JP6653330B2 - Pattern forming method, electronic device manufacturing method, and laminate - Google Patents

Description

The present invention relates to a pattern forming method, a method for manufacturing an electronic device, and a laminate.
More specifically, the present invention relates to a pattern that can be used in a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit substrate such as a liquid crystal and a thermal head, and a lithography process in other photo applications. The present invention relates to a forming method, a method for manufacturing an electronic device including the pattern forming method, and a laminate.

  2. Description of the Related Art Conventionally, in a process of manufacturing a semiconductor device such as an IC or an LSI (Large Scale Integrated circuit), fine processing by lithography using a resist composition is performed.

  Patent Documents 1 and 2 disclose providing an upper layer film containing an additive on a resist film.

JP 2008-65304 A Japanese Patent Application Laid-Open No. 2010-160283

  However, there is room for study on the resolution in forming an extremely fine residual pattern (for example, a dot pattern with a diameter of 30 nm or less, a line and space pattern with a line width of 30 nm or less, etc.). In particular, when an extremely fine residual pattern is formed using extreme ultraviolet light, it is preferable to use a dark mask having a large number of light-shielding portions in consideration of the influence of flare light. Although a method is conceivable, in forming an extremely fine residual pattern, it is easy to reduce the film thickness of the pattern, and it is difficult to obtain high resolution.

  The present invention relates to a pattern forming method capable of obtaining a high resolution with a small film loss, particularly in forming an extremely fine residual pattern (for example, a dot pattern having a diameter of 30 nm or less or a line and space pattern having a line width of 30 nm or less). An object of the present invention is to provide a method for manufacturing an electronic device including the pattern forming method, and a laminate for forming the pattern.

The present inventors have found that the above problem can be solved by the following means.
<1>
(A) forming an actinic ray-sensitive or radiation-sensitive film with the actinic ray-sensitive or radiation-sensitive resin composition;
(B) a step of forming an upper film on the actinic ray-sensitive or radiation-sensitive film with the composition for forming an upper film;
(C) exposing the actinic ray-sensitive or radiation-sensitive film having the upper layer film formed thereon, and (d) developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer. A pattern forming method comprising:
The actinic ray-sensitive or radiation-sensitive resin composition contains a resin containing a repeating unit having an aromatic ring, and a photoacid generator,
The resin containing a repeating unit having an aromatic ring is a resin containing a repeating unit having a phenolic hydroxyl group,
The compound for forming the upper layer film, which does not generate an acid by actinic rays or radiation and has a molecular weight of 5,000 or less, comprises 1% by mass or more and 40% by mass based on the total solid content of the composition for forming the upper layer film. Including
The compound (Q) is at least one compound selected from the following X1 to X6, TQ-1 to TQ-18, and A-1 to A-35,
The composition for forming an upper layer film contains a solvent, and the solvent is an alcohol solvent, an ether solvent, an ester solvent, a fluorine solvent, a hydrocarbon solvent, or an organic solvent obtained by mixing a plurality of these solvents. The solvent contained in the film-forming composition may or may not contain a solvent having a hydroxyl group, and when containing a solvent having a hydroxyl group, the content ratio of the solvent having a hydroxyl group to the total solvent. Is 50% by mass or less.

X3: tri-N-octylamine, X4: 1- (tert-butoxycarbonyl) -4-hydroxypiperidine, X5: tert-butyl 1-pyrrolidinecarboxylate, X6: triisopropanolamine






<2>
The pattern forming method according to <1>, wherein the compound (Q) has a molecular weight of 1500 or less.
<3>
The pattern forming method according to <1> or <2>, wherein the content of the compound (Q) is 30% by mass or less based on the total solid content of the composition for forming an upper layer film.
<4>
The pattern forming method according to <1> or <2>, wherein the content of the compound (Q) is 20% by mass or less based on the total solid content of the composition for forming an upper layer film.
<5>
The pattern forming method according to <1>, wherein the compound (Q) is at least one compound selected from the above TQ-1 to TQ-18, A-22 to A-27, and A-33.
<6>
The pattern forming method according to any one of <1> to <5>, wherein the content of the organic solvent is 50% by mass or more based on all solvents contained in the composition for forming an upper layer film.
<7>
The pattern forming method according to any one of <1> to <6>, wherein the actinic ray-sensitive or radiation-sensitive resin composition contains a crosslinking agent.
<8>
The pattern forming method according to any one of <1> to <7>, wherein the developer is a developer containing an organic solvent.
<9>
<8> The pattern forming method according to <8>, wherein the developer containing an organic solvent includes at least one solvent selected from an ester solvent, a ketone solvent, an ether solvent, and a hydrocarbon solvent.
<10>
The pattern forming method according to <9>, wherein the developer containing the organic solvent contains an ester solvent.
<11>
After the above step (d),
(E) rinsing the developed actinic ray-sensitive or radiation-sensitive film with a rinsing liquid,
The pattern forming method according to any one of <1> to <10>, wherein the rinsing liquid contains a hydrocarbon-based solvent.
<12>
The pattern forming method according to any one of <1> to <11>, wherein the exposure is performed using an electron beam or extreme ultraviolet light.
<13>
A method for manufacturing an electronic device, comprising the pattern forming method according to any one of <1> to <12>.
<14>
A laminate comprising an actinic ray-sensitive or radiation-sensitive film and an upper layer film,
The actinic ray-sensitive or radiation-sensitive film includes a resin containing a repeating unit having an aromatic ring, and a photoacid generator,
The resin containing a repeating unit having an aromatic ring is a resin containing a repeating unit having a phenolic hydroxyl group,
The upper layer film contains a compound (Q) having a molecular weight of 5,000 or less, which does not generate an acid by actinic rays or radiation, in an amount of 1% by mass to 40% by mass based on the total mass of the upper layer film,
The above compound (Q) is at least one compound selected from the lower Symbol T Q-1~TQ-18, A -22~A-27 and A-33,, laminate.



Although the present invention relates to the above <1> to <14>, other matters are also described in this specification for reference.

[1]
(A) forming an actinic ray-sensitive or radiation-sensitive film with the actinic ray-sensitive or radiation-sensitive resin composition;
(B) a step of forming an upper film on the actinic ray-sensitive or radiation-sensitive film with the composition for forming an upper film;
(C) exposing the actinic ray-sensitive or radiation-sensitive film having the upper layer film formed thereon, and (d) developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer. A pattern forming method comprising:
The actinic ray-sensitive or radiation-sensitive resin composition contains a resin containing a repeating unit having an aromatic ring,
The compound for forming the upper layer film, which does not generate an acid by actinic rays or radiation and has a molecular weight of 5,000 or less, comprises 1% by mass or more and 40% by mass based on the total solid content of the composition for forming the upper layer film. A pattern forming method including the following.
[2]
The pattern forming method according to [1], wherein the compound (Q) has a molecular weight of 1500 or less.
[3]
The pattern forming method according to [1] or [2], wherein the content of the compound (Q) is 30% by mass or less based on the total solid content of the composition for forming an upper layer film.
[4]
The pattern forming method according to any one of [1] to [3], wherein the content of the compound (Q) is 20% by mass or less based on the total solid content of the composition for forming an upper layer film.
[5]
The pattern forming method according to any one of [1] to [4], wherein the composition for forming an upper layer film contains an organic solvent.
[6]
The pattern forming method according to [5], wherein the content of the organic solvent is 50% by mass or more based on all the solvents contained in the composition for forming an upper layer film.
[7]
The composition for forming an upper layer film contains a solvent, and the content ratio of the solvent having a hydroxyl group to the total solvent contained in the composition for forming an upper layer film is 50% by mass or less, [1] to [6]. ] The pattern formation method as described in any one of the above.
[8]
The pattern forming method according to any one of [1] to [7], wherein the actinic ray-sensitive or radiation-sensitive resin composition contains a crosslinking agent.
[9]
The pattern forming method according to any one of [1] to [8], wherein the developer is a developer containing an organic solvent.
[10]
The pattern forming method according to [9], wherein the developer containing the organic solvent includes at least one solvent selected from an ester solvent, a ketone solvent, an ether solvent, and a hydrocarbon solvent.
[11]
The pattern forming method according to [10], wherein the developer containing an organic solvent contains an ester solvent.
[12]
After the above step (d),
(E) rinsing the developed actinic ray-sensitive or radiation-sensitive film with a rinsing liquid,
The pattern forming method according to any one of [1] to [11], wherein the rinsing liquid contains a hydrocarbon-based solvent.
[13]
The pattern forming method according to any one of [1] to [12], wherein the exposure is performed using an electron beam or extreme ultraviolet light.
[14]
A method for manufacturing an electronic device, comprising the pattern forming method according to any one of [1] to [13].
[15]
A laminate comprising an actinic ray-sensitive or radiation-sensitive film and an upper layer film,
The actinic ray-sensitive or radiation-sensitive film contains a resin containing a repeating unit having an aromatic ring,
A laminate, wherein the upper layer film contains a compound (Q) having a molecular weight of 5,000 or less, which does not generate an acid by actinic rays or radiation, in an amount of 1% by mass to 40% by mass based on the total mass of the upper layer film.

  According to the present invention, particularly in the formation of an extremely fine pattern (for example, a dot or a line and space having a diameter of 30 nm or less), a pattern forming method capable of obtaining a high resolution with a small film loss and an electronic device including the pattern forming method A device manufacturing method and a laminate for forming the pattern can be provided.

Hereinafter, embodiments for carrying out the present invention will be described.
In addition, in the description of the group (atomic group) in this specification, the notation that does not indicate substituted or unsubstituted includes not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The term “actinic ray” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, the term “exposure” in the present specification means not only exposure using far-ultraviolet rays such as a mercury lamp and an excimer laser, X-rays, and EUV light, but also drawing using particle beams such as electron beams and ion beams. Is also included in the exposure.
In this specification, "(meth) acrylic monomer" means at least one monomer having the structure of _"CH 2 = _CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " I do. Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.
In this specification, a molecular weight is represented by a weight average molecular weight when it has a distribution.
In the present specification, the weight average molecular weight of the resin is a value in terms of polystyrene measured by a GPC (gel permeation chromatography) method. GPC uses HLC-8120 (manufactured by Tosoh Corporation), and uses TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID × 30.0 cm) as a column and THF (tetrahydrofuran) as an eluent. You can follow the method you used.

<Pattern forming method>
The pattern forming method of the present invention comprises:
(A) forming an actinic ray-sensitive or radiation-sensitive film with the actinic ray-sensitive or radiation-sensitive resin composition;
(B) a step of forming an upper film on the actinic ray-sensitive or radiation-sensitive film with the composition for forming an upper film;
(C) exposing the actinic ray-sensitive or radiation-sensitive film having the upper layer film formed thereon, and (d) developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer. A pattern forming method comprising:
The actinic ray-sensitive or radiation-sensitive resin composition contains a resin containing a repeating unit having an aromatic ring,
The compound for forming the upper layer film, which does not generate an acid by actinic rays or radiation and has a molecular weight of 5,000 or less, comprises 1% by mass or more and 40% by mass based on the total solid content of the composition for forming the upper layer film. A pattern forming method including the following.

<Step (a)>
Step (a) of the pattern forming method of the present invention is a step of forming an actinic ray-sensitive or radiation-sensitive film with an actinic ray-sensitive or radiation-sensitive resin composition, and preferably, an actinic ray-sensitive film on a substrate. This is a step of forming an actinic ray-sensitive or radiation-sensitive film by applying a photosensitive or radiation-sensitive resin composition.
The actinic ray-sensitive or radiation-sensitive resin composition is preferably a resist composition, and the actinic ray-sensitive or radiation-sensitive film is preferably a resist film.

[Actinic ray-sensitive or radiation-sensitive resin composition]
In the pattern forming method of the present invention, it is preferable that an actinic ray-sensitive or radiation-sensitive resin composition is applied on a substrate to form an actinic ray-sensitive or radiation-sensitive film.
The actinic ray-sensitive or radiation-sensitive resin composition is an actinic ray-sensitive or radiation-sensitive resin composition for organic solvent development using a developer containing an organic solvent and / or alkali development using an alkali developer. It is preferred that Here, “for organic solvent development” means a use provided in a step of developing using at least a developer containing an organic solvent. The term "for alkali development" means at least the use provided in the step of developing using an alkali developer.
The actinic ray-sensitive or radiation-sensitive resin composition is preferably a resist composition, and more preferably a chemically amplified resist composition. The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may be a positive resist composition or a negative resist composition, but is preferably a negative resist composition.
The radiation-sensitive or actinic ray-sensitive composition of the present invention is preferably used for electron beam or extreme ultraviolet exposure.

<(A) Resin containing repeating unit having aromatic ring>
The actinic ray-sensitive or radiation-sensitive resin composition contains a resin containing a repeating unit having an aromatic ring (also referred to as “resin (A)”).
The resin (A) preferably has a repeating unit (a) having an aromatic ring group and a repeating unit (b) having a silicon atom in a side chain.

[Repeating unit (a) having aromatic ring group]
As the repeating unit (a) having an aromatic ring group, a repeating unit having a phenolic hydroxyl group can be preferably exemplified.
In the present specification, the phenolic hydroxyl group is a group formed by replacing a hydrogen atom of an aromatic ring group with a hydroxy group. The aromatic ring of the aromatic ring group is a monocyclic or polycyclic aromatic ring, such as a benzene ring or a naphthalene ring.

  In particular, when the actinic ray-sensitive or radiation-sensitive resin composition contains a crosslinking agent described below (for example, the actinic ray-sensitive or radiation-sensitive resin composition is a negative resist composition for alkali development. In the case, the resin (A) preferably has a repeating unit having a phenolic hydroxyl group.

  Examples of the repeating unit having a phenolic hydroxyl group include a repeating unit represented by the following general formula (I) or (I-1).

Where:
R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₄₂ may combine with Ar ₄ to form a ring, in which case R ₄₂ represents a single bond or an alkylene group.
X ₄ represents a single bond, —COO—, or —CONR ₆₄ —, and R ₆₄ represents a hydrogen atom or an alkyl group.
L ₄ each independently represents a single bond or a divalent linking group.
Ar ₄ represents a (n + 1) -valent aromatic ring group, and when it is bonded to R ₄₂ to form a ring, represents an (n + 2) -valent aromatic ring group.
n represents an integer of 1 to 5.
For the purpose of increasing the polarity of the repeating unit of the general formula (I) or (I-1), it is also preferable that n is an integer of 2 or more, or X ₄ is —COO— or —CONR ₆₄ —.

As the alkyl group of R ₄₁ , R ₄₂ and R _{43 in} the general formulas (I) and (I-1), preferably an optionally substituted methyl group, ethyl group, propyl group, isopropyl group, n Alkyl groups having 20 or less carbon atoms such as -butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, and particularly preferably alkyl groups having 8 or less carbon atoms. And 3 or less alkyl groups.

The cycloalkyl group of R ₄₁ , R ₄₂ and R _{43 in} the general formulas (I) and (I-1) may be a monocyclic type or a polycyclic type. Preferably, a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent is exemplified.
Examples of the halogen atom of R ₄₁ , R ₄₂ and R _{43 in} the general formulas (I) and (I-1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferred.
As the alkyl group contained in the alkoxycarbonyl group of R ₄₁ , R ₄₂ , and R _{43 in} the general formulas (I) and (I-1), the same alkyl groups as those described above for R ₄₁ , R ₄₂ , and R ₄₃ are preferable. .

