituent that each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. Etc.

As the ring structure that two R ₁₅ may be bonded to each other, a 5-membered or 6-membered ring formed by two R ₁₅ together with a sulfur atom in the general formula (ZI-4), particularly preferably Includes a 5-membered ring (that is, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring), and may be condensed with an aryl group or a cycloalkyl group. This divalent R ₁₅ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group. Group, alkoxycarbonyloxy group and the like. There may be a plurality of substituents for the ring structure, or they may be bonded to each other to form a ring.

R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, or a divalent group in which two R ¹⁵ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom. A divalent group in which two R ¹⁵ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom is particularly preferable.

The substituent that R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).

l is preferably 0 or 1, and more preferably 1.
r is preferably from 0 to 2.

Specific examples of the cation structure possessed by the compound represented by the general formula (ZI-3) or (ZI-4) described above include the above-mentioned JP-A-2004-233661, JP-A-2003-35948, In addition to cationic structures such as compounds exemplified in US Patent Application Publication No. 2003 / 0224288A1 and US Patent Application Publication No. 2003 / 0077540A1, for example, paragraphs 0046 and 0047 of JP2011-53360A Cation structures in chemical structures and the like exemplified in 0072-0077 and 0107-0110, and cation structures in chemical structures exemplified in paragraphs 0135 to 0137, 0151 and 0196 to 0199 of JP2011-53430, etc. Is mentioned.

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group, or a cycloalkyl group.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ are the same as the aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the aforementioned compound (ZI).

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of this substituent include those that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the aforementioned compound (ZI) may have.

Next, a preferred structure of the non-nucleophilic anion Z ⁻ will be described.
The non-nucleophilic anion Z ⁻ is preferably a sulfonate anion represented by the general formula (2).

In general formula (2), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₇ and R ₈ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of R ₇ and R ₈ , R ₇ and R ₈ are the same But it can be different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents an organic group containing a cyclic structure.
x represents an integer of 1 to 20. y represents an integer of 0 to 10. z represents an integer of 0 to 10.

The anion of the general formula (2) will be described in more detail.
Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom as described above, and the alkyl group in the alkyl group substituted with a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms, An alkyl group having 1 to 4 carbon atoms is more preferable. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, a fluorine atom or CF ₃ is preferable. In particular, it is preferable that both Xf are fluorine atoms.

As described above, R ₇ and R ₈ represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and the alkyl group preferably has 1 to 4 carbon atoms. More preferred is a perfluoroalkyl group having 1 to 4 carbon atoms. As a specific example of the alkyl group substituted with at least one fluorine atom of R ₇ and R ₈ , CF ₃ is preferable.

L represents a divalent linking group, and represents —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, —N (Ri) — (wherein Ri represents a hydrogen atom or alkyl), an alkylene group (preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 10 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), or a plurality of these And a divalent linking group in combination of —COO—, —OCO—, —CO—, —SO ₂ —, —CON (Ri) —, —SO ₂ N (Ri) —, —CON (Ri ) -Alkylene group-, -N (Ri) CO-alkylene group-, -COO-alkylene group- or -OCO-alkylene group-, preferably -COO-, -OCO-, -SO ₂ -,- CON (Ri)-or -SO ₂ N (Ri)- Is more preferable. When there are a plurality of L, they may be the same or different.

The alkyl group as Ri is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. Specific examples include straight chain alkyl groups and branched alkyl groups. Examples of the alkyl group having a substituent include a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group, and an ethoxycarbonylmethyl group.

The organic group containing the cyclic structure of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having an aromatic attribute but also aromaticity). For example, a tetrahydropyran ring and a lactone ring structure are also included.

The alicyclic group may be monocyclic or polycyclic. Also preferred are nitrogen atom-containing alicyclic groups such as piperidine group, decahydroquinoline group, decahydroisoquinoline group. Among them, an alicyclic group having a bulky structure of 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, a decahydroquinoline group, and a decahydroisoquinoline group. And diffusibility in the film in the PEB (post-exposure heating) step can be suppressed, which is preferable from the viewpoint of improving exposure latitude.

Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Of these, naphthalene having low absorbance is preferred from the viewpoint of light absorbance at 193 nm.

Examples of the heterocyclic group include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, a furan ring, a thiophene ring, and a pyridine ring are preferable.

The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear, branched or cyclic, preferably 1 to 12 carbon atoms), aryl Group (preferably having 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group, cyano group and the like.

Note that the carbon constituting the organic group containing a cyclic structure (carbon contributing to ring formation) may be a carbonyl carbon.

X is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1. y is preferably 0 to 4, more preferably 0 or 1, and still more preferably 0. z is preferably 0 to 8, more preferably 0 to 4, and still more preferably 1.

In one embodiment of the present invention, the number of fluorine atoms contained in the anion represented by the general formula (2) is preferably 2 or 3. Thereby, the effect of the present invention can be further enhanced.

Specific examples of the sulfonate anion structure represented by the general formula (2) are given below, but the present invention is not limited thereto.

Z ⁻ is also preferably a sulfonate anion represented by the following general formula (B-1).

In the general formula (B-1),
R _b1 each independently represents a hydrogen atom, a fluorine atom or a trifluoromethyl group (CF ₃ ).

N represents an integer from 0 to 4.

N is preferably an integer of 0 to 3, more preferably 0 or 1.

X _b1 represents a single bond, an alkylene group, an ether bond, an ester bond (—OCO— or —COO—), a sulfonate ester bond (—OSO ₂ — or —SO ₃ —), or a combination thereof.

X _b1 is preferably an ester bond (—OCO— or —COO—) or a sulfonate bond (—OSO ₂ — or —SO ₃ —), and preferably an ester bond (—OCO— or —COO—). Is more preferable.

R _b2 represents an organic group having 6 or more carbon atoms.

The organic group having 6 or more carbon atoms for R _b2 is preferably a bulky group, and examples thereof include alkyl groups, alicyclic groups, aryl groups, and heterocyclic groups having 6 or more carbon atoms.

The alkyl group having 6 or more carbon atoms for R _b2 may be linear or branched, and is preferably a linear or branched alkyl group having 6 to 20 carbon atoms. Examples thereof include a linear or branched hexyl group, a linear or branched heptyl group, and a linear or branched octyl group. From the viewpoint of bulkiness, a branched alkyl group is preferable.

The alicyclic group having 6 or more carbon atoms for R _b2 may be monocyclic or polycyclic. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is used in a PEB (post-exposure heating) step. Of diffusion in membrane and MEEF (Mask)
It is preferable from the viewpoint of improving the error enhancement factor.

The aryl group having 6 or more carbon atoms for R _b2 may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. Among these, a naphthyl group having a relatively low light absorbance at 193 nm is preferable.

The heterocyclic group having 6 or more carbon atoms for R _b2 may be monocyclic or polycyclic, but polycyclic can suppress acid diffusion more. Moreover, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, and a dibenzothiophene ring. Examples of the heterocyclic ring not having aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.

The substituent having 6 or more carbon atoms for R _b2 may further have a substituent. Examples of the further substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms) and a cycloalkyl group (monocyclic, polycyclic or spiro ring). And preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group, And sulfonic acid ester groups. The carbon constituting the alicyclic group, aryl group, or heterocyclic group (carbon contributing to ring formation) may be a carbonyl carbon.