  Preferred substituents in each of the above groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, and an acyl group. Groups, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group and the like, and the substituent preferably has 8 or less carbon atoms.

Ar ₄ represents an (n + 1) -valent aromatic ring group. The divalent aromatic ring group in the case where n is 1 may have a substituent, for example, a phenylene group, a tolylene group, a naphthylene group, an arylene group having 6 to 18 carbon atoms such as an anthracenylene group, or For example, an aromatic ring group containing a hetero ring such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole can be mentioned as a preferable example.

When n is an integer of 2 or more, specific examples of the (n + 1) -valent aromatic ring group include the above-described specific examples of the divalent aromatic ring group obtained by removing (n-1) arbitrary hydrogen atoms. Preferred groups can be mentioned.
The (n + 1) -valent aromatic ring group may further have a substituent.

Examples of the substituent which the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group and (n + 1) -valent aromatic ring group may have include, for example, the alkyl groups mentioned for R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I). Groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups and other alkoxy groups; phenyl groups and other aryl groups;
_-CONR 64 represented by X ₄ - _{(R 64} represents a hydrogen atom, an alkyl group) The alkyl group for _{R 64} in, preferably an optionally substituted methyl group, an ethyl group, a propyl group An isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, an alkyl group having 20 or less carbon atoms such as a dodecyl group, and more preferably an alkyl group having 8 or less carbon atoms. No.
X ₄ is preferably a single bond, —COO—, or —CONH—, more preferably a single bond or —COO—.

The divalent linking group as L ₄ is preferably an alkylene group, and the alkylene group is preferably an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group. And octylene groups having 1 to 8 carbon atoms.
As Ar ₄ , an aromatic ring group having 6 to 18 carbon atoms which may have a substituent is more preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are particularly preferable.
The repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. That is, Ar ₄ is preferably a benzene ring group.

  The repeating unit having a phenolic hydroxyl group contained in the resin (A) preferably includes a repeating unit represented by the following general formula (p1).

  R in the general formula (p1) represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of Rs may be the same or different. As R in the general formula (p1), a hydrogen atom is particularly preferred.

  Ar in the general formula (p1) represents an aromatic ring, for example, an aromatic hydrocarbon which may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring and a phenanthrene ring. A hydrogen ring, or, for example, a hetero ring such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring; And aromatic heterocycles. Among them, a benzene ring is most preferable.

  M in the general formula (p1) represents an integer of 1 to 5, and is preferably 1.

  Hereinafter, specific examples of the repeating unit having a phenolic hydroxyl group included in the resin (A) will be shown, but the present invention is not limited thereto. In the formula, a represents 1 or 2.

  The resin (A) may have one type of the repeating unit (a) having a phenolic hydroxyl group, or may have two or more types of the repeating unit (a).

  The content of the repeating unit (a) having a phenolic hydroxyl group is preferably from 10 to 95 mol%, more preferably from 20 to 90 mol%, based on all repeating units of the resin (A). More preferably, it is 30 to 85 mol%.

  The repeating unit (a) having an aromatic ring group may be a repeating unit represented by the following general formula (X).

In the general formula (X),
R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₆₃ may be bonded to Ar to form a ring, in which case R ₆₂ represents a single bond or an alkylene group.
Ar is, (n + 1) -valent aromatic ring group, in the case of combining with R ₆₂ form a ring (n + 2) -valent aromatic ring group.
R ₇ is independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (—OCOR or -COOR: R represents an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group.
n represents an integer of 0 or more.

  The following general formula (X) is also preferably a repeating unit represented by the following general formula (V) or the following general formula (VI).

Wherein, _{n 3} is an integer of 0-4. n ₄ represents an integer of 0 to 6.
X ₄ is a methylene group, an oxygen atom or a sulfur atom.
R ₇ has the same meaning as _{R 7} in the general formula (X).

  Specific examples of the repeating unit represented by the general formula (X) are shown below, but are not limited thereto.

  The resin (A) may have one type of the repeating unit (a) represented by the general formula (X), or may have two or more types of the repeating unit (a).

  The content of the repeating unit represented by the general formula (X) is preferably from 5 to 50 mol%, more preferably from 5 to 40 mol%, based on all the repeating units of the resin (A). And more preferably 5 to 30 mol%.

  The repeating unit (a) having an aromatic ring group is a repeating unit (c) having a structure in which a polar group to be described later is protected by a leaving group which is decomposed and eliminated by the action of an acid and has an aromatic ring group. It may be something.

  The resin (A) may have one type of the repeating unit (a) having an aromatic ring group, or may have two or more types of the repeating unit (a).

  The content of the repeating unit (a) having an aromatic ring group is preferably from 5 to 100 mol%, more preferably from 7 to 98 mol%, based on all repeating units of the resin (A). More preferably, it is 8 to 96 mol%.

[Repeating unit having silicon atom in side chain (b)]
The repeating unit (b) having a silicon atom in the side chain is not particularly limited as long as it has a silicon atom in the side chain. Examples thereof include a (meth) acrylate-based repeating unit having a silicon atom and a vinyl-based repeating unit having a silicon atom. And the like.
The repeating unit (b) having a silicon atom is preferably a repeating unit having no structure (acid-decomposable group) in which a polar group is protected by a leaving group which is decomposed and eliminated by the action of an acid.

The repeating unit (b) having a silicon atom in the side chain is typically a repeating unit having a group having a silicon atom in the side chain. Examples of the group having a silicon atom include a trimethylsilyl group and a triethylsilyl group. , Triphenylsilyl group, tricyclohexylsilyl group, tristrimethylsiloxysilyl group, tristrimethylsilylsilyl group, methylbistrimethylsilylsilyl group, methylbistrimethylsiloxysilyl group, dimethyltrimethylsilylsilyl group, dimethyltrimethylsiloxysilyl group, or as described below A cyclic or linear polysiloxane, or a cage-type, ladder-type, or random-type silsesquioxane structure. In the formula, R and R ¹ each independently represent a monovalent substituent. * Represents a bond.

  Preferred examples of the repeating unit having the above group include a repeating unit derived from an acrylate or methacrylate compound having the above group and a repeating unit derived from a compound having the above group and a vinyl group.

The repeating unit having a silicon atom is preferably a repeating unit having a silsesquioxane structure, whereby it is ultrafine (for example, a line width of 50 nm or less) and has a high aspect ratio (for example, a line width of 50 nm or less). In the formation of a pattern having a film thickness / line width of 2 or more, extremely excellent falling performance can be exhibited.
Examples of the silsesquioxane structure include a cage-type silsesquioxane structure, a ladder-type silsesquioxane structure (ladder-type silsesquioxane structure), and a random silsesquioxane structure. Among them, a cage silsesquioxane structure is preferable.
Here, the cage silsesquioxane structure is a silsesquioxane structure having a cage-like skeleton. The cage silsesquioxane structure may be a complete cage silsesquioxane structure or an incomplete cage silsesquioxane structure, but may be a complete cage silsesquioxane structure. preferable.
The ladder-type silsesquioxane structure is a silsesquioxane structure having a ladder-like skeleton.
The random silsesquioxane structure is a silsesquioxane structure having a random skeleton.

  The cage silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).

In the above formula (S), R represents a monovalent substituent. A plurality of Rs may be the same or different.
The monovalent substituent is not particularly limited, but specific examples include a halogen atom, a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an amino group, a mercapto group, and a blocked mercapto group (for example, a block with an acyl group ( Protected) mercapto group), acyl group, imide group, phosphino group, phosphinyl group, silyl group, vinyl group, hydrocarbon group optionally having a hetero atom, (meth) acryl group-containing group and epoxy group-containing And the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Examples of the hetero atom of the hydrocarbon group which may have a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.
Examples of the hydrocarbon group of the hydrocarbon group which may have a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof.
The aliphatic hydrocarbon group may be linear, branched, or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly 1 to 30 carbon atoms), a linear or branched alkenyl group (particularly 2 to 30 carbon atoms), Examples thereof include a linear or branched alkynyl group (particularly, having 2 to 30 carbon atoms).
Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

  The repeating unit having a silicon atom is preferably represented by the following formula (I).

In the above formula (I), L represents a single bond or a divalent linking group.
Examples of the divalent linking group include an alkylene group, a -COO-Rt- group, a -O-Rt- group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
L is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, a — (CH ₂ ) ₂ — group, or a — (CH ₂ ) ₃ — group.
In the above formula (I), X represents a hydrogen atom or an organic group.
Examples of the organic group include an alkyl group which may have a substituent such as a fluorine atom and a hydroxyl group, and a hydrogen atom, a methyl group, a trifluoromethyl group, and a hydroxymethyl group are preferable.
In the above formula (I), A represents a silicon atom-containing group. Among them, a group represented by the following formula (a) or (b) is preferable.

  In the above formula (a), R represents a monovalent substituent. A plurality of Rs may be the same or different. Specific examples and preferred embodiments of R are the same as those in the above formula (S). In addition, when A in the above formula (I) is a group represented by the above formula (a), the above formula (I) is represented by the following formula (Ia).

In the above formula (b), R _b represents a hydrocarbon group which may have a hetero atom. Specific examples and preferred embodiments of the hydrocarbon group which may have a hetero atom are the same as those of R in the above formula (S).

The resin (A) may have one type of repeating unit having a silicon atom, or may have two or more types of repeating units.
The content of the repeating unit having a silicon atom is preferably from 1 to 30 mol%, more preferably from 1 to 20 mol%, and even more preferably from 1 to 10 mol%, based on all repeating units of the resin (A). % Is more preferable.

  In the specification of the present application, a repeating unit having a silicon atom and a structure (an acid-decomposable group) in which a polar group is protected by a leaving group which is decomposed and eliminated by the action of an acid is a repeating unit having a silicon atom This also applies to the repeating unit having an acid-decomposable group.

[A repeating unit (c) having a structure in which a polar group is protected by a leaving group which is decomposed and eliminated by the action of an acid]
In a preferred embodiment, the resin (A) has a repeating unit (c) having a structure in which a polar group is protected by a leaving group which is decomposed and eliminated by the action of an acid.
As the polar group in the repeating unit (c) having a structure (acid-decomposable group) protected by a leaving group in which the polar group is decomposed and eliminated by the action of an acid, a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, And a sulfonic acid group. Among these, the polar group is preferably a carboxyl group, an alcoholic hydroxyl group, or a phenolic hydroxyl group, and more preferably a carboxyl group or a phenolic hydroxyl group.
When the resin (A) has a repeating unit having an acid-decomposable group, the solubility in an alkali developing solution increases due to the action of an acid, and the solubility in an organic solvent decreases.

Examples of the leaving group that is decomposed and eliminated by the action of an acid include groups represented by formulas (Y1) to (Y4).
Formula (Y1): -C (Rx ₁ ) (Rx ₂ ) (Rx ₃ )
Formula _{(Y2): - C (=} O) O (Rx 1) (Rx 2) (Rx 3)
Formula _{(Y3): - C (R} 36) (R 37) (OR 38)
Formula (Y4): -C (Rn) (H) (Ar)

In Formulas (Y1) and (Y2), Rx _{1 to} Rx ₃ each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). _However, if all of Rx 1 to Rx ₃ is an alkyl group (linear or _branched), it is preferred that at least two of Rx 1 to Rx ₃ is a methyl group.
Repeat More preferably, independently is Rx ₁ to Rx ₃ each a repeating unit represents a linear or branched alkyl group, more preferably, the independently is Rx ₁ to Rx ₃ each represent a linear alkyl group Is a unit.
Two of Rx _{1 to} Rx ₃ may combine to form a monocyclic or polycyclic ring.
As the alkyl group for Rx _{1 to} Rx ₃ , an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group is preferable.
Examples of the cycloalkyl group of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Groups are preferred.
Examples of the cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ include 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. Polycyclic cycloalkyl groups such as groups are preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.
The cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ is, for example, a group in which one of methylene groups constituting a ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced.
Repeating unit represented by formula (Y1), (Y2) is, for example, Rx ₁ is a methyl group or an ethyl group, by bonding and Rx ₂ and Rx ₃ form a cycloalkyl radical as defined above Embodiments are preferred.

In Formula (Y3), R _{36 to} R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may combine with each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R ₃₆ is also preferably a hydrogen atom.

  As the preferable formula (Y3), a structure represented by the following general formula (Y3-1) is more preferable.

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group optionally containing a hetero atom, an aryl group optionally containing a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.
Preferably, at least one of L ₁ and L ₂ is a hydrogen atom, and at least one is an alkyl group, a cycloalkyl group, an aryl group, or a group obtained by combining an alkylene group and an aryl group.
At least two members of Q, M and L ₁ may combine to form a ring (preferably a 5- or 6-membered ring).
For improving the pattern collapse performance, L ₂ is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of the secondary alkyl group include an isopropyl group, a cyclohexyl group and norbornyl group, and examples of the tertiary alkyl group include a tert-butyl group and adamantane. In these embodiments, since Tg and activation energy are increased, fog can be suppressed in addition to ensuring film strength.

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

  As the repeating unit of the resin (A) having a group which is decomposed by the action of an acid to generate a polar group, a repeating unit represented by the following general formula (AI) or (AII) is preferable.

In the general formula (AI),
Xa ₁ represents a hydrogen atom or an alkyl group which may have a substituent.
T represents a single bond or a divalent linking group.
Y represents a group capable of leaving with an acid. Y is preferably the formulas (Y1) to (Y4).

Represented by xa _1, as the alkyl group which may have a substituent group, include groups represented by methyl group or _-CH 2 _{-R 11.} R ₁₁ represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, and preferably 3 or less carbon atoms. And more preferably a methyl group. In one embodiment, Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, or the like.
Examples of the divalent linking group of T include an alkylene group, a -COO-Rt- group, a -O-Rt- group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, a — (CH ₂ ) ₂ — group, or a — (CH ₂ ) ₃ — group.

In the general formula (AII),
R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₆₂ may be bonded to Ar ₆ to form a ring, in which case R ₆₂ represents a single bond or an alkylene group.
X ₆ represents a single bond, —COO—, or —CONR ₆₄ —. R ₆₄ represents a hydrogen atom or an alkyl group.
L ₆ represents a single bond or an alkylene group.
Ar ₆ represents an (n + 1) -valent aromatic ring group, and when it is bonded to R ₆₂ to form a ring, represents an (n + 2) -valent aromatic ring group.
Y ₂ independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ≧ 2. However, at least one of Y ₂ represents a group which is eliminated by the action of an acid. The group capable of leaving by the action of an acid as Y ₂ is preferably any of formulas (Y1) to (Y4).
n represents an integer of 1 to 4.

  Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxy group. Examples thereof include a carbonyl group (2 to 6 carbon atoms), and preferably 8 or less carbon atoms.

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

  The repeating unit represented by the general formula (AII) is preferably a repeating unit represented by the following general formula (AIII).

In the general formula (AIII),
Ar ₃ represents an aromatic ring group.
Y ₂ independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ≧ 2. However, at least one of Y ₂ represents a group which is eliminated by the action of an acid. The group capable of leaving by the action of an acid as Y ₂ is preferably any of formulas (Y1) to (Y4).
n represents an integer of 1 to 4.

The aromatic ring group represented by Ar ₆ and Ar ₃ is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

Specific examples of the repeating unit having an acid-decomposable group are shown below, but the present invention is not limited thereto.
In the specific examples, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of substituents, each is independent. p represents 0 or a positive integer. Examples of the substituent containing a polar group represented by Z include, for example, a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, a straight-chain or branched alkyl group, and a cycloalkyl group. Is an alkyl group having a hydroxyl group. An isopropyl group is particularly preferred as the branched alkyl group.

  The repeating unit having an acid-decomposable group may be one type, or two or more types may be used in combination.

  The content of the repeating unit having an acid-decomposable group in the resin (A) (when a plurality of types are contained, the total thereof) is from 5 mol% to 80 mol% with respect to all the repeating units in the resin (A). Preferably, it is 5 mol% or more and 75 mol% or less, more preferably 10 mol% or more and 65 mol% or less.

  In the specification of the present application, a repeating unit having an acid-decomposable group and an aromatic ring group applies to a repeating unit having an acid-decomposable group and a repeating unit having an aromatic ring group.

(Repeating unit having a lactone group or a sultone group)
The resin (A) preferably contains a repeating unit having a lactone group or a sultone (cyclic sulfonic acid ester) group. As the lactone group or the sultone group, any group may be used as long as it contains a lactone structure or a sultone structure, but a group containing a 5- to 7-membered lactone structure or a sultone structure is preferable. It is preferable that another ring structure is condensed with a 7-membered lactone structure or a sultone structure to form a bicyclo structure or a spiro structure.
A group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17) or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3) It is more preferred to have a repeating unit having the formula: Further, a group having a lactone structure or a sultone structure may be directly bonded to the main chain. Preferred lactone structures or sultone structures include groups represented by general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14). It is.

The lactone structure portion or the sultone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , A halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group, and the like. n2 represents the integer of 0-4. When n2 is 2 or more, Rb ₂ existing in plural numbers may be the same or different or may be bonded to form a ring Rb ₂ between the plurality of.

  Having a group having a lactone structure represented by any of formulas (LC1-1) to (LC1-17) or a sultone structure represented by any of formulas (SL1-1) to (SL1-3) Examples of the repeating unit include a repeating unit represented by the following general formula (AI).

In Formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Preferred substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom.
As the halogen atom represented by Rb _0, there can be mentioned a fluorine atom, a chlorine atom, a bromine atom, an iodine atom. Rb ₀ is preferably a hydrogen atom or a methyl group.
Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. Represent. Preferably, it is a single bond or a connecting group represented by —Ab ₁ —CO ₂ —. Ab ₁ is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.
V represents a group represented by any one of the general formulas (LC1-1) to (LC1-17) and (SL1-1) to (SL1-3).

  The repeating unit having a lactone group or a sultone group usually has an optical isomer, but any optical isomer may be used. Further, one kind of 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) is preferably 90 or more, more preferably 95 or more.

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

  The content of the repeating unit having a lactone group or a sultone group is preferably 1 to 30 mol%, more preferably 5 to 25 mol%, and still more preferably 5 to 20 mol%, based on all repeating units in the resin (A). %.

[Other repeating units]
The resin (A) may further have, as other repeating units, a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group.
Thereby, the substrate adhesion and the developer affinity are improved. The alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the polar group, a hydroxyl group and a cyano group are preferable. Specific examples of the repeating unit having a polar group are shown below, but the present invention is not limited thereto.

  When the resin (A) has a repeating unit containing an organic group having a polar group, the content is preferably 1 to 30 mol%, more preferably 5 to 30 mol%, based on all repeating units in the resin (A). ２５25 mol%, more preferably 5-20 mol%.

In addition, the resin (A) may include, as another repeating unit, a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (photoacid generating group). In this case, it can be considered that the repeating unit having the photoacid-generating group corresponds to the compound (B) which generates an acid upon irradiation with actinic rays or radiation described below.
Examples of such a repeating unit include a repeating unit represented by the following general formula (4).

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

  Hereinafter, specific examples of the repeating unit represented by the general formula (4) are shown, but the present invention is not limited thereto.

  In addition, examples of the repeating unit represented by the general formula (4) include the repeating units described in paragraphs [0094] to [0105] of JP-A-2014-041327.

  When the resin (A) contains a repeating unit having a photoacid-generating group, the content of the repeating unit having a photoacid-generating group is preferably from 1 to 40 mol% based on all the repeating units in the resin (A). , More preferably 5 to 35 mol%, and still more preferably 5 to 30 mol%.

The resin (A) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a batch polymerization method in which a monomer species and an initiator are dissolved in a solvent and polymerization is performed by heating, a solution of the monomer species and an initiator is dropped in a heating solvent over 1 to 10 hours. Drop polymerization method, and the like, and the drop polymerization method is preferable.
Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and 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; And a solvent that dissolves the actinic ray-sensitive or radiation-sensitive resin composition, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone. More preferably, the polymerization is carried out using the same solvent as that used for the actinic ray-sensitive or radiation-sensitive resin composition. Thereby, generation of particles during storage can be suppressed.

The polymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon. The polymerization is started using a commercially available radical initiator (such as an azo-based initiator or a peroxide) as the polymerization initiator. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, and a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, the mixture is poured 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 45% by mass.
The reaction temperature is usually from 10C to 150C, preferably from 30C to 120C, more preferably from 60C to 100C.
Purification is carried out by a liquid-liquid extraction method to remove residual monomer or oligomer components by washing with water or combining an appropriate solvent, a purification method in a solution state such as ultrafiltration to extract and remove only those having a specific molecular weight or less, In a solid state such as re-precipitation method of removing residual monomers and the like by coagulating the resin in the poor solvent by dropping the resin solution into the poor solvent, or washing the filtered resin slurry with the poor solvent, etc. Ordinary methods such as a purification method can be applied.

The weight average molecular weight of the resin (A) is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, most preferably from 5,000 to 15, as a value in terms of polystyrene by the GPC method. 000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated and viscosity is increased to deteriorate film formability. Can be prevented.
Another particularly preferred weight average molecular weight of the resin (A) is 3,000 to 9,500 in terms of polystyrene by GPC.
The dispersity (molecular weight distribution) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. . The smaller the degree of dispersion, the better the resolution and the resist shape, the smoother the side walls of the resist pattern, and the better the roughness.

In the actinic ray-sensitive or radiation-sensitive resin composition, the content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass based on the total solid content.
In the actinic ray-sensitive or radiation-sensitive resin composition, the resin (A) may be used alone or in combination of two or more.

<Compound (B) that generates an acid by actinic rays or radiation>
The actinic ray-sensitive or radiation-sensitive resin composition contains a compound that generates an acid by actinic ray or radiation (also referred to as “compound (B)”, “photoacid generator”, or “PAG (Photo Acid Generator)”). It is preferred to contain.
The photoacid generator may be in the form of a low-molecular compound or may be incorporated in a part of the polymer. Further, the form of the low molecular compound and the form incorporated in a part of the polymer may be used in combination.
When the photoacid generator is in the form of a low-molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.
When the photoacid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) that the actinic ray-sensitive or radiation-sensitive resin composition may contain. It may be incorporated in a resin different from A).
The photoacid generator is preferably in the form of a low molecular compound.
The photoacid generator is not particularly limited as long as it is a known one. However, by irradiation with actinic rays or radiation, preferably an electron beam or extreme ultraviolet rays, an organic acid such as sulfonic acid, bis (alkylsulfonyl) imide, or Compounds that generate at least one of tris (alkylsulfonyl) methides are preferred.
More preferred examples of the photoacid generator include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ generally has 1 to 30, preferably 1 to 20 carbon atoms.
Two of R _{201 to} R ₂₀₃ may combine 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 of R _{201 to} R ₂₀₃ include an alkylene group (for example, a butylene group and a pentylene group).
Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).

  Non-nucleophilic anions include, for example, sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphorsulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, aralkyl Carboxylate anion), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

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

  The aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylate anion preferably includes an aryl group having 6 to 14 carbon atoms, for example, a phenyl group, a tolyl group, and a naphthyl group.

  The above-mentioned alkyl group, cycloalkyl group and aryl group may have a substituent. Specific examples thereof include a halogen atom such as a nitro group and a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), and a cycloalkyl group (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to carbon atoms) 7), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), an aryloxysulfonyl group (preferably having 1 to 15 carbon atoms) 6-20), alkylaryloxysulfonyl group (preferably having 7-20 carbon atoms), cycloalkylaryl 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 can be given. . As for the aryl group and ring structure of each group, examples of the substituent further include an alkyl group (preferably having 1 to 15 carbon atoms).

  The aralkyl group in the aralkyl carboxylate anion preferably includes an aralkyl group having 7 to 12 carbon atoms, such as benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl.

  Examples of the sulfonylimide anion include a 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 the substituent of these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
Further, the alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.

Other non-nucleophilic anions include, for example, phosphorus fluorinated (eg, PF ₆ ⁻ ), boron fluorinated (eg, BF ₄ ⁻ ), antimony fluorinated (eg, SbF ₆ ⁻ ), and the like. .

  Examples of the non-nucleophilic anion include an aliphatic sulfonic acid anion in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group in which the alkyl group is a fluorine atom. And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted by a fluorine atom. As the non-nucleophilic anion, more preferably a perfluoroaliphatic sulfonic acid anion (more preferably 4 to 8 carbon atoms), a benzenesulfonic acid anion having a fluorine atom, even more preferably a nonafluorobutanesulfonic acid anion, a perfluorooctane Sulfonic acid anion, pentafluorobenzenesulfonic acid anion, and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

  From the viewpoint of acid strength, the generated acid preferably has a pKa of -1 or less for improving sensitivity.

  Further, as the non-nucleophilic anion, an anion represented by the following general formula (AN1) is also mentioned as a preferable embodiment.

Where:
Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when a plurality of R ¹ and R ² are present, R ¹ and R ² may be the same or different.
L represents a divalent linking group, and when a plurality of L are present, L may be the same or different.
A represents a cyclic organic group.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

General formula (AN1) will be described in more detail.
The alkyl group in the alkyl group substituted with a fluorine atom for Xf preferably has 1 to 10 carbon atoms, and more preferably has 1 to 4 carbon atoms. Further, the alkyl group substituted with a fluorine atom for Xf is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific of Xf, fluorine _{atom, CF 3, C 2 F 5} , C 3 F 7, C 4 F 9, CH 2 CF 3, CH 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH _{2 C 2 F 5, CH 2} C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9, CH 2 CH 2 C 4 F 9 . Of these fluorine atom, CF ₃ are preferred. In particular, it is preferable that both Xf are fluorine atoms.

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

x is preferably 1 to 10, more preferably 1 to 5.
y is preferably 0 to 4, and more preferably 0.
z is preferably from 0 to 5, and more preferably from 0 to 3.
Is not particularly restricted but includes divalent linking group of L, -COO -, - OCO - , - CO -, - O -, - S -, - SO -, - SO 2 -, an alkylene group, a cycloalkylene group, Examples thereof include an alkenylene group and a linking group in which a plurality thereof are linked, and a linking group having a total carbon number of 12 or less is preferable. Among them, -COO-, -OCO-, -CO-, and -O- are preferable, and -COO- and -OCO- are more preferable.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and is not limited to an alicyclic group, an aryl group, or a heterocyclic group (not only an aromatic group but also an aromatic group). And the like).
The alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododeca. Polycyclic cycloalkyl groups such as a nyl group and an adamantyl group are preferred. 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 present in the film in the post-exposure heating step. Diffusion can be suppressed, which is preferable from the viewpoint of improving MEEF (Mask Error Enhancement Factor).
Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Among them, those derived from a furan ring, a thiophene ring and a pyridine ring are preferred.

  Further, the cyclic organic group may also include a lactone structure, and specific examples thereof include lactone structures represented by general formulas (LC1-1) to (LC1-17).

  The cyclic organic group may have a substituent, and the substituent may be an alkyl group (which may be linear, branched, or cyclic, preferably having 1 to 12 carbon atoms), cycloalkyl, Alkyl group (which may be monocyclic, polycyclic or spiro ring, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide Groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, sulfonic acid ester groups, and the like. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

_Examples of the organic groups for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group, an alkyl group, and a cycloalkyl group.
At least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is preferably an aryl group, and more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group and a naphthyl group, a heteroaryl group such as an indole residue and a pyrrole residue can be used. As the alkyl group and cycloalkyl group of R _{201 to} R ₂₀₃ , preferably, a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms can be exemplified. More preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. More preferably, the cycloalkyl group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like. These groups may further have a substituent. Examples of the substituent include a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to carbon atoms) 7) and the like, but are not limited thereto.

Preferred examples of the anion represented by the general formula (AN1) include the following. In the following examples, A represents a cyclic organic group.
_{SO 3 -CF 2 -CH 2 -OCO-} A, SO 3 -CF 2 -CHF-CH 2 -OCO-A, SO 3 -CF 2 -COO-A, SO 3 -CF 2 -CF 2 -CH 2 - _{A, SO 3 -CF 2 -CH (} CF 3) -OCO-A

In the general formulas (ZII) and (ZIII),
R _{204 to} R ₂₀₇ each independently represent 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 groups, alkyl groups, and cycloalkyl groups of R _{201 to} R ₂₀₃ in compound (ZI).
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Examples of the substituent include those which the aryl group, alkyl group and cycloalkyl group of R _{201 to} R ₂₀₃ in compound (ZI) may have.

Z ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- can be the same as the non-nucleophilic anion.

In the present invention, photoacid generator, from the viewpoint of providing excellent diffuse inhibitory resolution of the non-exposed portion of the acid generated by exposure, by irradiation of an electron beam or extreme ultraviolet radiation, volume 130 Å ³ or more It is preferably a compound that generates an acid having a size (more preferably, sulfonic acid), more preferably a compound that generates an acid having a volume of 190 ³ or more (more preferably, sulfonic acid), and more preferably 270 °. more preferably ³ or more the size of the acid (more preferably sulfonic acid) is a compound which generates an, especially the (more preferably sulfonic acid) acid volume 400 Å ³ or more in size is a compound capable of generating an preferable. However, from the viewpoint of sensitivity and coating solvent solubility, the volume is more preferably preferably at 2000 Å ³ or less, and 1500 Å ³ or less. The value of the volume was determined using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as an initial structure, By performing molecular orbital calculations using the PM3 method for these most stable conformations, the “accessible volume” of each acid can be calculated.
In the present invention, a photoacid generator which generates an acid exemplified below by irradiation with actinic rays or radiation is preferable. In some of the examples, the calculated value of the volume is added (unit ^{３ 3} ). The calculated value obtained here is a volume value of an acid in which a proton is bonded to an anion portion.
1Å is 1 × 10 ⁻¹⁰ m.

  Examples of the photoacid generator include paragraphs [0368] to [0377] of JP-A-2014-41328 and paragraphs [0240] to [0262] of JP-A-2013-228681 (corresponding US Patent Application Publication No. 2015/004533). [0339]) of the specification can be incorporated by reference, and the contents thereof are incorporated herein. In addition, preferred specific examples include the following compounds, but are not limited thereto.

The photoacid generator can be used alone or in combination of two or more.
The content of the photoacid generator in the actinic ray-sensitive or radiation-sensitive resin composition is preferably from 0.1 to 50% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. , More preferably 5 to 50% by mass, and still more preferably 8 to 40% by mass. In particular, the content of the photoacid generator is more preferably 10 to 40% by mass, and most preferably 10 to 35% by mass, in order to achieve both high sensitivity and high resolution during electron beam or extreme ultraviolet exposure. It is.
The photoacid generators can be used alone or in combination of two or more.

<Resist solvent>
The actinic ray-sensitive or radiation-sensitive resin composition preferably contains a solvent (also referred to as a “resist solvent”). The solvent is a group consisting of (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable to include at least one of at least one selected from the following. The solvent may further contain components other than the components (M1) and (M2).