Specific examples of the sulfonate anion structure represented by formula (B-1) are shown below, but the present invention is not limited thereto. In addition, what corresponds to the sulfonate anion represented by General formula (2) mentioned above is also contained in the following specific example.

Z ⁻ is also preferably a sulfonate anion represented by the following general formula (AI).

In general formula (AI),
R ₁ is an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group, or a heteroaryl group.
R ₂ is a divalent linking group.
Rf is a fluorine atom or an alkyl group substituted with at least one fluorine atom.

n ₁ and n ₂ are each independently 0 or 1.

The alkyl group represented by R ₁ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. It is more preferable that the alkyl group has 1 to 4 carbon atoms.

The alkyl group may have a substituent (preferably a fluorine atom), and the alkyl group having a substituent is an alkyl group having 1 to 5 carbon atoms substituted with at least one fluorine atom. It is preferably a perfluoroalkyl group having 1 to 5 carbon atoms.

The alkyl group represented by R ₁ is preferably a methyl group, an ethyl group, or a trifluoromethyl group, and more preferably a methyl group or an ethyl group.

The monovalent alicyclic hydrocarbon group represented by R ₁ preferably has 5 or more carbon atoms. The monovalent alicyclic hydrocarbon group preferably has 20 or less carbon atoms, and more preferably 15 or less. The monovalent alicyclic hydrocarbon group may be a monocyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group. A part of —CH ₂ — of the alicyclic hydrocarbon group may be substituted with —O— or —C (═O) —.

The monocyclic alicyclic hydrocarbon group preferably has 5 to 12 carbon atoms, and is preferably a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group.
As the polycyclic alicyclic hydrocarbon group, those having 10 to 20 carbon atoms are preferable, and norbornyl group, adamantyl group and noradamantyl group are preferable.

The aryl group represented by R ₁ preferably has 6 or more carbon atoms. The aryl group preferably has 20 or less carbon atoms, and more preferably 15 or less.

The heteroaryl group represented by R ₁ preferably has 2 or more carbon atoms. The heteroaryl group preferably has 20 or less carbon atoms, more preferably 15 or less.

The aryl group and heteroaryl group may be a monocyclic aryl group or a monocyclic heteroaryl group, or may be a polycyclic aryl group or a polycyclic heteroaryl group.

Examples of the monocyclic aryl group include a phenyl group.
Examples of the polycyclic aryl group include a naphthyl group and an anthracenyl group.
Examples of the monocyclic heteroaryl group include a pyridyl group, a thienyl group, and a furanyl group.
Examples of the polycyclic heteroaryl group include a quinolyl group and an isoquinolyl group.

The monovalent alicyclic hydrocarbon group, aryl group, and heteroaryl group as R ₁ may further have a substituent. Examples of such a further substituent include a hydroxyl group, a halogen atom, Atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), nitro group, cyano group, amide group, sulfonamido group, alkyl group, alkoxy group, alkoxycarbonyl group, acyl group, acyloxy group, carboxy group .
R ₁ is particularly preferably a cyclohexyl group or an adamantyl group.

The divalent linking group represented by R ₂ is not particularly limited, but is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, alkylene. A group (preferably an alkylene group having 1 to 30 carbon atoms), a cycloalkylene group (preferably a cycloalkylene group having 3 to 30 carbon atoms), an alkenylene group (preferably an alkenylene group having 2 to 30 carbon atoms), an arylene group (preferably May be an arylene group having 6 to 30 carbon atoms), a heteroarylene group (preferably a heteroarylene group having 2 to 30 carbon atoms), or a group in which two or more of these are combined. The above alkylene group, cycloalkylene group, alkenylene group, arylene group and heteroarylene group may further have a substituent, and specific examples of such a substituent include a monovalent alicyclic ring as R _1. The substituents that the hydrocarbon group, aryl group, and heteroaryl group may further have are the same as those described above.

The divalent linking group represented by R ₂ is preferably an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group or a heteroarylene group, more preferably an alkylene group, and further an alkylene group having 1 to 10 carbon atoms. An alkylene group having 1 to 5 carbon atoms is preferable.

Rf is a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

Rf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More specifically, Rf is preferably a fluorine atom or CF ₃ .

n ₁ is preferably 1.

n ₂ is preferably 1.

Preferred specific examples of the sulfonate anion represented by the general formula (AI) are shown below, but the present invention is not limited thereto. In addition, what corresponds to the sulfonate anion represented by General formula (2) mentioned above is also contained in the following specific example.

The non-nucleophilic anion Z ⁻ may be a disulfonyl imido acid anion represented by the general formula (2 ′).

In general formula (2 ′),
Xf is as defined in the general formula (2), and preferred examples are also the same. In the general formula (2 ′), two Xf's may be linked to each other to form a ring structure.

Z ^- The disulfonylimide anion of, preferably a bis (alkylsulfonyl) imide anion.

The alkyl group in the bis (alkylsulfonyl) imide anion is preferably an alkyl group having 1 to 5 carbon atoms.

The two alkyl groups in the bis (alkylsulfonyl) imide anion may be linked to each other to form an alkylene group (preferably having 2 to 4 carbon atoms) and form a ring together with the imide group and the two sulfonyl groups. The ring structure that may be formed by the bis (alkylsulfonyl) imide anion is preferably a 5- to 7-membered ring, and more preferably a 6-membered ring.

These alkyl groups and alkylene groups formed by connecting two alkyl groups to each other can have a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryl Examples thereof include an oxysulfonyl group and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
Examples of the acid generator further include compounds represented by the following general formula (ZV).

In general formula (ZV),
R ₂₀₈ represents an alkyl group, a cycloalkyl group or an aryl group.

A represents an alkylene group, an alkenylene group or an arylene group.

Specific examples of the aryl group of R ₂₀₈ include the same examples as the specific examples of the aryl group as R ₂₀₁ to R ₂₀₃ in the general formula (ZI).

Specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₈ include the same examples as the specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₁ to R ₂₀₃ in the general formula (ZI).

The alkylene group of A is an alkylene group having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 carbon atoms. To 12 alkenylene groups (for example, vinylene group, propenylene group, butenylene group, etc.), and as the arylene group for A, arylene groups having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, naphthylene group, etc.) Each can be mentioned.
Examples of acid generators are listed below. However, the present invention is not limited to these.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the composition is preferably 0.1 to 30% by mass, more preferably 5 to 28% by mass, still more preferably 10 to 25% by mass, based on the total solid content of the composition. is there.

[Hydrophobic resin]
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is also referred to as a hydrophobic resin (hereinafter referred to as “hydrophobic resin (HR)” or simply “resin (HR)”), particularly when applied to immersion exposure. ) May be contained. The hydrophobic resin (HR) is preferably different from the resin (A).

As a result, the hydrophobic resin (HR) is unevenly distributed on the surface layer of the film, and when the immersion medium is water, the static / dynamic contact angle of the resist film surface with water is improved, and the immersion liquid followability is improved. be able to. In particular, when exposure is performed with EUV light, an effect of suppressing so-called outgas can be expected.