  By using such a solvent in combination with the resin (A), the present inventors can improve the coatability of the actinic ray-sensitive or radiation-sensitive resin composition and form a pattern with a small number of development defects. It is found that it becomes. Although the reason is not necessarily clear, the present inventors have found that these solvents have a good balance of the solubility, boiling point, and viscosity of the resin (A). It is thought that this is because the generation of precipitates can be suppressed.

  As the component (M1), at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate is preferable, and propylene glycol monomethyl ether acetate is particularly preferable.

The following are preferable as the component (M2).
As the propylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.
As the lactic acid ester, ethyl lactate, butyl lactate, or propyl lactate is preferable.
As the acetate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate are preferred.
Butyl butyrate is also preferred.
As the alkoxypropionate, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
Examples of the chain ketone include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methylethylketone, and methylisobutyl. Ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, or methylamylketone is preferred.
As the cyclic ketone, methylcyclohexanone, isophorone or cyclohexanone is preferable.
As the lactone, γ-butyrolactone is preferred.
As the alkylene carbonate, propylene carbonate is preferred.

  As the component (M2), propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, γ-butyrolactone or propylene carbonate is more preferable.

  In addition to the above components, it is preferable to use an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and still more preferably 7 to 10), and having 2 or less hetero atoms.

  Preferred examples of the ester solvent having 7 or more carbon atoms and 2 or less hetero atoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, and butyl propionate. , Isobutyl isobutyrate, heptyl propionate, butyl butanoate, etc., and it is particularly preferable to use isoamyl acetate.

  As the component (M2), it is preferable to use one having a flash point (hereinafter, also referred to as fp) of 37 ° C. or higher. As such a component (M2), propylene glycol monomethyl ether (fp: 47 ° C.), ethyl lactate (fp: 53 ° C.), ethyl 3-ethoxypropionate (fp: 49 ° C.), methyl amyl ketone (fp: 42 ° C.) ° C), cyclohexanone (fp: 44 ° C), pentyl acetate (fp: 45 ° C), methyl 2-hydroxyisobutyrate (fp: 45 ° C), γ-butyrolactone (fp: 101 ° C) or propylene carbonate (fp: 132 ° C) Is preferred. Of these, propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred. Here, “flash point” means a value described in a reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich.

  The solvent preferably contains the component (M1). More preferably, the solvent consists essentially of the component (M1) or is a mixed solvent of the component (M1) and other components. In the latter case, the solvent more preferably contains both the component (M1) and the component (M2).

  The mass ratio between component (M1) and component (M2) is preferably in the range of 100: 0 to 15:85, more preferably in the range of 100: 0 to 40:60, and 100: More preferably, it is in the range of 0 to 60:40. That is, the solvent is preferably composed of only the component (M1) or contains both the component (M1) and the component (M2), and their mass ratio is as follows. That is, in the latter case, the mass ratio of the component (M1) to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and further preferably 60/40 or more. preferable. By adopting such a configuration, it is possible to further reduce the number of development defects.

  When the solvent contains both the component (M1) and the component (M2), the mass ratio of the component (M1) to the component (M2) is, for example, 99/1 or less.

  As described above, the solvent may further include components other than the components (M1) and (M2). In this case, the content of the components other than the components (M1) and (M2) is preferably in the range of 5 to 30% by mass based on the total amount of the solvent.

  The content of the solvent in the actinic ray-sensitive or radiation-sensitive resin composition is preferably determined so that the solid content concentration of all components is 0.5 to 30% by mass, and is 1 to 20% by mass. It is more preferable to determine In this case, the coatability of the actinic ray-sensitive or radiation-sensitive resin composition can be further improved.

<Crosslinking agent>
The actinic ray-sensitive or radiation-sensitive resin composition may contain a crosslinking agent.
In this specification, a crosslinking agent typically refers to a compound that reacts with a resin by the action of an acid to form a crosslinked structure.
As the cross-linking agent, a compound having two or more cross-linkable groups in a molecule is preferable, and a methylol-based cross-linking agent (a cross-linking agent having at least one of a methylol group (hydroxymethyl group) and an alkoxymethyl group), an epoxy-based cross-linking agent (Crosslinking agent having an epoxy group), oxetane-based crosslinking agent (crosslinking agent having an oxetanyl group), isocyanate-based crosslinking agent (crosslinking agent having an isocyanate group) and the like, and a methylol-based crosslinking agent and an epoxy-based crosslinking agent are preferable. , A methylol-based crosslinking agent is more preferred, a crosslinking agent having two or more methylol groups, a crosslinking agent having two or more alkoxymethyl groups, or a crosslinking agent having one or more methylol groups and one or more alkoxymethyl groups More preferably, it is an agent.

The crosslinking agent may be a low molecular compound or a high molecular compound (for example, a compound having a crosslinkable group supported on a high molecular compound, a compound having a repeating unit having a crosslinkable group, or the like). When the crosslinking agent has a low molecular weight, the molecular weight is preferably from 100 to 1,000, more preferably from 200 to 900, and most preferably from 300 to 800.
Preferred examples of the crosslinking agent include hydroxymethylated or alkoxymethylated phenol compounds, alkoxymethylated melamine-based compounds, alkoxymethylglycoluril-based compounds, and alkoxymethylated urea-based compounds. Particularly preferred crosslinking agents include phenol derivatives and alkoxymethylglycoluril derivatives having 3 to 5 benzene rings in the molecule, further having 2 or more hydroxymethyl groups or alkoxymethyl groups in total, and having a molecular weight of 1200 or less. No.
As the alkoxymethyl group, a methoxymethyl group and an ethoxymethyl group are preferable.

  Among the examples of the crosslinking agent, a phenol derivative having a hydroxymethyl group can be obtained by reacting a corresponding phenol compound having no hydroxymethyl group with formaldehyde under a base catalyst. Further, a phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst.

  Examples of other preferred crosslinking agents further include compounds having an N-hydroxymethyl group or an N-alkoxymethyl group such as alkoxymethylated melamine compounds, alkoxymethylglycoluril compounds and alkoxymethylated urea compounds. be able to.

Such compounds include hexamethoxymethylmelamine, hexaethoxymethylmelamine, tetramethoxymethylglycoluril, 1,3-bismethoxymethyl-4,5-bismethoxyethyleneurea, bismethoxymethylurea and the like. No. 3,133,216A, West German Patent Nos. 3,634,671, 3,711,264 and EP0,212,482A.
Particularly preferred examples of the cross-linking agent are shown below.

In the formula, L _{1 to} L ₈ each independently represent a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, or an alkyl group having 1 to 6 carbon atoms.
In one embodiment of the present invention, the crosslinking agent is preferably a compound represented by the following general formula (CI).

In the general formula (CI),
R ₁ and R ₆ each independently represent a hydrogen atom or a hydrocarbon group having 5 or less carbon atoms.
R ₂ and R ₅ each independently represent an alkyl group, a cycloalkyl group, an aryl group, or an acyl group.
R ₃ and R ₄ each independently represent a hydrogen atom or an organic group having 2 or more carbon atoms. R ₃ and R ₄ may combine with each other to form a ring.

In one embodiment of the present invention, R ₁ and R ₆ are preferably a hydrocarbon group having 5 or less carbon atoms, more preferably a hydrocarbon group having 4 or less carbon atoms, particularly preferably a methyl group, an ethyl group, A propyl group and an isopropyl group.

As the alkyl group represented by R ₂ and R ₅ , for example, an alkyl group having 1 to 6 or less carbon atoms is preferable, and as a cycloalkyl group, for example, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and as an aryl group, Is preferably, for example, an aryl group having 6 to 12 carbon atoms, and as the acyl group, for example, one having 1 to 6 carbon atoms in the alkyl moiety is preferable.
In one embodiment of the present invention, R ₂ and R ₅ are preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

Examples of the organic group having 2 or more carbon atoms represented by R ₃ and R ₄ include an alkyl group, a cycloalkyl group, and an aryl group having 2 or more carbon atoms, and R ₃ and R ₄ are bonded to each other. To form a ring which will be described in detail below.

Examples of the ring formed by combining R ₃ and R ₄ with each other include, for example, an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, or a combination of two or more of these rings. And polycondensed rings.

  These rings may have a substituent, and examples of such a substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, an aryl group, an alkoxymethyl group, an acyl group, and an alkoxycarbonyl group. , A nitro group, a halogen, or a hydroxy group.

The following are specific examples of the ring formed by combining R ₃ and R ₄ with each other. * In the formula represents a linking site with the phenol nucleus.

In one embodiment of the present invention, R ₃ and R ₄ in the general formula (CI) preferably combine to form a polycyclic fused ring including a benzene ring, and more preferably form a fluorene structure. preferable.
The cross-linking agent preferably forms, for example, a fluorene structure represented by the following general formula (Ia) by combining R ₃ and R ₄ in the general formula (CI).

Where:
R ₇ and R ₈ each independently represent a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an alkoxymethyl group, an acyl group, an alkoxycarbonyl group, a nitro group, a halogen, and a hydroxy group.
n1 and n2 each independently represent an integer of 0 to 4, preferably 0 or 1.
* Represents a linking site with the phenol nucleus.

  In one embodiment of the present invention, the crosslinking agent is preferably represented by the following general formula (Ib).

Where:
R _1b and R _6b each independently represent an alkyl group having 5 or less carbon atoms.
R _2b and R _5b each independently represent an alkyl group having 6 or less carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms.
Z represents a group of atoms necessary to form a ring together with the carbon atoms in the formula.
The ring formed by Z together with the carbon atom in the formula is the same as that described for the ring formed by combining R ₃ and R ₄ with each other in the description of the above general formula (CI).

  In one embodiment of the present invention, the crosslinking agent is preferably a compound having four or more aromatic rings and two alkoxymethyl groups and / or hydroxymethyl groups in the molecule.

Next, a method for producing the crosslinking agent represented by the general formula (CI) will be described.
The bisphenol compound serving as a core of the crosslinking agent represented by the general formula (CI) is generally obtained by subjecting two corresponding molecules of a phenol compound and one corresponding molecule of a ketone to a dehydration condensation reaction in the presence of an acid catalyst. Synthesized.

  The obtained bisphenol compound is treated with paraformaldehyde and dimethylamine and aminomethylated to obtain an intermediate represented by the following general formula (IC). Subsequently, the desired acid crosslinking agent is obtained through acetylation, deacetylation, and alkylation.

In the formula, R ₁ , R ₃ , R ₄ and R ₆ have the same meaning as each group in the general formula (CI).

In the present synthesis method, an oligomer is less likely to be generated than in a conventional synthesis method via a hydroxymethyl compound under basic conditions (for example, JP-A-2008-273844), and thus has an effect of suppressing particle formation. .
Hereinafter, specific examples of the crosslinking agent will be described.

  The crosslinking agents may be used alone or in combination of two or more. From the viewpoint of good pattern shape, it is preferable to use two or more kinds in combination.

  When the actinic ray-sensitive or radiation-sensitive resin composition contains a crosslinking agent, the content of the crosslinking agent is 0.1 to 40 mass with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. %, More preferably 1 to 35% by mass, even more preferably 5 to 30% by mass.

(Basic compound)
The actinic ray-sensitive or radiation-sensitive resin composition preferably contains a basic compound in order to reduce a change in performance over time from exposure to heating.
Preferred examples of the basic compound include compounds having structures represented by the following formulas (E-1) to (E-5).

In the general formula (E-1), R ²⁰⁰ , R ^201, and R ²⁰² may be the same or different and include a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 carbon atoms). To 20) or an aryl group (preferably having 6 to 20 carbon atoms), wherein R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

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.
In the general formula (E-5), R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and represent an alkyl group having 1 to 20 carbon atoms.
The alkyl groups in these general formulas (E-1) and (E-5) are more preferably unsubstituted.

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

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole. Compounds having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene and 1,8-diazabicyclo [5,4,0 ] Undec-7-ene and the like. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and a sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, and tris (t-butylphenyl) sulfonium. Hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide and the like. The compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety has become a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the aniline compound 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, and tris (methoxyethoxyethyl) amine. Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.

  Preferable basic compounds further include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.

As the amine compound, primary, secondary, and tertiary amine compounds can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound has, in addition to the alkyl group, a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group ( Preferably, carbon atoms having 6 to 12) may be bonded to the nitrogen atom.
Further, it is preferable that the amine compound has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more, preferably 3 to 9, and more preferably 4 to 6 in the molecule. Oxyethylene group _(-CH 2 _CH 2 O-) or an oxypropylene group _{(-CH (CH 3) CH 2} O- or _-CH 2 _CH 2 _CH 2 O-) are preferred among the oxyalkylene groups, more preferably oxy It is an ethylene group.

As the ammonium salt compound, primary, secondary, tertiary, and quaternary ammonium salt compounds can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the ammonium salt compound may be a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group. (Preferably 6 to 12 carbon atoms) may be bonded to the nitrogen atom.
The ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more, preferably 3 to 9, and more preferably 4 to 6 in the molecule. Oxyethylene group _(-CH 2 _CH 2 O-) or an oxypropylene group _{(-CH (CH 3) CH 2} O- or _-CH 2 _CH 2 _CH 2 O-) are preferred among the oxyalkylene groups, more preferably oxy It is an ethylene group.
Examples of the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate, and a phosphate, and among them, a halogen atom and a sulfonate are preferable. As the halogen atom, chloride, bromide and iodide are particularly preferable, and as the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include an alkyl sulfonate having 1 to 20 carbon atoms and an aryl sulfonate. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, an alkoxy group, an acyl group, and an aryl group. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, nonafluorobutane sulfonate, and the like. The aryl group of the arylsulfonate includes a benzene ring, a naphthalene ring and an anthracene ring. The benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and the cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, an acyloxy group and the like.

  The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or the ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylate group, a sulfonate group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. And the like. The substituent may be substituted at any of positions 2 to 6. The number of substituents may be any number in the range of 1 to 5.

It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is one or more, preferably 3 to 9, and more preferably 4 to 6 in the molecule. Oxyethylene group _(-CH 2 _CH 2 O-) or an oxypropylene group _{(-CH (CH 3) CH 2} O- or _-CH 2 _CH 2 _CH 2 O-) are preferred among the oxyalkylene groups, more preferably oxy It is an ethylene group.

  The amine compound having a phenoxy group is obtained by heating and reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether, and then adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium. , Ethyl acetate, chloroform and the like. Or, after heating and reacting a haloalkyl ether having a phenoxy group at the terminal with a primary or secondary amine, sodium hydroxide, potassium hydroxide, after adding an aqueous solution of a strong base such as tetraalkylammonium, ethyl acetate, It can be obtained by extraction with an organic solvent such as chloroform.

(A compound having a proton-accepting functional group and decomposing upon irradiation with actinic rays or radiation to generate a compound whose proton-accepting property has been reduced or eliminated, or has been changed from proton-accepting property to acidic (PA) )
The actinic ray-sensitive or radiation-sensitive resin composition has, as a basic compound, a proton acceptor functional group, and is decomposed by irradiation with actinic ray or radiation to lower the proton acceptor property, disappear, or It may further include a compound that generates a compound changed from a proton acceptor property to an acidic one (hereinafter, also referred to as compound (PA)).

  The proton acceptor functional group is a group having an electron capable of interacting electrostatically with a proton or a functional group having an electron, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a π conjugate. A functional group having a nitrogen atom with an unshared electron pair that does not contribute. The nitrogen atom having a lone pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.