The hydrophobic resin (HR) is preferably designed to be unevenly distributed at the interface as described above. However, unlike the surfactant, the hydrophobic resin (HR) is not necessarily required to have a hydrophilic group in the molecule. There is no need to contribute to uniform mixing.

Hydrophobic resin (HR) is any one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in side chain portion of resin” from the viewpoint of uneven distribution in the surface layer of the film It is preferable to have the above, and it is more preferable to have two or more.

When the hydrophobic resin (HR) contains a fluorine atom and / or a silicon atom, the fluorine atom and / or silicon atom in the hydrophobic resin (HR) may be contained in the main chain of the resin. , May be contained in the side chain.

When the hydrophobic resin (HR) contains a fluorine atom, the partial structure having a fluorine atom is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. Preferably there is.

The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. It may have a substituent other than.

The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. .

Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The invention is not limited to this.

In general formulas (F2) to (F4),
R ₅₇ to R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). However, at least one of R ₅₇ to R _61, at least one of R ₆₂ to R ₆₄ , and at least one of R ₆₅ to R ₆₈ are each independently a fluorine atom or at least one hydrogen atom substituted with a fluorine atom. Represents an alkyl group (preferably having 1 to 4 carbon atoms).

All of R ₅₇ to R ₆₁ and R ₆₅ to R ₆₇ are preferably fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.

Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.

Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, —CH (CF ₃ ) OH and the like can be mentioned, and —C (CF ₃ ) ₂ OH is preferable.

The partial structure containing a fluorine atom may be directly bonded to the main chain, and further from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond. You may couple | bond with a principal chain through the group selected or the group which combined these 2 or more.

Hereinafter, although the specific example of the repeating unit which has a fluorine atom is shown, this invention is not limited to this.
In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ . X ₂ represents —F or —CF ₃ .

The hydrophobic resin (HR) may contain a silicon atom. The partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.

Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R ₁₂ to R ₂₆ each independently represents a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).

L ₃ to L _{5 each} represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, and a urea bond, or a combination of two or more ( Preferably, the total carbon number is 12 or less).
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

Specific examples of the repeating unit having groups represented by general formulas (CS-1) to (CS-3) will be given below, but the present invention is not limited thereto. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

Further, as described above, the hydrophobic resin (HR) also preferably includes a CH ₃ partial structure in the side chain portion.

Here, the CH ₃ partial structure possessed by the side chain moiety in the resin (HR) (hereinafter also simply referred to as “side chain CH ₃ partial structure”) has a CH ₃ partial structure possessed by an ethyl group, a propyl group, or the like. It is included.

On the other hand, a methyl group directly bonded to the main chain of the resin (HR) (for example, α-methyl group of a repeating unit having a methacrylic acid structure) causes the surface uneven distribution of the resin (HR) due to the influence of the main chain. Since the contribution is small, it is not included in the CH ₃ partial structure in the present invention.

More specifically, the resin (HR) includes a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M). In the case where R ₁₁ to R ₁₄ are CH ₃ “as is”, the CH ₃ is not included in the CH ₃ partial structure of the side chain moiety in the present invention.

Meanwhile, CH ₃ partial structure exists through some atoms from C-C backbone, and those falling under CH ₃ partial structures in the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it is assumed that it has “one” CH ₃ partial structure in the present invention.

In the general formula (M),
R ₁₁ to R ₁₄ each independently represents a side chain portion.

Examples of R ₁₁ to R _{14 in the} side chain portion include a hydrogen atom and a monovalent organic group.

Examples of the monovalent organic group for R ₁₁ to R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl. Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.

The hydrophobic resin (HR) is preferably a resin having a repeating unit having a CH ₃ partial structure in the side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II), and It is more preferable to have at least one repeating unit (x) among repeating units represented by the following general formula (V).

Hereinafter, the repeating unit represented by formula (II) will be described in detail.

In the general formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R ₂ has one or more CH ₃ partial structure represents a stable organic radical to acid. Here, the organic group that is stable to acid is more specifically an organic group that does not have the “group that decomposes by the action of an acid to generate a polar group” described in the resin (A). Is preferred.

The alkyl group of _Xb1 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.

X _b1 is preferably a hydrogen atom or a methyl group.

Examples of R ₂ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH ₃ partial structures. The above cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and aralkyl group may further have an alkyl group as a substituent.

R ₂ is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH ₃ partial structures.

The acid-stable organic group having one or more CH ₃ partial structures as R ₂ preferably has 2 or more and 10 or less CH ₃ partial structures, and more preferably 2 or more and 8 or less.

The alkyl group having one or more CH ₃ partial structures in R ₂ is preferably a branched alkyl group having 3 to 20 carbon atoms.

The cycloalkyl group having one or more CH ₃ partial structures in R ₂ may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The number of carbon atoms is preferably 6-30, and particularly preferably 7-25. Preferably, they are a norbornyl group, a cyclopentyl group, and a cyclohexyl group.

The alkenyl group having one or more CH ₃ partial structures in R ₂ is preferably a linear or branched alkenyl group having 1 to 20 carbon atoms, and more preferably a branched alkenyl group.

The aryl group having one or more CH ₃ partial structures in R ₂ is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. is there.

The aralkyl group having one or more CH ₃ partial structures in R ₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

Specific examples of the hydrocarbon group having two or more CH ₃ partial structures in R ₂ include isobutyl, t-butyl, 2-methyl-3-butyl, 2,3-dimethyl- 2-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2 , 6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group, 3,5-dimethylcyclohexyl group, 3,5-ditert-butyl A cyclohexyl group, a 4-isopropylcyclohexyl group, a 4-tbutylcyclohexyl group, and an isobornyl group.

Preferred specific examples of the repeating unit represented by the general formula (II) are shown below. Note that the present invention is not limited to this.

The repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

Hereinafter, the repeating unit represented by formula (V) will be described in detail.

In the general formula (V), X _b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, R ₃ represents an organic group that is stable against an acid having one or more CH ₃ partial structures, n represents an integer of 1 to 5.

The alkyl group of _Xb2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom is preferable.

X _b2 is preferably a hydrogen atom.

Since R ₃ is an organic group that is stable to an acid, more specifically, the organic group that does not have the “group that decomposes by the action of an acid to generate a polar group” described in the resin (A). It is preferable that

R ₃ includes an alkyl group having one or more CH ₃ partial structures.

The acid-stable organic group having one or more CH ₃ partial structures as R ₃ preferably has 1 or more and 10 or less CH ₃ partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.

The alkyl group having one or more CH ₃ partial structures in R ₃ is preferably a branched alkyl group having 3 to 20 carbon atoms.

Specific examples of the alkyl group having two or more CH ₃ partial structures in R ₃ include isopropyl group, t-butyl group, 2-methyl-3-butyl group, 2-methyl-3-pentyl. Group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl A -3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group, and a 2,6-dimethylheptyl group;

N represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.

Preferred specific examples of the repeating unit represented by the general formula (V) are shown below. Note that the present invention is not limited to this.

The repeating unit represented by the general formula (V) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

In the case where the resin (HR) contains a CH ₃ partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II) and the general formula The content of at least one repeating unit (x) among the repeating units represented by (V) is preferably 90 mol% or more, and 95 mol% or more with respect to all the repeating units of the resin (C). It is more preferable that The content is usually 100 mol% or less with respect to all repeating units of the resin (C).