  Preferred partial structures of the proton acceptor functional group include, for example, crown ether, azacrown ether, primary to tertiary amine, pyridine, imidazole, and pyrazine structures.

  The compound (PA) is decomposed by irradiation with actinic rays or radiation to generate a compound in which the proton acceptor property has been reduced or eliminated, or the proton acceptor property has been changed to acidic. Here, the decrease in proton acceptor property, disappearance, or change from proton acceptor property to acidic means a change in proton acceptor property due to addition of a proton to the proton acceptor functional group, and specifically, Specifically, it means that when a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.

  Specific examples of the compound (PA) include, for example, the following compounds. Further, as specific examples of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP-A-2014-41328 and paragraphs 0108 to 0116 of JP-A-2014-134686 can be referred to. , The contents of which are incorporated herein.

  These basic compounds may be used alone or in a combination of two or more.

  The content of the basic compound is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 5% by mass, based on the solid content of the actinic ray-sensitive or radiation-sensitive resin composition.

  The ratio of the photoacid generator and the basic compound used in the actinic ray-sensitive or radiation-sensitive resin composition is preferably photoacid generator / basic compound (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing a decrease in resolution due to the thickening of the pattern over time from exposure to heating. The photoacid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.

  As the basic compound, for example, compounds described in paragraphs 0140 to 0144 of JP2013-11833A (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like) can be used.

<Hydrophobic resin>
The actinic ray-sensitive or radiation-sensitive resin composition may have a hydrophobic resin different from the resin (A), separately from the resin (A).
As the hydrophobic resin, the same resin as the resin preferably contained in the composition for forming an upper layer can also be used.
The hydrophobic resin is preferably designed so as to be unevenly distributed on the surface of the actinic ray-sensitive or radiation-sensitive film, but unlike a surfactant, it does not necessarily need to have a hydrophilic group in the molecule, and may be polar / non-polar. It is not necessary to contribute to uniformly mixing the polar substance.
The effects of adding the hydrophobic resin include controlling the static / dynamic contact angle of the actinic ray-sensitive or radiation-sensitive film surface to water, suppressing outgassing, and the like.

The hydrophobic resin has at least one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution on the film surface layer. And more preferably two or more. Further, the hydrophobic resin preferably contains a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the hydrophobic resin or may be substituted on the side chain.

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

When the hydrophobic resin contains a fluorine atom, as a partial structure having a fluorine atom, it may be 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. preferable.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably having 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, and further having a fluorine atom May have a substituent other than the above.
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 and a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. .
Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in paragraph 0519 of US2012 / 0251948A1.

In addition, as described above, the hydrophobic resin preferably includes a CH ₃ partial structure in a side chain portion.
Here, the CH ₃ partial structure contained in the side chain portion of the hydrophobic resin, is intended to encompass CH ₃ partial structure an ethyl group, and a propyl group having.
On the other hand, a methyl group directly bonded to the main chain of the hydrophobic resin (for example, an α-methyl group of a repeating unit having a methacrylic acid structure) contributes to uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. Because of its small size, it is not included in the CH ₃ partial structure in the present invention.

  Regarding the hydrophobic resin, the descriptions of [0348] to [0415] of JP-A-2014-010245 can be referred to, and the contents thereof are incorporated in the present specification.

  In addition, the thing of Unexamined-Japanese-Patent No. 2011-248019, Unexamined-Japanese-Patent No. 2010-175859, and Unexamined-Japanese-Patent No. 2012-032544 can also be used preferably as a hydrophobic resin.

  As the hydrophobic resin, a resin having the following structure can also be used.

(Surfactant)
The actinic ray-sensitive or radiation-sensitive resin composition may further contain a surfactant. By containing a surfactant, a wavelength of 250 nm or less, particularly when using an exposure light source of 220 nm or less, with good sensitivity and resolution, it is possible to form a pattern with less adhesion and less development defects. Become.
It is particularly preferable to use a fluorine-based and / or silicon-based surfactant as the surfactant.
As the fluorine-based and / or silicon-based surfactant, for example, the surfactant described in [0276] of US Patent Application Publication No. 2008/0248425 is exemplified. Also, F-top EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florad FC430, 431 or 4430 (manufactured by Sumitomo 3M Limited); Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troysol S-366 (manufactured by Troy Chemical Corporation); GF-300 or GF-150 (manufactured by Toagosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); 01 (manufactured by Gemco); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos) May be used. In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

The surfactant may be a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method) in addition to the known surfactants described above. They may be synthesized. Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound may be used as the surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.
Further, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 may be used.

  One of these surfactants may be used alone, or two or more thereof may be used in combination.

  When the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, its content is preferably from 0 to 2 based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. %, More preferably 0.0001 to 2% by mass, even more preferably 0.0005 to 1% by mass.

(Other additives)
The actinic ray-sensitive or radiation-sensitive resin composition comprises a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a compound having a molecular weight of 1,000 or less). A phenolic compound or an alicyclic or aliphatic compound containing a carboxy group).

  The actinic ray-sensitive or radiation-sensitive resin composition may further contain a dissolution inhibiting compound. Here, the “dissolution inhibiting compound” is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce the solubility in an organic developer.

(G) Onium Carboxylate The actinic ray-sensitive or radiation-sensitive resin composition may contain (G) an onium carboxylate. Examples of the onium carboxylate include sulfonium carboxylate, iodonium carboxylate, ammonium carboxylate and the like. Particularly, as the onium carboxylate (G), an iodonium salt and a sulfonium salt are preferable. Furthermore, it is preferable that the carboxylate residue of the onium carboxylate (G) does not contain an aromatic group and a carbon-carbon double bond. As a particularly preferred anion portion, a linear, branched, monocyclic or polycyclic alkyl carboxylate anion having 1 to 30 carbon atoms is preferred. More preferably, an anion of a carboxylic acid in which some or all of these alkyl groups are substituted with fluorine is preferred. An oxygen atom may be contained in the alkyl chain. As a result, transparency to light of 220 nm or less is ensured, sensitivity and resolution are improved, and dependency on density and exposure margin are improved.

  Examples of the anion of the fluorine-substituted carboxylic acid include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorocyclohexanecarboxylic acid, And the anion of 2,2-bistrifluoromethylpropionic acid.

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

  (G) The content of the onium carboxylate in the composition is generally from 0.1 to 20% by mass, preferably from 0.5 to 20% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. 10 to 10% by mass, more preferably 1 to 7% by mass.

  In order to form an actinic ray-sensitive or radiation-sensitive film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition, each component is dissolved in a solvent to form an actinic ray-sensitive or radiation-sensitive resin. It is preferable to prepare the composition, filter it if necessary, and then apply it on a substrate. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less.

  The actinic ray-sensitive or radiation-sensitive resin composition is applied onto a substrate (eg, silicon or silicon dioxide coating) used in the production of precision integrated circuit devices by an appropriate application method such as a spinner or a coater. Is preferred. Then, it is preferable to dry and form an actinic ray-sensitive or radiation-sensitive film. If necessary, various base films (inorganic film, organic film, antireflection film) may be formed below the actinic ray-sensitive or radiation-sensitive film. Further, it is preferable to dry the actinic ray-sensitive or radiation-sensitive film before forming the upper layer film. As a result, a film from which unnecessary residual solvents have been removed can be formed uniformly.

  As a drying method, a method of drying by heating (prebaking) is generally used. Heating can be carried out by means provided in a usual exposure / developing machine, and may be carried out using a hot plate or the like. The heating temperature is not particularly limited, but is preferably from 50 ° C to 160 ° C, and more preferably from 60 ° C to 140 ° C. The heating time is preferably from 30 to 1000 seconds, more preferably from 60 to 800 seconds, even more preferably from 60 to 600 seconds.

The thickness of the actinic ray-sensitive or radiation-sensitive film is generally 200 nm or less, and preferably 10 to 100 nm.
The film thickness is more preferably in the range of 15 nm to 45 nm. If the film thickness is 15 nm or more, sufficient etching resistance can be obtained. The film thickness is more preferably 15 nm to 40 nm. When the film thickness is in this range, etching resistance and better resolution performance can be satisfied simultaneously.

<Step (b)>
Step (b) of the pattern forming method of the present invention is a step of forming an upper layer film on the actinic ray-sensitive or radiation-sensitive film using the composition for forming an upper layer film.
In the step (b), a composition for forming an upper layer film (also referred to as a “top coat composition”) is applied on the actinic ray-sensitive or radiation-sensitive film formed in the step (a), and then, if necessary. It is preferable to form an upper layer film (also referred to as “top coat”) by heating (prebaking (PB)).

[Composition for forming upper layer film]
The composition for forming an upper layer film used in the pattern forming method of the present invention will be described.
The composition for forming an upper layer film is prepared by adding a compound (Q) having a molecular weight of 5,000 or less (also referred to as “compound (Q)”) that does not generate an acid by actinic rays or radiation to the total solid content of the composition for forming an upper layer film. 1% by mass to 40% by mass. Although the details of the reason why the resolution is improved even in an extremely fine residual pattern according to the present invention have not been clarified, the upper layer film formed by the composition for forming an upper layer film may be actinic ray-sensitive or radiation-sensitive. By disposing on the film, the compound (Q) in the upper layer film interacts with the acid generated in the exposed portion, thereby suppressing the diffusion of the acid and improving the resolution even in an extremely fine residual pattern. It is thought to be.

(Compound (Q) having a molecular weight of 5,000 or less that does not generate an acid by actinic rays or radiation)
The molecular weight of the compound (Q) is preferably 1500 or less, more preferably 1000 or less.
The compound (Q) is a non-polymeric compound, and is preferably a compound having a certain molecular weight (a compound having substantially no molecular weight distribution).
The compound (Q) is preferably a compound that hardly volatilizes in the heating process, and preferably has a boiling point at 101325 Pa of 250 ° C. or higher, more preferably 300 ° C. or higher.
Compound (Q) is preferably solid at 101325 Pa and 20 ° C.
Specific examples of the compound (Q) are shown below, but it should not be construed that the invention is limited thereto.

X3: tri-N-octylamine, X4: 1- (tert-butoxycarbonyl) -4-hydroxypiperidine, X5: tert-butyl 1-pyrrolidinecarboxylate, X6: triisopropanolamine

  The content of the compound (Q) is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total solid content of the composition for forming an upper layer film.

  The composition for forming an upper layer film used in the pattern forming method of the present invention may be a composition further containing a resin and a solvent in order to uniformly form the composition on an actinic ray-sensitive or radiation-sensitive film. preferable.

(resin)
The composition for forming an upper layer film preferably contains a resin. The resin that can be contained in the composition for forming an upper layer film is not particularly limited, and the same resin as the hydrophobic resin that can be contained in the actinic ray-sensitive or radiation-sensitive resin composition can be used.
Regarding the hydrophobic resin, JP-A Nos. 2013-61647, [0017] to [0023] (corresponding U.S. Patent Publication No. 2013/244438, [0017] to [0023]), and JP-A-2014-56194. [0016] to [0165] and the descriptions of [0014] to [0077] in JP-A-2015-152773 can be referred to, and the contents thereof are incorporated in the present specification.
In the present invention, when the composition for forming an upper layer film contains a resin containing a repeating unit having an aromatic ring, it absorbs OOB (Out of Band) light contained in EUV light and leads to improvement in resolution. It is preferred in that respect.

  The weight average molecular weight of the resin is preferably from 1,000 to 200,000, more preferably from 3,000 to 50,000, and most preferably from 5,000 to 30,000. The compounding amount of the resin is preferably 95% by mass or less, more preferably 40 to 90% by mass, and still more preferably 50 to 80% by mass in the total solid content of the composition for forming an upper layer film.

[Resin (X)]
It is also preferable that the composition for forming an upper layer film contains the resin (X) described below. The resin (X) is preferably transparent with respect to the exposure light source to be used, since light reaches the actinic ray-sensitive or radiation-sensitive film through the upper layer film at the time of exposure.

  In one embodiment of the present invention, the resin (X) preferably has a fluorine atom content of 20% by mass or less. Specifically, the content of fluorine atoms in the resin (X) is preferably not more than 20% by mass, more preferably not more than 10% by mass, and ideally substantially not more than the weight average molecular weight of the resin (X). 0% by mass.

In another embodiment of the present invention, the resin (X) is preferably a resin having a CH ₃ partial structure in a side chain portion.
Here, the CH ₃ partial structure of the side chain portion in the resin (X) (hereinafter, also simply referred to as “side chain CH ₃ partial structure”) includes the CH ₃ partial structure of an ethyl group, a propyl group, and the like. Things.

On the other hand, a methyl group (for example, an α-methyl group of a repeating unit having a methacrylic acid structure) directly bonded to the main chain of the resin (X) is not included in the CH ₃ partial structure in the present invention.

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

Meanwhile, CH ₃ partial structure exists through some atoms from C-C backbone shall apply to 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 the compound has one CH ₃ partial structure in the present invention.

In the above general formula (M),
R _{11 to} R ₁₄ each independently represent a side chain portion.

Examples of R _{11 to} R _{14 in the} side chain 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 And an arylaminocarbonyl group. These groups may further have a substituent.

The resin (X) is preferably a resin having a repeating unit having a CH ₃ partial structure in a side chain portion. As such a repeating unit, a repeating unit represented by the following general formula (II), More preferably, it has at least one kind of repeating unit (x) among the repeating units represented by the general formula (III). In particular, when KrF, EUV, or electron beam (EB) is used as the exposure light source, the resin (X) may preferably contain a repeating unit represented by the general formula (III).

  Hereinafter, the repeating unit represented by the general 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, and R ₂ represents an acid-stable organic group having at least one CH ₃ partial structure. Here, the acid-stable organic group is more specifically, “decomposed by the action of acid” described in the acid-decomposable resin contained in the actinic ray-sensitive or radiation-sensitive resin composition described below. It is preferable that the organic group does not have a group that produces an alkali-soluble group.

The alkyl group for X _b1 preferably has 1 to 4 carbon atoms, and includes a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a trifluoromethyl group, and the like, and is preferably a methyl group.

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

R ₂ includes 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-mentioned 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 to 10 CH ₃ partial structures, more preferably 3 to 8 CH ₃ partial structures.

As the alkyl group having one or more CH ₃ partial structures in R ₂ , a branched alkyl group having 3 to 20 carbon atoms is preferable. Preferable examples of the alkyl group include isopropyl, isobutyl, 3-pentyl, 2-methyl-3-butyl, 3-hexyl, 2-methyl-3-pentyl, and 3-methyl-4. -Hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl 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 and the like. More preferably, an isobutyl group, a t-butyl group, a 2-methyl-3-butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 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 is there.

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 from 6 to 30, particularly preferably from 7 to 25. Preferred cycloalkyl groups include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, Examples thereof include a cyclodecanyl group and a cyclododecanyl group. More preferably, an adamantyl group, a norbornyl group, a cyclohexyl group, a cyclopentyl group, a tetracyclododecanyl group, and a tricyclodecanyl group can be exemplified. More preferred are a norbornyl group, a cyclopentyl group and a cyclohexyl group. As R ₂ , a cycloalkyl group having one or more CH ₃ partial structures is preferable. More preferably a polycyclic cycloalkyl group having one or more CH ₃ partial structure, having a polycyclic more preferably a cycloalkyl group, three or more CH ₃ partial structure having two or more CH ₃ partial structure Polycyclic cycloalkyl groups are particularly preferred. Among them, a polycyclic cycloalkyl group substituted with three or more alkyl groups is preferable.

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

As the aryl group having one or more CH ₃ partial structures in R ₂ , an aryl group having 6 to 20 carbon atoms is preferable, 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 isopropyl, isobutyl, t-butyl, 3-pentyl, 2-methyl-3-butyl Group, 3-hexyl group, 2,3-dimethyl-2-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl 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, Examples thereof include a 3,5-dimethylcyclohexyl group, a 4-isopropylcyclohexyl group, a 4-tbutylcyclohexyl group, and an isobornyl group. More preferably, an isobutyl group, a t-butyl group, a 2-methyl-3-butyl group, a 2,3-dimethyl-2-butyl group, a 2-methyl-3-pentyl group, a 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-butylcyclohexyl group, 4-isopropylcyclohexyl group, 4-tbutylcyclohexyl group, and 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 which is decomposed by the action of an acid to generate a polar group Is preferably a repeating unit having no.

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

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

The alkyl group of _Xb2 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 hydrogen atom is preferable.

X _b2 is preferably a hydrogen atom.

R ₃ is an acid-stable organic group, and more specifically, does not have a “group that is decomposed by the action of an acid to generate an alkali-soluble group” described in the acid-decomposable resin described below. It is preferably an organic group.

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 to 10 CH ₃ partial structures, more preferably 1 to 8 CH ₃ partial structures, It is more preferable to have one or more and four or less.

As the alkyl group having one or more CH ₃ partial structures in R ₃ , a branched alkyl group having 3 to 20 carbon atoms is preferable. Preferable examples of the alkyl group include isopropyl, isobutyl, 3-pentyl, 2-methyl-3-butyl, 3-hexyl, 2-methyl-3-pentyl, and 3-methyl-4. -Hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl 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 and the like. More preferably, an isobutyl group, a t-butyl group, a 2-methyl-3-butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 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 is there.

Specific examples of the alkyl group having two or more CH ₃ partial structures in R ₃ include an isopropyl group, an isobutyl group, a t-butyl group, a 3-pentyl group, a 2,3-dimethylbutyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4,4 4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group, and the like. . More preferably, it has 5 to 20 carbon atoms, 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-3-heptyl group, 2,3, 5,7-tetramethyl-4-heptyl group and 2,6-dimethylheptyl group.

  n represents an integer of 1 to 5, more preferably represents an integer of 1 to 3, and further preferably represents 1 or 2.

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

  The repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group which is decomposed by the action of an acid to generate a polar group Is preferably a repeating unit having no.

In the case where the resin (X) contains a CH ₃ partial structure in the side chain portion, and especially when it does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II), The content of at least one kind of the repeating unit (x) among the repeating units represented by (III) is preferably at least 90 mol%, more preferably at least 95 mol%, based on all repeating units of the resin (X). Is more preferable. The content is usually 100 mol% or less based on all repeating units of the resin (X).

  In another embodiment of the present invention, the resin (X) is preferably a resin containing a repeating unit derived from a monomer containing at least one fluorine atom and / or at least one silicon atom. It is further preferred that the resin is a water-insoluble resin containing a repeating unit derived from a monomer containing two fluorine atoms and / or at least one silicon atom. By containing a repeating unit derived from a monomer containing at least one fluorine atom and / or at least one silicon atom, good solubility in an organic solvent developer can be obtained, and the effect of the present invention can be sufficiently obtained. .

  The fluorine atom or silicon atom in the resin (X) may be present in the main chain of the resin or may be substituted on the side chain.

  The resin (X) is preferably a resin having a fluorine atom-containing alkyl group, a fluorine atom-containing cycloalkyl group, or a fluorine atom-containing aryl group as a fluorine atom-containing partial structure.

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

  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 another substituent.

  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 and a naphthyl group is substituted with a fluorine atom, and may further have another substituent.

  Specific examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom are shown below, but the present invention is not limited thereto.

In the general formulas (F2) to (F3),
R _{57 to} R ₆₄ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R _{57 to} R ₆₁ and R _{62 to} R ₆₄ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom (preferably having 1 to 4 carbon atoms). It is preferable that all of R _{57 to} R ₆₁ are fluorine atoms. R ₆₂ and R ₆₃ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom has been substituted with a fluorine atom, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. R ₆₂ and R ₆₃ may be linked 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, a 3,5-di (trifluoromethyl) phenyl group, and the like.

  Specific examples of the group represented by the general formula (F3) include a trifluoroethyl group, a pentafluoropropyl group, a pentafluoroethyl group, a heptafluorobutyl group, a hexafluoroisopropyl group, a heptafluoroisopropyl group, and a 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. A hexafluoroisopropyl group, a heptafluoroisopropyl group, a hexafluoro (2-methyl) isopropyl group, an octafluoroisobutyl group, a nonafluoro-t-butyl group, and a perfluoroisopentyl group are preferable, and a hexafluoroisopropyl group and a heptafluoroisopropyl group are preferable. More preferred.

  The resin (X) is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure as a partial structure having a silicon atom.

  Examples of the resin (X) include a resin having at least one selected from the group of repeating units represented by the following general formulas (CI) to (CV).

In the general formulas (C-I) to (C-V),
R _{1 to} R ₃ each independently represent a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms. Represents a group.

W _{1 to} W ₂ represent an organic group having at least one of a fluorine atom and a silicon atom.

R _{4 to} R ₇ each independently represent a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms. Represents a group. However, at least one of R _{4 to} R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may form a ring.

R ₈ represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.

R ₉ represents a linear or branched alkyl group having 1 to 4 carbon atoms or a fluorinated linear or branched alkyl group having 1 to 4 carbon atoms.

L _{1 to} L ₂ represent a single bond or a divalent linking group, and are the same as L _{3 to} L ₅ described above.

  Q represents a monocyclic or polycyclic aliphatic group. That is, it represents an atomic group containing two bonded carbon atoms (C-C) and forming an alicyclic structure.

R ₃₀ and R ₃₁ each independently represent a hydrogen or a fluorine atom.

R ₃₂ and R ₃₃ each independently represents an alkyl group, a cycloalkyl group, a fluorinated alkyl group or a fluorinated cycloalkyl group.

However, the repeating unit represented by the general formula (CV) has at least one fluorine atom in at least one of R ₃₀ , R ₃₁ , R _32, and R ₃₃ .

  The resin (X) preferably has a repeating unit represented by the general formula (C-I), and further has a repeating unit represented by the following general formulas (C-Ia) to (C-Id). preferable.

In the general formulas (C-Ia) to (C-Id),
R ₁₀ and R _{11 each} represent a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms.

W _{3 to} W ₆ represent an organic group having at least one of a fluorine atom and a silicon atom.

When W _{1 to} W ₆ are an organic group having a fluorine atom, a fluorinated linear or branched alkyl group or cycloalkyl group having 1 to 20 carbon atoms, or a fluorinated group having 1 to 20 carbon atoms It is preferably a linear, branched, or cyclic alkyl ether group.

Examples of the fluorinated alkyl group of W _{1 to} W ₆ include a trifluoroethyl group, a pentafluoropropyl group, a hexafluoroisopropyl group, a hexafluoro (2-methyl) isopropyl group, a heptafluorobutyl group, a heptafluoroisopropyl group, and an octafluoro group. Examples include an isobutyl group, a nonafluorohexyl group, a nonafluoro-t-butyl group, a perfluoroisopentyl group, a perfluorooctyl group, a perfluoro (trimethyl) hexyl group, and the like.

When W _{1 to} W ₆ are an organic group having a silicon atom, it is preferably an alkylsilyl structure or a cyclic siloxane structure. Specific examples include groups represented by the above general formulas (CS-1) to (CS-3).

Hereinafter, specific examples of the repeating unit represented by the general formula (CI) are shown. X is a hydrogen atom, _-CH 3, -F, or represents a -CF _3.

  The resin (X) may have a repeating unit represented by the following general formula (Ia) in order to adjust solubility in an organic solvent developer.

In the general formula (Ia),
Rf represents a fluorine atom or an alkyl group in which at least one hydrogen atom has been replaced by a fluorine atom.

R ₁ represents an alkyl group.

R ₂ represents a hydrogen atom or an alkyl group.

  In formula (Ia), the alkyl group in which at least one hydrogen atom of Rf is substituted with a fluorine atom preferably has 1 to 3 carbon atoms, and more preferably a trifluoromethyl group.

The alkyl group for R ₁ is preferably a straight-chain or branched alkyl group having 3 to 10 carbon atoms, and more preferably a branched alkyl group having 3 to 10 carbon atoms.

R ₂ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 3 to 10 carbon atoms.

  Hereinafter, specific examples of the repeating unit represented by the general formula (Ia) will be described, but the present invention is not limited thereto.

  The resin (X) may further have a repeating unit represented by the following general formula (III).

In the general formula (III),
R ₄ represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a trialkylsilyl group, or a group having a cyclic siloxane structure.

L ₆ represents a single bond or a divalent linking group.

In formula (III), the alkyl group of R ₄ is preferably a straight-chain 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 trialkylsilyl group is preferably a trialkylsilyl group having 3 to 20 carbon atoms.

  The group having a cyclic siloxane structure is preferably a group having a cyclic siloxane structure having 3 to 20 carbon atoms.

The divalent linking group for L ₆ is preferably an alkylene group (preferably having 1 to 5 carbon atoms) or an oxy group.

  The resin (X) may have a lactone group, an ester group, an acid anhydride or a group similar to an acid-decomposable group in an acid-decomposable resin described below. The resin (X) may further have a repeating unit represented by the following general formula (VIII).

  The resin (X) preferably contains a repeating unit (d) derived from a monomer having an alkali-soluble group. Thereby, the solubility in the coating solvent can be controlled. Examples of the alkali-soluble group include phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, 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 (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group And the like.

  The monomer having an alkali-soluble group is preferably a monomer having an acid dissociation index pKa of 4 or more, more preferably a monomer having a pKa of 4 to 13, and most preferably a monomer having a pKa of 8 to 13. By containing a monomer having a pKa of 4 or more, swelling during negative-type and positive-type development is suppressed, and not only good developability with an organic solvent developer but also use of a weakly basic alkali developer , Good developability is obtained.

  The acid dissociation constant pKa is described in Chemical Handbook (II) (Revised 4th edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). The pKa value of a monomer containing an alkali-soluble group is, for example, infinity It can be measured at 25 ° C. using a diluting solvent.

pKa is 4 or more monomers is not particularly limited, for example, phenolic hydroxyl group, sulfonamide group, -COCH 2 _CO-, fluoroalcohol group, a monomer having an acid group such as a carboxylic acid group (alkali-soluble group) No. Particularly, a monomer containing a fluoroalcohol group is preferable. The fluoroalcohol group is a fluoroalkyl group substituted by at least one hydroxyl group, preferably has 1 to 10 carbon atoms, and more preferably has 1 to 5 carbon atoms. Specific examples of the fluoro alcohol group, for _{example, -CF 2 OH, -CH 2 CF} 2 OH, -CH 2 CF 2 CF 2 OH, -C (CF 3) 2 OH, -CF 2 CF (CF 3) OH _{, -CH 2 C (CF 3)} 2 OH, and the like. Particularly preferred as the fluoroalcohol group is a hexafluoroisopropanol group.

  The total amount of the repeating units derived from the monomer having an alkali-soluble group in the resin (X) is preferably 0 to 90 mol%, more preferably 0 to 80 mol%, based on all the repeating units constituting the resin (X). Mol%, even more preferably 0-70 mol%.

  The monomer having an alkali-soluble group may contain only one acid group or two or more acid groups. The repeating unit derived from this monomer preferably has two or more acid groups per repeating unit, more preferably has 2 to 5 acid groups, and has 2 to 3 acid groups. Is particularly preferred.

  Preferred specific examples of the repeating unit derived from a monomer having an alkali-soluble group are shown below, but are not limited thereto.

  The resin (X) is preferably any resin selected from the following (X-1) to (X-8).

  (X-1) A resin having a repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms), more preferably a resin having only a repeating unit (a).

  (X-2) A resin having a repeating unit (b) having a trialkylsilyl group or a cyclic siloxane structure, more preferably a resin having only a repeating unit (b).

  (X-3) a repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms), a branched alkyl group (preferably having 4 to 20 carbon atoms) and a cycloalkyl group (preferably having 4 carbon atoms) To 20), a repeating unit (c) having a branched alkenyl group (preferably having 4 to 20 carbon atoms), a cycloalkenyl group (preferably having 4 to 20 carbon atoms) or an aryl group (preferably having 4 to 20 carbon atoms). And more preferably a copolymer resin of the repeating unit (a) and the repeating unit (c).

  (X-4) a repeating unit (b) having a trialkylsilyl group or a cyclic siloxane structure, a branched alkyl group (preferably having 4 to 20 carbon atoms), a cycloalkyl group (preferably having 4 to 20 carbon atoms), Resin having a repeating unit (c) having a branched alkenyl group (preferably having 4 to 20 carbon atoms), a cycloalkenyl group (preferably having 4 to 20 carbon atoms) or an aryl group (preferably having 4 to 20 carbon atoms) And more preferably a copolymer resin of a repeating unit (b) and a repeating unit (c).

  (X-5) a resin having a repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms) and a repeating unit (b) having a trialkylsilyl group or a cyclic siloxane structure, more preferably a repeating unit A copolymer resin of the unit (a) and the repeating unit (b).

  (X-6) a repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms), a repeating unit (b) having a trialkylsilyl group or a cyclic siloxane structure, and a branched alkyl group (preferably Represents 4 to 20 carbon atoms, a cycloalkyl group (preferably 4 to 20 carbon atoms), a branched alkenyl group (preferably 4 to 20 carbon atoms), a cycloalkenyl group (preferably 4 to 20 carbon atoms), or aryl A resin having a repeating unit (c) having a group (preferably having 4 to 20 carbon atoms), more preferably a copolymer resin of a repeating unit (a), a repeating unit (b) and a repeating unit (c).

  The repeating unit (c) having a branched alkyl group, a cycloalkyl group, a branched alkenyl group, a cycloalkenyl group, or an aryl group in the resins (X-3), (X-4), and (X-6). For example, an appropriate functional group can be introduced in consideration of hydrophilicity / hydrophobicity, interaction, and the like.

  (X-7) A repeating unit having an alkali-soluble group (d) (preferably having an alkali-soluble group having a pKa of 4 or more) in the repeating units constituting (X-1) to (X-6). Having a repeating unit).

  (X-8) A resin having only a repeating unit having an alkali-soluble group (d) having a fluoroalcohol group.

  In the resin (X-3), (X-4), (X-6), or (X-7), the resin has a repeating unit (a) having a fluoroalkyl group and / or a trialkylsilyl group, or a cyclic siloxane structure. The content of the repeating unit (b) is preferably from 10 to 99 mol%, more preferably from 20 to 80 mol%.

  Further, by having an alkali-soluble group (d) in the resin (X-7), not only the ease of peeling when using an organic solvent developer but also other peeling liquids such as an alkaline aqueous solution as a peeling liquid The ease of peeling when used is improved.

  The resin (X) is preferably solid at room temperature (25 ° C.). Further, the glass transition temperature (Tg) is preferably from 50 to 200C, more preferably from 80 to 160C.

  Being solid at 25 ° C. means that the melting point is 25 ° C. or higher.