The resin (HR) is a repeating unit represented by the general formula (II), and at least one repeating unit (x) among the repeating units represented by the general formula (V) is all the repeating units of the resin (HR). By containing 90 mol% or more with respect to the unit, the surface free energy of the resin (C) increases. As a result, the resin (HR) is less likely to be unevenly distributed on the surface of the resist film, so that the static / dynamic contact angle of the resist film with respect to water can be reliably improved and the immersion liquid followability can be improved.

Further, the hydrophobic resin (HR) includes the following (x) to (z) even when (i) contains a fluorine atom and / or a silicon atom, and (ii) contains a CH ₃ partial structure in the side chain portion. ) May have at least one group selected from the group of

(X) an acid group,
(Y) a group having a lactone structure, an acid anhydride group, or an acid imide group,
(Z) A group capable of decomposing by the action of an acid As the acid group (x), a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) ) Methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkyl) A carbonyl) methylene group, a tris (alkylsulfonyl) methylene group, and the like.

Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

The repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.

The content of the repeating unit having an acid group (x) is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, still more preferably 5 to 5 mol% with respect to all repeating units in the hydrophobic resin (HR). 20 mol%.

Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

As the group having a lactone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure is particularly preferable.

The repeating unit containing these groups is a repeating unit in which this group is bonded directly to the main chain of the resin, such as a repeating unit of acrylic ester and methacrylic ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.

Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the acid-decomposable resin (A).

The content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol% based on all repeating units in the hydrophobic resin (HR). The content is more preferably 3 to 98 mol%, further preferably 5 to 95 mol%.

Examples of the repeating unit having a group (z) that is decomposed by the action of an acid in the hydrophobic resin (HR) include the same repeating units having an acid-decomposable group as mentioned in the resin (A). The repeating unit having a group (z) that is decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom. In the hydrophobic resin (HR), the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol% with respect to all repeating units in the resin (HR). The amount is preferably 10 to 80 mol%, more preferably 20 to 60 mol%.

The hydrophobic resin (HR) may further have a repeating unit represented by the following general formula (VI).

In general formula (VI):
R _c31 represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom or the like), a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group containing a fluorine atom or a silicon atom.

L _c3 represents a single bond or a divalent linking group.

In general formula (VI), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.

The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.

The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and these may have a substituent.

R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.

The divalent linking group of L _c3 is preferably an alkylene group (preferably having a carbon number of 1 to 5), an ether bond, a phenylene group, or an ester bond (a group represented by —COO—).

The content of the repeating unit represented by the general formula (VI) is preferably 1 to 100 mol%, more preferably 10 to 90 mol%, based on all repeating units in the hydrophobic resin. 30 to 70 mol% is more preferable.

The hydrophobic resin (HR) preferably further has a repeating unit represented by the following general formula (CII-AB).

In the formula (CII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).

The content of the repeating unit represented by the general formula (CII-AB) is preferably 1 to 100 mol%, based on all repeating units in the hydrophobic resin, and preferably 10 to 90 mol%. More preferred is 30 to 70 mol%.

Specific examples of the repeating unit represented by the general formulas (VI) and (CII-AB) are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

When the hydrophobic resin (HR) has a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass with respect to the weight average molecular weight of the hydrophobic resin (HR), and is 10 to 80% by mass. More preferably. Further, the repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all repeating units contained in the hydrophobic resin (HR).

When the hydrophobic resin (HR) has a silicon atom, the silicon atom content is preferably 2 to 50% by mass, preferably 2 to 30% by mass, based on the weight average molecular weight of the hydrophobic resin (HR). More preferably. In addition, the repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol% in all repeating units contained in the hydrophobic resin (HR).

On the other hand, particularly when the resin (HR) includes a CH ₃ partial structure in the side chain portion, it is also preferable that the resin (HR) does not substantially contain a fluorine atom and a silicon atom. In this case, specifically, The content of the repeating unit having a fluorine atom or a silicon atom is preferably 5 mol% or less, more preferably 3 mol% or less, more preferably 1 mol based on all repeating units in the resin (HR). % Or less, ideally 0 mol%, that is, no fluorine atom and no silicon atom. Moreover, it is preferable that resin (HR) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom. More specifically, the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom may be 95 mol% or more in all the repeating units of the resin (HR). Preferably, it is 97 mol% or more, more preferably 99 mol% or more, and ideally 100 mol%.

The weight average molecular weight of the hydrophobic resin (HR) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000. is there.

Moreover, the hydrophobic resin (HR) may be used alone or in combination.
The content of the hydrophobic resin (HR) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition of the present invention. More preferably, it is 1 to 7% by mass.

The hydrophobic resin (HR), like the resin (A), naturally has few impurities such as metals, and the residual monomer and oligomer components are preferably 0.01 to 5% by mass, and more preferably Is more preferably 0.01 to 3% by mass and 0.05 to 1% by mass. As a result, an actinic ray-sensitive or radiation-sensitive resin composition that does not change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is in the range of 1-2.

As the hydrophobic resin (HR), various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.

The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as described in the resin (A), but in the synthesis of the hydrophobic resin (HR), The concentration of the reaction is preferably 30 to 50% by mass.

Specific examples of the hydrophobic resin (HR) are shown below. The following table shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

[Basic compounds]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound in order to reduce changes in performance over time from exposure to heating. Usable basic compounds are not particularly limited, and for example, compounds classified into the following (1) to (6) can be used.

(1) Basic compound (N)
Preferred examples of the basic compound include compounds (N) having structures represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and are 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). 6-20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring.

R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
Regarding the 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.

Preferable compound (N) includes guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, and more preferable compound (N) includes imidazole structure, diazabicyclo structure, onium hydroxy group. Compound (N) having an alkyl group structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, etc. be able to.

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

Preferred examples of the basic compound (N) 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. Examples of these compounds include compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of US Patent Application Publication No. 2007 / 0224539A1.
The following compounds are also preferable as the basic compound (N).

As the basic compound (N), in addition to the compounds described above, JP2011-22560A [0180] to [0225], JP2012-137735A [0218] to [0219], International Publication Pamphlet WO2011. / 158687A1 [0416] to [0438] can also be used. The basic compound (N) may be a basic compound or an ammonium salt compound whose basicity is lowered by irradiation with actinic rays or radiation.

These basic compounds (N) may be used alone or in combination of two or more.

The composition of the present invention may or may not contain the basic compound (N), but when it is contained, the content of the basic compound (N) is the actinic ray-sensitive or radiation-sensitive resin composition. Is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content.

The use ratio of the acid generator and the basic compound (N) 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 resolution from being reduced due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / basic compound (N) (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.

(2) Basic compound or ammonium salt compound (F) whose basicity is reduced by irradiation with actinic rays or radiation
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention contains a basic compound or an ammonium salt compound (hereinafter also referred to as “compound (F)”) whose basicity is lowered by irradiation with actinic rays or radiation. It is preferable to do.

The compound (F) is preferably a compound (F-1) having a basic functional group or an ammonium group and a group capable of generating an acidic functional group upon irradiation with actinic rays or radiation. That is, the compound (F) is a basic compound having a basic functional group and a group capable of generating an acidic functional group upon irradiation with actinic light or radiation, or an acidic functional group upon irradiation with an ammonium group and active light or radiation. An ammonium salt compound having a group to be generated is preferable.

Compounds with reduced basicity generated by the decomposition of compound (F) or (F-1) upon irradiation with actinic rays or radiation are represented by the following general formulas (PA-I), (PA-II) or (PAIII) In particular, from the viewpoint of achieving excellent effects on LWR, local pattern dimension uniformity and DOF at a high level, in particular, the compound represented by formula (PA-II) or (PA Compounds represented by -III) are preferred.

First, the compound represented by formula (PA-I) will be described.
QA _1- (X) _n -BR (PA-I)
In the general formula (PA-I),
A ₁ represents a single bond or a divalent linking group.
Q represents —SO ₃ H or —CO ₂ H. Q corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom or —N (Rx) —.
Rx represents a hydrogen atom or a monovalent organic group.
R represents a monovalent organic group having a basic functional group or a monovalent organic group having an ammonium group.

Next, the compound represented by formula (PA-II) will be described.
Q ₁ -X ₁ -NH-X ₂ -Q ₂ (PA-II)
In general formula (PA-II),
Q ₁ and Q ₂ each independently represents a monovalent organic group. However, either Q ₁ or Q ₂ has a basic functional group. Q ₁ and Q ₂ may combine to form a ring, and the formed ring may have a basic functional group.
X ₁ and X ₂ each independently represents —CO— or —SO ₂ —.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

Next, the compound represented by formula (PA-III) will be described.
Q ₁ -X ₁ -NH-X ₂ -A _2- (X ₃ ) _m -BQ ₃ (PA-III)
In the general formula (PA-III),
Q ₁ and Q ₃ each independently represents a monovalent organic group. However, either one of Q ₁ and Q ₃ are a basic functional group. Q ₁ and Q ₃ may combine to form a ring, and the formed ring may have a basic functional group.
X ₁ , X ₂ and X ₃ each independently represents —CO— or —SO ₂ —.
A ₂ represents a divalent linking group.
B represents a single bond, an oxygen atom or —N (Qx) —.
Qx represents a hydrogen atom or a monovalent organic group.
When B is —N (Qx) —, Q ₃ and Qx may combine to form a ring.
m represents 0 or 1.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

Hereinafter, although the specific example of a compound (F) is given, it is not limited to these. In addition to the exemplified compounds, preferred specific examples of the compound (E) include compounds (A-1) to (A-44) of US Patent Application Publication No. 2010/0233629, US Pat. (A-1) to (A-23) of 2012/0156617.

The molecular weight of the compound (F) is preferably 500 to 1,000.

The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not contain the compound (F), but when it is contained, the content of the compound (F) is actinic ray-sensitive or sensitive. The content is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on the solid content of the radiation resin composition.

Further, as one embodiment of the compound (F), a compound (F-2) that generates an acid (weak acid) having a strength that does not decompose the acid-decomposable group of the resin (A) by acid irradiation or irradiation. Can also be mentioned.

Examples of this compound include onium salts of carboxylic acids having no fluorine atom (preferably sulfonium salts), onium salts of sulfonic acids having no fluorine atoms (preferably sulfonium salts), and the like. As the cation structure of the sulfonium salt, the sulfonium cation structure mentioned in the acid generator (B) can be preferably mentioned.

More specifically, examples of the compound (F-2) include compounds described in [0170] of WO2012 / 053527A, compounds [0268] to [0269] of JP2012-173419A, and the like.

(3) Low molecular weight compound (G) having a nitrogen atom and a group capable of leaving by the action of an acid
The composition of the present invention may contain a compound having a nitrogen atom and a group capable of leaving by the action of an acid (hereinafter also referred to as “compound (G)”).

The group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.

The molecular weight of the compound (N ″) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.

The compound (G) is preferably an amine derivative having a group on the nitrogen atom that is eliminated by the action of an acid.

Compound (G) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
Rb independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group ( Preferably, it represents 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb may be connected to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are substituted with a functional group such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group, alkoxy group, or halogen atom. It may be. The same applies to the alkoxyalkyl group represented by Rb.

Rb is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.

Examples of the ring formed by connecting two Rb to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.

Specific examples of the group represented by the general formula (d-1) include a structure disclosed in paragraph [0466] of US Patent Application Publication No. 2012 / 0135348A1, and examples thereof include: It is not limited.

The compound (G) particularly preferably has a structure represented by the following general formula (6).

In the general formula (6), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, two Ras may be the same or different, and two Ras may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.

Rb has the same meaning as Rb in formula (d-1), and preferred examples are also the same.
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.

In the general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra are described above as the groups in which the alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb may be substituted. It may be substituted with a group similar to the group.

Preferred examples of the Ra alkyl group, cycloalkyl group, aryl group, and aralkyl group (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above groups) include: The same group as the preferable example mentioned above about Rb is mentioned.

In addition, the heterocyclic ring formed by connecting the Ra to each other preferably has 20 or less carbon atoms. For example, pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 1,2,3 , 4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7 Triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2,5-diazabicyclo [2.2.1] Heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, indole, indoline, 1,2 Groups derived from heterocyclic compounds such as 3,4-tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane, and groups derived from these heterocyclic compounds are linear or branched. Groups derived from alkanes, groups derived from cycloalkanes, groups derived from aromatic compounds, groups derived from heterocyclic compounds, hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups, etc. Or a group substituted with one or more of the functional groups.

Specific examples of the particularly preferable compound (G) in the present invention include compounds disclosed in paragraph [0475] of US Patent Application Publication No. 2012 / 0135348A1, but are not limited thereto. Absent.

The compound represented by the general formula (6) can be synthesized based on JP2007-298569A, JP2009-199021A, and the like.

In the present invention, the low molecular compound (G) can be used alone or in combination of two or more.

The content of the compound (G) in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably 0.001 to 20% by mass, more preferably based on the total solid content of the composition. The amount is 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

(4) Onium salt Moreover, the composition of this invention may also contain the onium salt represented by the following general formula (6A) or (6B) as a basic compound. This onium salt is expected to control the diffusion of the generated acid in the resist system in relation to the acid strength of the photoacid generator usually used in the resist composition.

In general formula (6A),
Ra represents an organic group. However, those in which a fluorine atom is substituted for a carbon atom directly bonded to a carboxylic acid group in the formula are excluded.
X ⁺ represents an onium cation.

In general formula (6B),
Rb represents an organic group. However, those in which a fluorine atom is substituted for a carbon atom directly bonded to the sulfonic acid group in the formula are excluded.
X ⁺ represents an onium cation.

In the organic group represented by Ra and Rb, the atom directly bonded to the carboxylic acid group or sulfonic acid group in the formula is preferably a carbon atom. However, in this case, in order to make the acid relatively weaker than the acid generated from the above-mentioned photoacid generator, the fluorine atom does not substitute for the carbon atom directly bonded to the sulfonic acid group or carboxylic acid group.