  The glass transition temperature (Tg) can be measured by Differential Scanning Calorimeter. For example, the specific volume changes when the sample is once heated, cooled, and then heated again at 5 ° C./min. It can be measured by analyzing the values.

  The resin (X) is preferably soluble in an organic solvent developer (preferably a developer containing an ester solvent). When the pattern forming method of the present invention further includes a step of developing using an alkali developer, the resin (X) can be used with respect to the alkali developer from the viewpoint that development and peeling can be performed using an alkali developer. Preferably, it is soluble.

  When the resin (X) has a silicon atom, the content of the silicon atom is preferably from 2 to 50% by mass, more preferably from 2 to 30% by mass, based on the molecular weight of the resin (X). The content of the repeating unit containing a silicon atom in the resin (X) is preferably from 10 to 100% by mass, and more preferably from 20 to 100% by mass.

  By setting the content of the silicon atom and the content of the repeating unit containing the silicon atom in the above range, the ease of peeling off the upper layer film when using an organic solvent developer, furthermore, actinic ray-sensitive or radiation-sensitive Any incompatibility with the membrane can be improved.

  By setting the content of the fluorine atom and the content of the repeating unit containing a fluorine atom to the above ranges, the ease of peeling off the upper layer film when using an organic solvent developer, furthermore, actinic ray-sensitive or radiation-sensitive. Any incompatibility with the membrane can be improved.

  The weight average molecular weight of the resin (X) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, still more preferably 2,000 to 15,000, and particularly preferably. Is 3,000 to 15,000.

  The resin (X) preferably has a residual monomer amount of 0 to 10% by mass, more preferably 0 to 5% by mass, and still more preferably 0 to 1% by mass. The molecular weight distribution (Mw / Mn, also referred to as the degree of dispersion) is preferably from 1 to 5, more preferably from 1 to 3, and even more preferably from 1 to 1.5.

  Various commercially available resins can be used as the resin (X), and the resin (X) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a batch polymerization method in which a monomer species and an initiator are dissolved in a solvent and polymerization is performed by heating, a solution of the monomer species and an initiator is dropped in a heating solvent over 1 to 10 hours. Drop polymerization method, and the like, and the drop polymerization method is preferable. As the reaction solvent, for example, ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether and the like, methyl ethyl ketone, ketones such as methyl isobutyl ketone, ester solvents such as ethyl acetate, dimethylformamide, amide solvents such as dimethylacetamide, Further, a solvent that dissolves the composition of the present invention, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone described below, may be used.

  The polymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon. The polymerization is started using a commercially available radical initiator (such as an azo-based initiator or a peroxide) as the polymerization initiator. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, and a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. If necessary, a chain transfer agent can be used. The concentration of the reaction is usually 5 to 50% by mass, preferably 20 to 50% by mass, more preferably 30 to 50% by mass. The reaction temperature is usually from 10C to 150C, preferably from 30C to 120C, more preferably from 60C to 100C.

  After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification is a liquid-liquid extraction method that removes residual monomer and oligomer components by washing with water or combining an appropriate solvent, a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less, Purification in solid state, such as re-precipitation method to remove residual monomers etc. by coagulating resin in poor solvent by dropping resin solution into poor solvent or washing filtered resin slurry with poor solvent An ordinary method such as a method can be applied. For example, by contacting a solvent in which the resin is hardly soluble or insoluble (poor solvent) in a volume of 10 times or less, preferably 10 to 5 times the volume of the reaction solution, the resin is precipitated as a solid.

  The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for this polymer, and depending on the type of the polymer, for example, a hydrocarbon (pentane, hexane, Aliphatic hydrocarbons such as heptane and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons (such as methylene chloride, chloroform and carbon tetrachloride) Halogenated aliphatic hydrocarbons; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, etc., nitro compounds (nitromethane, nitroethane, etc.), nitriles (acetonitrile, benzonitrile, etc.), ethers (diethyl ether, diisopropyl ether, dimethoxyethane) Chain d Ter; cyclic ethers such as tetrahydrofuran and dioxane), ketones (acetone, methyl ethyl ketone, diisobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.), carbonates (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), alcohols ( Methanol, ethanol, propanol, isopropyl alcohol, butanol, etc.), carboxylic acid (acetic acid, etc.), water, a mixed solvent containing these solvents, and the like. Among them, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable as the precipitation or reprecipitation solvent. In such a solvent containing at least hydrocarbon, the ratio of alcohol (particularly, methanol, etc.) to another solvent (eg, esters such as ethyl acetate, ethers such as tetrahydrofuran, etc.) is, for example, the former / the latter (volume ratio). ; 25 ° C) = 10/90 to 99/1, preferably the former / latter (volume ratio; 25 ° C) = 30/70 to 98/2, more preferably the former / latter (volume ratio; 25 ° C) = 50 /. It is about 50 to 97/3.

  The amount of the precipitation or reprecipitation solvent can be appropriately selected in consideration of efficiency, yield, and the like, but is generally 100 to 10,000 parts by mass, preferably 200 to 2,000 parts by mass, based on 100 parts by mass of the polymer solution. More preferably, it is 300 to 1000 parts by mass.

  The nozzle diameter when supplying the polymer solution into the precipitation or reprecipitation solvent (poor solvent) is preferably 4 mmφ or less (for example, 0.2 to 4 mmφ). The feeding speed (dropping speed) of the polymer solution into the poor solvent is, for example, about 0.1 to 10 m / sec, preferably about 0.3 to 5 m / sec as a linear velocity.

  The precipitation or reprecipitation operation is preferably performed under stirring. As a stirring blade used for stirring, for example, a desk turbine, a fan turbine (including a paddle), a curved blade turbine, an arrow blade turbine, a faudler type, a bull margin type, an angled blade fan turbine, a propeller, a multistage type, an anchor type (or Horseshoe type), gate type, double ribbon, screw, etc. can be used. The stirring is preferably performed for 10 minutes or more, especially for 20 minutes or more after the supply of the polymer solution is completed. If the stirring time is short, the monomer content in the polymer particles may not be sufficiently reduced. Alternatively, the polymer solution and the poor solvent can be mixed and stirred using a line mixer instead of the stirring blade.

  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.

  The precipitated or reprecipitated particulate polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, dried, and used. The filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at normal pressure or under reduced pressure (preferably under reduced pressure) at a temperature of about 30 to 100 ° C, preferably about 30 to 50 ° C.

  In addition, once the resin is precipitated and separated, the resin may be dissolved again in a solvent and brought into contact with a solvent in which the resin is hardly soluble or insoluble.

  That is, after the completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact to precipitate the resin (step a), the resin is separated from the solution (step b), and the resin solution A is dissolved again in the solvent to form the resin solution A. Preparation (step c), and then contacting the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume of less than 10 times (preferably 5 times or less) the volume of the resin solution A, A method including depositing a solid (step d) and separating the deposited resin (step e) may be used.

  The solvent used for preparing the resin solution A can be the same as the solvent that dissolves the monomer in the polymerization reaction, and may be the same or different from the solvent used in the polymerization reaction.

  The resin (X) may be used alone or in combination of two or more.

  When the topcoat composition contains a plurality of resins (X), it is preferable that the topcoat composition contains at least one resin (XA) having a fluorine atom and / or a silicon atom. The topcoat composition may include at least one resin (XA) having a fluorine atom and / or a silicon atom, and a resin (XB) having a lower content of fluorine atoms and / or silicon atoms than the resin (XA). More preferred. Thereby, when the top coat film is formed, the resin (XA) is unevenly distributed on the surface of the top coat film, so that performance such as development characteristics can be improved.

  The content of the resin (XA) is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass, and more preferably 0.1 to 8% by mass based on the total solid content contained in the top coat composition. % Is more preferable, and 0.1 to 5% by mass is particularly preferable. The content of the resin (XB) is preferably 50.0 to 99.9% by mass, more preferably 60 to 99.9% by mass, and more preferably 70 to 99.9% by mass, based on the total solid content contained in the top coat composition. 9 mass% is more preferable, and 80 to 99.9 mass% is particularly preferable.

  The preferred ranges of the content of fluorine atoms and silicon atoms contained in the resin (XA) are the same as the preferred ranges when the resin (X) has a fluorine atom and when the resin (X) has a silicon atom.

  As the resin (XB), a form substantially not containing a fluorine atom and a silicon atom is preferable. In this case, specifically, the total content of the repeating unit having a fluorine atom and the repeating unit having a silicon atom is, It is preferably from 0 to 20 mol%, more preferably from 0 to 10 mol%, even more preferably from 0 to 5 mol%, particularly preferably from 0 to 3 mol%, ideally based on all repeating units in the resin (XB). Has 0 mol%, that is, contains no fluorine atom and no silicon atom.

  The amount of the resin (X) in the entire topcoat composition is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content.

<Topcoat solvent>
The composition for forming an upper layer film may contain a solvent. In this specification, the solvent contained in the composition for forming an upper layer film is also referred to as a topcoat solvent.
In order to form a good pattern without dissolving the actinic ray-sensitive or radiation-sensitive film, the top coat solvent is preferably a solvent that does not dissolve the actinic ray-sensitive or radiation-sensitive film, and is preferably used in organic development. More preferably, the solvent is different from the liquid.
From the viewpoint of uniformly coating the upper layer film, the upper layer film forming composition preferably has a solid content concentration of 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, More preferably, it is 10% by mass.

As the solvent for the top coat, the developing solution and the rinsing solution of the present application can be used.
The topcoat solvent is not particularly limited as long as the resin contained in the composition for forming an upper layer film is dissolved and the actinic ray-sensitive or radiation-sensitive film is not dissolved.
The composition for forming an upper layer film preferably contains an organic solvent.
The content of the organic solvent in the composition for forming an upper layer film is preferably 50% by mass or more, more preferably 70% by mass or more, based on all solvents contained in the composition for forming an upper layer film, More preferably, it is 90% by mass or more.
Preferred examples of the organic solvent include alcohol solvents, ether solvents, ester solvents, fluorine solvents, and hydrocarbon solvents. The viscosity of the topcoat solvent is preferably 5 cP (centipoise) or less, more preferably 3 cP or less, still more preferably 2 cP or less, and particularly preferably 1 cP or less. Note that the following formula can be used to convert centipoise to Pascal second.
1000 cP = 1 Pa · s.

As the alcohol-based solvent, a monohydric alcohol is preferable from the viewpoint of applicability, and more preferably a monohydric alcohol having 4 to 8 carbon atoms. As the monohydric alcohol having 4 to 8 carbon atoms, a linear, branched or cyclic alcohol can be used, but a linear or branched alcohol is preferable. Such alcohol solvents include, for example, 1-butanol, 2-butanol, 3-methyl-1-butanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, isobutyl alcohol, tert- Butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4 Alcohols such as octanol; glycols such as ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether Glycol ethers such as triethylene glycol monoethyl ether and methoxymethyl butanol; and the like, among which alcohols and glycol ethers are preferable, and 1-butanol, 1-hexanol, 1-pentanol, and 3-methyl-1 are preferable. -Butanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, propylene glycol monomethyl ether are more preferred.
Further, it is preferable to use a non-fluorine-based alcohol-based solvent as the alcohol-based solvent, whereby the insolubility in the actinic ray-sensitive or radiation-sensitive film is further improved, and the composition for forming the upper layer film is activated. When applied on a light-sensitive or radiation-sensitive film, the upper layer film can be formed more uniformly without dissolving the actinic-light-sensitive or radiation-sensitive film.

Examples of the fluorinated solvent include 2,2,3,3,4,4-hexafluoro-1-butanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol 2,2,3,3,4,4,5,5,6,6-decafluoro-1-hexanol, 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4,4,5,5,6,6,7,7- Dodecafluoro-1,8-octanediol, 2-fluoroanisole, 2,3-difluoroanisole, perfluorohexane, perfluoroheptane, perfluoro-2-pentanone, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, perflu B tributylamine, include perfluoro tetrapentyl amine or the like, and among this, can be preferably used a fluorinated alcohol or fluorinated hydrocarbon solvent.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene, xylene, and anisole; n-heptane, n-nonane, n-octane, n-decane, 2-methylheptane, 3-methylheptane, 3 And aliphatic hydrocarbon solvents such as 2,3-dimethylhexane, 2,3,4-trimethylpentane and undecane; and the like.
Examples of the ether-based solvent include, in addition to the glycol ether-based solvent, dioxane, tetrahydrofuran, isoamyl ether, and the like. Among the ether solvents, an ether solvent having a branched structure is preferable.
Examples of the ester solvent include methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate (n-butyl acetate), pentyl acetate, hexyl acetate, isoamyl acetate, butyl propionate (n-butyl propionate), butyl butyrate, and butyric acid. Isobutyl, butyl butanoate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3 -Methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, methyl 2-hydroxyisobutyrate, 2- Dorokishiiso butyric acid methyl, isobutyl isobutyrate, and butyl propionate. Among the ester solvents, an ester solvent having a branched structure is preferable.

The topcoat solvent may be used alone or in combination of two or more.
When a solvent other than the above is mixed, the mixing ratio is usually from 0 to 30% by mass, preferably from 0 to 20% by mass, more preferably from 0 to 10% by mass, based on the total amount of the solvent in the composition for forming an upper layer film. %. By mixing a solvent other than the above, the solubility in the actinic ray-sensitive or radiation-sensitive film, the solubility of the resin in the composition for forming the upper layer film, the elution characteristics from the actinic ray-sensitive or radiation-sensitive film, Can be appropriately adjusted.

  The content of the solvent having a hydroxyl group is preferably 50% by mass or less, more preferably 40% by mass or less, and preferably 30% by mass or less, based on the total solvent contained in the composition for forming an upper layer film. Is more preferred. When the content of the solvent having a hydroxyl group in the composition for forming an upper layer film is 50% by mass or less, the resin in the actinic ray-sensitive or radiation-sensitive composition dissolves in the top coat solvent in the composition for forming an upper layer film. Can be prevented, and the resolution can be improved.

The composition for forming an upper layer film may further contain a compound represented by any of the following (A1) to (A4) in addition to the resin and the topcoat solvent.
(A1) Basic compound or base generator (A2) Compound containing a bond or group selected from the group consisting of ether bond, thioether bond, hydroxyl group, thiol group, carbonyl bond and ester bond (A3) Ionic compound (A4) Compound having a radical trap group

<(A1) Basic compound or base generator>
The composition for forming an upper layer film preferably further contains at least one of a basic compound and a base generator (hereinafter, these may be collectively referred to as “compound (A1)”).

(Basic compound)
The basic compound that can be contained in the composition for forming an upper layer film is preferably an organic basic compound, and more preferably a nitrogen-containing basic compound. For example, those described as the basic compound which may be contained in the actinic ray-sensitive or radiation-sensitive resin composition can be used, and specifically, represented by formulas (E-1) to (E-5). Compounds having a structure are preferred.
Further, for example, compounds classified into the following (1) to (7) can be used.

  (1) Compound represented by general formula (BS-1)

In the general formula (BS-1),
R each independently represents a hydrogen atom or an organic group. However, at least one of the three Rs is an organic group. This organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group or an aralkyl group.

The number of carbon atoms of the alkyl group as R is not particularly limited, but is usually 1 to 20, and preferably 1 to 12.
The number of carbon atoms of the cycloalkyl group as R is not particularly limited, but is usually 3 to 20, and preferably 5 to 15.

The carbon number of the aryl group as R is not particularly limited, but is usually 6 to 20, and preferably 6 to 10. Specific examples include a phenyl group and a naphthyl group.
Although the carbon number of the aralkyl group as R is not particularly limited, it is usually 7 to 20, preferably 7 to 11. Specific examples include a benzyl group.