Examples of the organic group represented by Ra and Rb include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. Alternatively, a heterocyclic group having 3 to 30 carbon atoms can be used. In these groups, some or all of the hydrogen atoms may be substituted.

Examples of the substituent that the alkyl group, cycloalkyl group, aryl group, aralkyl group and heterocyclic group may have include a hydroxyl group, a halogen atom, an alkoxy group, a lactone group, and an alkylcarbonyl group.

Examples of the onium cation represented by X ⁺ in the general formulas (6A) and (6B) include a sulfonium cation, an ammonium cation, an iodonium cation, a phosphonium cation, and a diazonium cation. Among these, a sulfonium cation is more preferable.

As the sulfonium cation, for example, an arylsulfonium cation having at least one aryl group is preferable, and a triarylsulfonium cation is more preferable. The aryl group may have a substituent, and the aryl group is preferably a phenyl group.

Preferred examples of the sulfonium cation and the iodonium cation include the aforementioned sulfonium cation structure of the general formula (ZI) and the iodonium structure of the general formula (ZII) in the compound (B).
A specific structure of the onium salt represented by the general formula (6A) or (6B) is shown below.

When the composition of the present invention contains an onium salt represented by the general formula (6A) or (6B), the content is usually based on the solid content of the actinic ray-sensitive or radiation-sensitive resin composition. 0.01 to 10% by mass, preferably 0.1 to 5% by mass.

(5) Betaine Compound Further, the composition of the present invention includes a compound contained in the formula (I) of JP2012-189777A, a compound represented by the formula (I) of JP2013-6827A, An onium salt structure and an acid anion structure in one molecule such as a compound represented by the formula (I) of Kaikai 2013-8020 and a compound represented by the formula (I) of JP 2012-252124 A A compound having both of these (hereinafter also referred to as betaine compounds) can be preferably used. Examples of the onium salt structure include a sulfonium, iodonium, and ammonium structure, and a sulfonium or iodonium salt structure is preferable. The acid anion structure is preferably a sulfonate anion or a carboxylic acid anion. Examples of this compound include the following.

[solvent]
Examples of the solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactate alkyl ester, alkoxy An organic solvent such as alkyl propionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound having a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate, etc. Can be mentioned.

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 and a solvent not containing a hydroxyl group may be used as the organic solvent.

As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be selected as appropriate. 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), ethyl lactate is more preferred. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, 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), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate are particularly preferred, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 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 not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.

The solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate (PGMEA) single solvent or a mixed solvent containing two or more kinds of propylene glycol monomethyl ether acetate (PGMEA). Preferred specific examples of the mixed solvent include a mixed solvent containing PGMEA and a ketone solvent (cyclohexanone, 2-heptanone, etc.), a mixed solvent containing PGMEA and a lactone solvent (γ-butyrolactone, etc.), and a mixed solvent containing PGMEA and PGME. , A mixed solvent containing three types of PGMEA / ketone solvent / lactone solvent, a mixed solvent containing three types of PGMEA / PGME / lactone solvent, a mixed solvent containing three types of PGMEA / PGME / ketone solvent, etc. For example, but not limited to.

[Surfactant]
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not further contain a surfactant. When it is contained, fluorine and / or silicon-based surfactant (fluorinated 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 thereof.

When the actinic ray-sensitive or radiation-sensitive resin composition in the present invention contains a surfactant, adhesion and development defects can be obtained with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. A small resist pattern can be provided.

Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. For example, F-top EF301, EF303, (Shin-Akita Kasei Co., Ltd.) ), Florard FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by DIC Corporation), 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 (Toagosei Chemical Co., Ltd.) ), Surflon S-393 (Seimi Chemical Co., Ltd.), Ftop EF121, E 122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 230G, 218G, 218G 204D, 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

As surfactants corresponding to the above, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by DIC Corporation), acrylates having C ₆ F ₁₃ groups (or methacrylate) and (poly (oxyalkylene)) acrylate (copolymer of or methacrylate), and acrylate having a C ₃ F ₇ group (or methacrylate) (poly (oxyethylene) and) acrylate (or methacrylate) (poly ( And a copolymer with oxypropylene)) acrylate (or methacrylate).

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

These surfactants may be used alone or in some combination.

When the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, the amount of the surfactant used is preferably relative to the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). Is 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass.

On the other hand, the surface unevenness of the hydrophobic resin is increased by setting the addition amount of the surfactant to 10 ppm or less with respect to the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). The surface of the resist film can be made more hydrophobic, and the water followability during immersion exposure can be improved.

The composition of the present invention can be prepared by appropriately mixing the above components. During the preparation, a process of reducing metal impurities in the composition to the ppb level using an ion exchange membrane, a process of filtering impurities such as various particles using an appropriate filter, a deaeration process, etc. Good. Specifics of these steps are described in JP 2012-88574 A, JP 2010-189563 A, JP 2001-12529 A, JP 2001-350266 A, and JP 2002-99076 A. JP-A-5-307263, JP-A-2010-164980, WO2006 / 121162A, JP-A-2010-243866, JP-A-2010-020297, and the like.

Further, the composition of the present invention preferably has a low moisture content. Specifically, the water content is preferably 2.5% by mass or less, more preferably 1.0% by mass or less, and still more preferably 0.3% by mass or less in the total weight of the composition.

Hereinafter, the present invention will be described in detail by way of examples, but the contents of the present invention are not limited thereto.

<Resist preparation 1>
The components shown in Table 4 below were dissolved in a solvent to prepare a solution having a solid content concentration shown in the same table, and this was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare a resist solution.

<Resin (A)>
As the resin (A), P-1 to P-15 described later were used. The synthesis example of resin P-4 is shown below.

1-Cyclohexyl-1-methylethanol 22.8 g, 1,8-diazabicyclo [5,4,0] -unde-7-ene 36.5 g, water 951 mg are dissolved in N-methylpyrrolidone 590 g and cooled to 0 ° C. did. 80.7 g of 2-bromoacetyl bromide was added dropwise at 0 ° C., and the reaction mixture was stirred at room temperature for 3 hours. After the reaction mixture was cooled to 0 ° C., 300 mL of water was added, and the temperature was raised to room temperature. After stirring for 10 minutes, the aqueous phase was extracted 5 times with 100 mL of ethyl acetate. The organic phases were combined, washed with saturated multistory water and water, and then the solvent was distilled off to obtain 42.1 g of Compound 1 (yield> 99%).

41.6 g of Compound 1, 15 g of methacrylic acid, 150 mg of dibutylhydroxytoluene and 28.9 g of potassium carbonate were dissolved in 130 mL of dimethylacetamide and heated to 40 ° C. After stirring for 3 hours, the mixture was cooled to room temperature, and 300 mL of water was added. The aqueous phase was extracted 5 times with 100 mL of ethyl acetate, the organic phases were combined, washed with water, and then the solvent was distilled off. The obtained crude product was purified by silica gel chromatography (eluent: hexane / ethyl acetate = volume ratio 20/1) to obtain 42.4 g of monomer M-2 (yield> 99%%) ¹ H NMR (CDCl ₃ , 300 MHz): δ 0.96-1.28 (m, 6H), 1.43 (s, 6H), 1.65 to 1.85 (m, 5H), 1.98 (s, 3H) , 4.58 (s, 2H), 5.64 (dq, 1H), 6.21 (d, 1H).
[Synthesis of Polymer P-4]

156.6 parts by mass of cyclohexanone was heated to 80 ° C. under a nitrogen stream. While stirring this liquid, 30.6 parts by mass of monomer M-1, 48.3 parts by mass of monomer M-2, 290.7 parts by mass of cyclohexanone, dimethyl 2,2′-azobisisobutyrate [V-601, Wako Pure Chemical Industries, Ltd. [Manufactured by Kogyo Co., Ltd.] 2.05 parts by mass of a mixed solution was added dropwise over 6 hours. After completion of dropping, the mixture was further stirred at 80 ° C. for 2 hours. The reaction solution is allowed to cool, then re-precipitated with a large amount of hexane / ethyl acetate (mass ratio 7: 3), filtered, and the obtained solid is vacuum-dried to obtain 55.3 parts by mass of resin (P-4). Obtained. With respect to the obtained resin (P-4), the weight average molecular weight (Mw: converted to polystyrene), the number average molecular weight (Mn: converted to polystyrene) and the dispersity (Mw / Mn, hereinafter “Pd” were measured by GPC (solvent: THF) measurement. )) Was calculated. The composition ratio (molar ratio) was calculated by ¹ H-NMR measurement.

<Acid generator (B)>
As the acid generator (B), the following PAG-1 to PAG-16 were used.

[Compounds that generate components that form ionic bonds with polar groups]
B-1 to B-5 shown below were used as compounds that generate components that form ionic bonds with polar groups. The decomposition products of these compounds and the pKa values of their conjugate acids are also shown. The pKa shown here is a value obtained by calculation using ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08).

<Hydrophobic resin>
As the hydrophobic resin, the following 1b to 4b were used.

<Basic compound>
As basic compounds, the following compounds N-1 to N-11 were used.

<Surfactant>
As surfactants, W-1 and W-2 shown below were used.

W-1: MegaFuck F176 (Dainippon Ink & Chemicals, Inc .; fluorine-based)
W-2: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc .; fluorine system)
<Solvent>
As the solvent, those shown below were used.

SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Butyl lactate SL-3: Propylene glycol monomethyl ether (PGME)
SL-4: Cyclohexanone SL-5: γ-Butyrolactone The pattern formation method is as follows. In the following, “thermal decomposition” means thermal decomposition of a compound that generates a component that forms an ionic bond with a polar group.

<Pattern Formation 1> Examples 1 to 8, Comparative Example 1
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 having a thickness of 86 nm. On top of that, the above resist solution was applied and baked at 100 ° C. for 60 seconds. In this way, a resist film having a thickness of 85 nm was formed.

Next, an ArF excimer laser scanner (manufactured by ASML; PAS5500, NA0.75, Annular, outer sigma 0.89, inner sigma 0.65) is passed through the resist film through a 75 nm 1: 1 line and space mask. The exposure used was performed.

Then, after baking (PEB) under the conditions shown in Table 5-1, it was cooled to room temperature. Subsequently, baking for thermal decomposition was performed except for Comparative Example 1 and allowed to cool to room temperature. Then, when developing with an organic solvent developer for 20 seconds and rinsing, after rinsing with a rinsing liquid, the wafer is rotated at a rotation speed of 4000 rpm for 30 seconds to obtain a line and space of 75 nm (1: 1). A resist pattern was obtained.

<Pattern Formation 2> Examples 9 to 15 and Comparative Example 2
On the silicon wafer, an organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied and baked at 205 ° C. for 60 seconds. As a result, an antireflection film having a film thickness of 98 nm was formed on the silicon wafer. On top of this, the above resist solution was applied and baked at 90 ° C. for 60 seconds. Thereby, a resist film having a film thickness of 85 nm was formed.

The resulting resist film was subjected to pattern exposure using an ArF excimer laser immersion scanner (SMTL XT1700i, NA 1.20, C-Quad, outer sigma 0.960, inner sigma 0.709, XY deflection). went. As the reticle, a 6% halftone mask having a line size = 44 nm and a line: space = 1: 1 was used. Moreover, ultrapure water was used as the immersion liquid.
Then, after baking (PEB) under the conditions shown in Table 5-2, it was cooled to room temperature. Then, except for the comparative example 2, baking for thermal decomposition was performed and it was made to cool to room temperature. Then, it developed with the organic solvent type developing solution for 20 seconds, and when rinsed, it rinsed with the rinse solution. Next, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds to obtain a 44 nm (1: 1) line-and-space resist pattern.

<Pattern Formation 3> Examples 16 to 20, 22 and Comparative Example 3
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 having a thickness of 86 nm. On top of that, the above resist solution was applied and baked at 100 ° C. for 60 seconds. In this way, a resist film having a thickness of 50 nm was formed.

Next, an ArF excimer laser scanner (manufactured by ASML; PAS5500, NA0.75, Annular, outer sigma 0.89, inner sigma 0.65) is passed through this resist film through an 80 nm 1: 1 line and space mask. The exposure used was performed.

Then, after baking (PEB) under the conditions shown in Table 6-1, it was cooled to room temperature. Subsequently, it developed for 10 second using alkaline aqueous solution, and rinsed with the pure water for 30 second.

Next, baking for thermal decomposition was performed except for Comparative Example 3, and the mixture was cooled to room temperature. Then, when developing with an organic solvent developer for 20 seconds and rinsing, after rinsing with a rinsing liquid, the wafer is rotated for 30 seconds at a rotation speed of 4000 rpm, so that the line and space of 40 nm (1: 1) A resist pattern was obtained.

<Pattern Formation 4> Examples 23 to 28 and 30, Comparative Examples 4 and 5
On the silicon wafer, an organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied and baked at 205 ° C. for 60 seconds. As a result, an antireflection film having a film thickness of 98 nm was formed on the silicon wafer. On top of this, the above resist solution was applied and baked at 90 ° C. for 60 seconds. Thereby, a resist film having a thickness of 50 nm was formed.

The resulting resist film was subjected to pattern exposure using an ArF excimer laser immersion scanner (SMTL XT1700i, NA 1.20, C-Quad, outer sigma 0.960, inner sigma 0.709, XY deflection). went. As the reticle, a 6% halftone mask having a line size = 60 nm and a line: space = 1: 1 was used. Moreover, ultrapure water was used as the immersion liquid.
Then, after baking (PEB) under the conditions shown in Table 6-2, the mixture was cooled to room temperature. Development was carried out for 10 seconds using an aqueous alkaline solution, followed by rinsing with pure water for 30 seconds.

Subsequently, baking for thermal decomposition was performed except for Comparative Examples 4 and 5, and the mixture was cooled to room temperature. For Comparative Example 5, PEB was performed and cooled to room temperature. Then, when developing with an organic solvent developer for 20 seconds and rinsing, after rinsing with a rinsing liquid, the wafer is rotated at a rotation speed of 4000 rpm for 30 seconds, so that the line-and-space of 30 nm (1: 1) A resist pattern was obtained.

<Pattern Formation 5> Example 21
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 having a thickness of 86 nm. On top of that, the above resist solution was applied and baked at 100 ° C. for 60 seconds. In this way, a resist film having a thickness of 50 nm was formed.

Then, after baking (PEB) under the conditions shown in Table 6-1, it was cooled to room temperature. Subsequently, baking for thermal decomposition was performed and the mixture was cooled to room temperature. Then, it developed for 20 seconds with the organic solvent type developing solution, and rotated the wafer for 30 seconds at the rotation speed of 4000 rpm. Thereafter, development was performed for 10 seconds using an alkaline aqueous solution described in Table 6-1 and rinsing with pure water for 30 seconds to obtain a 40 nm (1: 1) line-and-space resist pattern.

<Pattern Formation 6> Example 29
On the silicon wafer, an organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied and baked at 205 ° C. for 60 seconds. As a result, an antireflection film having a film thickness of 98 nm was formed on the silicon wafer. On top of this, the above resist solution was applied and baked at 90 ° C. for 60 seconds. Thereby, a resist film having a thickness of 50 nm was formed.

The resulting resist film was subjected to pattern exposure using an ArF excimer laser immersion scanner (SMTL XT1700i, NA 1.20, C-Quad, outer sigma 0.960, inner sigma 0.709, XY deflection). went. As the reticle, a 6% halftone mask having a line size = 60 nm and a line: space = 1: 1 was used. Moreover, ultrapure water was used as the immersion liquid.
Then, after baking (PEB) under the conditions shown in Table 6-2, the mixture was cooled to room temperature. Subsequently, baking for thermal decomposition was performed and the mixture was cooled to room temperature. Thereafter, development was performed with an organic solvent developer for 20 seconds, and the wafer was rotated at 4000 rpm for 30 seconds. Thereafter, development was performed for 10 seconds using an alkaline aqueous solution described in the following table, followed by rinsing with pure water for 30 seconds to obtain a 40 nm (1: 1) line-and-space resist pattern.

<Evaluation method>
Evaluation was carried out by the following evaluation methods, and the results are shown in Tables 5-1, 5-2, 6-1 and 6-2.

[LWR evaluation]
The obtained line-and-space pattern was observed using a length-measuring scanning electron microscope (SEM, Hitachi, Ltd. S-9380II), and the 50-dot line width was measured at equal intervals in the range of 2 μm in the longitudinal direction of the space pattern. The measurement was performed by calculating 3σ from the standard deviation. A smaller value indicates better performance.

[Evaluation of pattern thickness]
Regarding the resist pattern formed on the silicon wafer, the wafer was divided perpendicularly to the pattern, and the side surface of the pattern was observed with a scanning electron microscope (Hitachi, Ltd. S-9380) to measure the pattern film thickness. A larger film thickness is preferable because it means that the amount of film reduction is smaller.

[Dual development pattern (DTD pattern) formation evaluation]
The resist pattern after double development was observed with a length-measuring scanning electron microscope (SEM, Hitachi, Ltd. S-9380II), and the following three-level evaluation was performed.

A: When a line and space pattern is formed without disconnection due to film slippage.

B: Line and space pattern is formed, but disconnection due to film slippage is confirmed. C: Resist film is completely dissolved and no pattern is formed.

<Resist preparation 2>
The components shown in Table 7 below were dissolved in the solvent shown in the same table so that the solid content was 1.6% by mass, and each was filtered through a polyethylene filter having a pore size of 0.05 μm. Light-sensitive or radiation-sensitive resin compositions (chemically amplified resist compositions) Ar-36 and Ar-37 were prepared.

Regarding the abbreviations in Table 7, those not described above are as follows.

<Example 31>
Compared to Example 1, the resist composition was changed to Ar-36 shown in Table 7 and the pattern was formed in accordance with Example 1 except that the exposure light source was changed to EUV light (extreme ultraviolet light). As a result of the same evaluation, it was found that a good pattern was obtained.

<Example 32>
Compared to Example 1, the resist composition was changed to Ar-37 shown in Table 7 and the pattern was formed in accordance with Example 1 except that the exposure light source was changed to EUV light (extreme ultraviolet light). As a result of the same evaluation, it was found that a good pattern was obtained.

<Example 33>
Evaluation was conducted in the same manner as in Example 15 except that a developer in which 1% by mass of n-octylamine was added to the butyl acetate developer was used. Even in this case, a good pattern could be formed.

Claims

A substrate having an actinic ray-sensitive or radiation-sensitive resin composition comprising a resin whose solubility in an organic solvent is reduced by the action of an acid, a solvent, and a compound that generates a component that forms an ionic bond with a polar group in the resin; A process of applying actinic ray-sensitive or radiation-sensitive film by coating on the surface;
-Exposing the actinic ray-sensitive or radiation-sensitive film; and
A pattern forming method comprising: developing the actinic ray-sensitive or radiation-sensitive film exposed using a developer containing an organic solvent to form a negative pattern;
The pattern forming method according to claim 1, further comprising a step of developing using an alkali developer to form a positive pattern.
Each of the steps included in the pattern forming method according to claim 1 is included in the order as described, and further, the step of developing using an alkali developer to form a positive pattern includes the exposure step and the organic solvent. The pattern forming method according to claim 1, wherein the pattern forming method is included during the developing step using the developer.
The pattern forming method according to claim 1, further comprising a step of decomposing the compound that generates a component that forms an ionic bond with a polar group.
A process comprising the steps included in the pattern forming method according to claim 1 in the order as described, and further comprising the step of decomposing the compound generating a component that forms an ionic bond with the polar group, the exposure step and the organic step The pattern forming method according to claim 1, wherein the pattern forming method is included during the developing step using a developer containing a solvent.
4. The pattern forming method according to claim 3, wherein a component that forms an ionic bond with a polar group is generated between the developing step using an alkali developer and the developing step using a developer containing an organic solvent. A pattern forming method, further comprising the step of decomposing the compound.
5. The pattern forming method according to claim 4, wherein decomposition of the compound that generates a component that forms an ionic bond with the polar group is performed by heating.
The pattern forming method according to claim 7, wherein the heating is performed at a temperature of 120 ° C. or more.
The pattern forming method according to claim 1, wherein the exposure is performed through an immersion liquid.
The pattern forming method according to claim 1, wherein the compound that generates a component that forms an ionic bond with a polar group is represented by the following general formula (1).

Where
R 1 and R 2 each independently represents a hydrogen atom or a substituent.
R 3 represents a substituent.
At least two of R 1 , R 2 and R 3 may be connected to each other to form a ring.
An actinic ray-sensitive or radiation-sensitive resin comprising: a resin whose solubility in an organic solvent is reduced by the action of an acid; a solvent; and a compound that generates a component that forms an ionic bond with a polar group in the resin. Composition.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 11, wherein the compound that generates a component that forms an ionic bond with a polar group is represented by the following general formula (1).

Where
R 1 and R 2 each independently represents a hydrogen atom or a substituent.
R 3 represents a substituent.
At least two of R 1 , R 2 and R 3 may be connected to each other to form a ring.
The content of the compound that generates a component that forms an ionic bond with a polar group is 2 to 10% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 11.
An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive composition according to claim 11.
An electronic device manufacturing method including the pattern forming method according to claim 1.
An electronic device manufactured by the electronic device manufacturing method according to claim 15.