  In the alkyl group, cycloalkyl group, aryl group and aralkyl group as R, a hydrogen atom may be substituted by a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.

  In the compound represented by the formula (BS-1), it is preferable that at least two of Rs are organic groups.

  Specific examples of the compound represented by the general formula (BS-1) include tri-n-butylamine, tri-isopropylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, Isodecylamine, dicyclohexylmethylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N -Dibutylaniline, N, N-dihexylaniline, 2,6-diisopropylaniline, and 2,4,6-tri (t-butyl) aniline.

  Further, as a preferable basic compound represented by the general formula (BS-1), a compound in which at least one R is an alkyl group substituted with a hydroxy group can be mentioned. Specific examples include triethanolamine and N, N-dihydroxyethylaniline.

In addition, the alkyl group as R may have an oxygen atom in the alkyl chain. That is, an oxyalkylene chain may be formed. The oxyalkylene _chain, -CH 2 _CH 2 O- are preferable. Specifically, for example, tris (methoxyethoxyethyl) amine and the compounds exemplified in column 3, line 60 and subsequent rows of US Pat. No. 6,040,112 can be mentioned.

  Examples of the basic compound represented by Formula (BS-1) include the following.

(2) Compound Having a Nitrogen-Containing Heterocyclic Structure This is the same as the basic compound that can be contained in the actinic ray-sensitive or radiation-sensitive resin composition.

(4) Ammonium salt The same as described for the basic compound that the actinic ray-sensitive or radiation-sensitive resin composition may contain.

(5) a compound having a proton acceptor functional group and decomposing by irradiation with actinic rays or radiation to generate a compound having a reduced or eliminated proton acceptor property or changed from a proton acceptor property to an acidic one ( PA)
It is the same as that described as the basic compound that the actinic ray-sensitive or radiation-sensitive resin composition can contain.

  In the composition for forming an upper layer film, the compounding ratio of the compound (PA) in the entire composition is preferably from 0.1 to 10% by mass, more preferably from 1 to 8% by mass, based on the total solid content.

(6) Guanidine compound The composition for forming an upper layer film may contain a guanidine compound having a structure represented by the following formula as a basic compound.

The guanidine compound exhibits strong basicity because the positive charge of the conjugate acid is dispersed and stabilized by the three nitrogens.
As the basicity of the guanidine compound, it is preferable that the pKa of the conjugate acid is 6.0 or more, and it is preferably 7.0 to 20.0 because the neutralization reactivity with the acid is high and the roughness property is excellent. , 8.0 to 16.0.

  Due to such strong basicity, acid diffusibility can be suppressed, and it can contribute to the formation of an excellent pattern shape.

  In the present invention, logP is a logarithmic value of the n-octanol / water partition coefficient (P), and is an effective parameter that can characterize the hydrophilicity / hydrophobicity of a wide range of compounds. Generally, the distribution coefficient is obtained by calculation without experiment, and in the present invention, CSChemDrawUltraVer. 8.0 indicates a value calculated by softwarepackage (Crippen's sfragmentationmethod).

  Further, it is preferable that log P of the guanidine compound is 10 or less. When the content is equal to or less than the above value, it can be uniformly contained in the actinic ray-sensitive or radiation-sensitive film.

  The log P of the guanidine compound in the present invention is preferably in the range of 2 to 10, more preferably in the range of 3 to 8, and even more preferably in the range of 4 to 8.

  The guanidine compound in the present invention preferably has no nitrogen atom other than the guanidine structure.

  Specific examples of the guanidine compound include, but are not limited to, the compounds described in paragraphs [0765] to [0768] of JP-A-2013-83966.

(7) Low-molecular compound having a nitrogen atom and having a group capable of leaving by the action of an acid The composition for forming an upper layer film comprises a low-molecular compound having a nitrogen atom and having a group capable of leaving by the action of an acid. Can be contained. The low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid preferably has basicity after the group capable of leaving by the action of an acid is removed.

  The group which is eliminated 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 is preferably a carbamate group or a hemiaminal ether group. It is particularly preferred that there is.

  The molecular weight of the low molecular compound having a group capable of leaving by the action of an acid is preferably from 100 to 1,000, more preferably from 100 to 700, and particularly preferably from 100 to 500.

  As the low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid, an amine derivative having a group capable of leaving by the action of an acid on a nitrogen atom is preferable.

  The low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid 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 the general formula (d-1),
R ′ each independently represents a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. R's may be mutually bonded to form a ring.

  R '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.

  The low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid can also be constituted by arbitrarily combining a basic compound and the structure represented by the general formula (d-1).

  It is particularly preferable that the low molecular compound having a nitrogen atom and having a group capable of leaving by the action of an acid has a structure represented by the following general formula (J).

Note that a low molecular compound having a nitrogen atom and having a group capable of leaving by the action of an acid is equivalent to the above basic compound as long as it is a low molecular compound having a group capable of leaving by the action of an acid. There may be.
General formula (J)

  In the general formula (J), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When n = 2, the two Ras may be the same or different, and the two Ras are mutually bonded to form a divalent heterocyclic hydrocarbon group (preferably having 20 or less carbon atoms) or a derivative thereof. May be formed.

  Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. However, when one or more Rb in -C (Rb) (Rb) (Rb) is a hydrogen atom, at least one of the remaining Rb is a cyclopropyl group, a 1-alkoxyalkyl group or an aryl group.

  At least two Rb may combine to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.

  n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

  In the general formula (J), the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Ra and Rb are a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, and an oxo group. , An alkoxy group or a halogen atom. The same applies to the alkoxyalkyl group represented by Rb.

  Specific examples of the low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid according to the invention are described in, for example, paragraphs [0786] to [0788] of JP-A-2013-83966. However, the present invention is not limited thereto.

The compound represented by the general formula (J) can be synthesized based on JP-A-2007-298569, JP-A-2009-199021, and the like.
In the present invention, the low molecular compound having a nitrogen atom and having a group capable of leaving by the action of an acid can be used alone or in combination of two or more.

Other usable compounds include the compounds synthesized in the examples of JP-A-2002-363146 and the compounds described in paragraph 0108 of JP-A-2007-298569.
As the basic compound, a photosensitive basic compound may be used. Examples of the photosensitive basic compound include, for example, JP-T-2003-524799 and J.P. Photopolym. Sci & Tech. Vol. 8, p. 543-553 (1995) and the like.
As the basic compound, a compound called a so-called photodegradable base may be used. Examples of the photodisintegrable base include an onium salt of a carboxylic acid and an onium salt of a sulfonic acid in which the α-position is not fluorinated. Specific examples of the photodisintegrable base include paragraph 0145 of WO2014 / 133048A1, JP-A-2008-158339 and Patent 399146.

(Content of basic compound)
The content of the basic compound in the composition for forming an upper layer film is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and more preferably 1 to 10% by mass, based on the solid content of the composition for forming an upper layer film. -5% by mass is more preferred.

(Base generator)
Examples of the base generator (preferably a photo base generator) that can be contained in the composition for forming an upper layer film include, for example, JP-A-4-151156, JP-A-4-162040, JP-A-5-197148, JP-A-5-59995, Compounds described in JP-A-6-194834, JP-A-8-146608, JP-A-10-83079, and EP 622682 are exemplified.
Further, the compounds described in JP-A-2010-243773 can be used as appropriate.
Specific examples of the photobase generator include 2-nitrobenzyl carbamate, 2,5-dinitrobenzylcyclohexyl carbamate, N-cyclohexyl-4-methylphenylsulfonamide, and 1,1-dimethyl-2-phenylethyl Preferred is -N-isopropyl carbamate, but is not limited thereto.

(Content of base generator)
The content of the base generator in the composition for forming an upper layer film is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and more preferably 1 to 10% by mass, based on the solid content of the composition for forming an upper layer film. -5% by mass is more preferred.

<(A2) Compound containing bond or group selected from the group consisting of ether bond, thioether bond, hydroxyl group, thiol group, carbonyl bond and ester bond>
A compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond (hereinafter, also referred to as compound (A2)) is described below.

  As described above, the compound (A2) is a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond. Since the oxygen atom or sulfur atom contained in these groups or bonds has an unshared electron pair, the acid can be trapped by the interaction with the acid diffused from the actinic ray-sensitive or radiation-sensitive film.

  In one embodiment of the present invention, compound (A2) preferably has two or more groups or bonds selected from the above group, more preferably three or more, and still more preferably four or more. In this case, the groups or bonds selected from the ether bond, thioether bond, hydroxyl group, thiol group, carbonyl bond and ester bond contained in the compound (A2) may be the same or different. Good.

  In one embodiment of the present invention, the compound (A2) preferably has a molecular weight of 3,000 or less, more preferably 2,500 or less, further preferably 2,000 or less, and particularly preferably 1500 or less.

In one embodiment of the present invention, the number of carbon atoms contained in the compound (A2) is preferably 8 or more, more preferably 9 or more, and still more preferably 10 or more.
In one embodiment of the present invention, the number of carbon atoms contained in the compound (A2) is preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less.

  In one embodiment of the present invention, the compound (A2) is preferably a compound having a boiling point of 200 ° C or higher, more preferably a compound having a boiling point of 220 ° C or higher, and a compound having a boiling point of 240 ° C or higher. It is even more preferred.

In one embodiment of the present invention, the compound (A2) is preferably a compound having an ether bond, preferably has two or more ether bonds, more preferably has three or more ether bonds, and more preferably has four or more ether bonds. Is more preferred.
In one embodiment of the present invention, the compound (A2) further preferably contains a repeating unit having an oxyalkylene structure represented by the following general formula (1).

Where:
R ₁₁ represents an alkylene group which may have a substituent,
n represents an integer of 2 or more;
* Represents a bond.

The carbon number of the alkylene group represented by R ₁₁ in the general formula (1) is not particularly limited, but is preferably 1 to 15, more preferably 1 to 5, and preferably 2 or 3. More preferably, it is particularly preferably 2. When the alkylene group has a substituent, the substituent is not particularly limited, but is preferably, for example, an alkyl group (preferably having 1 to 10 carbon atoms).
n is preferably an integer of 2 to 20, and among them, it is more preferably 10 or less because DOF (depth of focus) becomes larger.
The average value of n is preferably 20 or less, more preferably 2 to 10, more preferably 2 to 8, and particularly preferably 4 to 6, because the DOF becomes larger. preferable. Here, the “average value of n” means a value of n determined by measuring the weight average molecular weight of the compound (A2) by GPC so that the obtained weight average molecular weight matches the general formula. If n is not an integer, the value is rounded off.
A plurality of R ₁₁ may be the same or different.

  Further, the compound having a partial structure represented by the above general formula (1) is preferably a compound represented by the following general formula (1-1) because DOF becomes larger.

Where:
Definition of R _11, specific examples and preferred embodiment is the same as R ₁₁ in general formula (1).
R ₁₂ and R ₁₃ each independently represent a hydrogen atom or an alkyl group. The carbon number of the alkyl group is not particularly limited, but is preferably 1 to 15. R ₁₂ and R ₁₃ may combine with each other to form a ring.
m represents an integer of 1 or more. m is preferably an integer of 1 to 20, and among them, it is more preferably 10 or less because the DOF becomes larger.
The average value of m is preferably 20 or less, more preferably 1 to 10, more preferably 1 to 8, further preferably 4 to 6, for the reason that the DOF becomes larger. preferable. Here, the “average value of m” is synonymous with the “average value of n” described above.
When m is 2 or more, a plurality of R ₁₁ may be the same or different.

  In one embodiment of the present invention, the compound having a partial structure represented by the general formula (1) is preferably an alkylene glycol containing at least two ether bonds.

  As the compound (A2), a commercially available product may be used, or may be synthesized by a known method.

  Hereinafter, specific examples of the compound (A2) will be given, but the present invention is not limited thereto.

  The content of the compound (A2) is preferably from 0.1 to 30% by mass, more preferably from 1 to 25% by mass, still more preferably from 2 to 20% by mass, based on the total solid content in the upper layer film. 18% by weight is particularly preferred.

<(A3) Ionic compound>
The composition for forming the upper layer film may contain an ionic compound which becomes a weak acid relatively to the acid generator contained in the actinic ray-sensitive or radiation-sensitive resin composition. Onium salts are preferred as the ionic compound. When an acid generated from an acid generator upon irradiation with actinic rays or radiation collides with an unreacted onium salt having a weak acid anion, a weak acid is released by salt exchange to produce an onium salt having a strong acid anion. In this process, the strong acid is exchanged for a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.

  As the onium salt that becomes a relatively weak acid with respect to the acid generator, a compound represented by the following general formulas (d1-1) to (d1-3) is preferable.

In the formula, R ⁵¹ is a hydrocarbon group which may have a substituent, and Z ^2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that carbon atoms adjacent to S , A fluorine atom is not substituted), R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or an arylene group, and Rf is a fluorine atom. And each M ⁺ is independently a sulfonium or iodonium cation.

Preferred examples of the sulfonium cation or iodonium cation represented by M ⁺ include a sulfonium cation exemplified by the general formula (ZI) and an iodonium cation exemplified by the general formula (ZII).

Preferred examples of the anion portion of the compound represented by the general formula (d1-1) include a structure exemplified in paragraph [0198] of JP-A-2012-242799.
Preferred examples of the anion portion of the compound represented by the general formula (d1-2) include a structure exemplified in paragraph [0201] of JP-A-2012-242799.
Preferred examples of the anion part of the compound represented by the general formula (d1-3) include the structures exemplified in paragraphs [0209] and [0210] of JP-A-2012-242799.

The onium salt which becomes a relatively weak acid with respect to the acid generator is (C) a compound having a cation site and an anion site in the same molecule, and wherein the cation site and the anion site are linked by a covalent bond ( Hereinafter, it may be referred to as “compound (CA)”).
The compound (CA) is preferably a compound represented by any of the following formulas (C-1) to (C-3).

In the general formulas (C-1) to (C-3),
R ₁ , R ₂ and R ₃ represent a substituent having 1 or more carbon atoms.
L ₁ represents a divalent linking group or a single bond linking the cation site and the anion site.
-X ^{- is,} -COO _^-, -SO 3 _- represents an anion portion selected from ^{_{-R 4 -, -SO 2 -,}} -N. R ₄ has a carbonyl group: —C (＝ O) —, a sulfonyl group: —S (＝ O) ₂ —, and a sulfinyl group: —S (＝ O) — at a linking site with an adjacent N atom. Represents a valent substituent.
R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may combine with each other to form a ring structure. In (C-3), two of R _{1 to} R ₃ may be combined to form a double bond with an N atom.

Examples of the substituent having 1 or more carbon atoms in R _{1 to} R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino. Examples include a carbonyl group and an arylaminocarbonyl group. Preferably, they are an alkyl group, a cycloalkyl group, and an aryl group.

L ₁ as a divalent linking group includes a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and a mixture of these two types. Examples include groups obtained by combining the above. L ₁ is more preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.
Preferred examples of the compound represented by the general formula (C-1) include paragraphs [0037] to [0039] of JP-A-2013-6827 and paragraphs [0027] to [0029] of JP-A-2013-8020. ] Can be mentioned.
Preferred examples of the compound represented by the general formula (C-2) include the compounds exemplified in paragraphs [0012] to [0013] of JP-A-2012-189977.
Preferred examples of the compound represented by the general formula (C-3) include the compounds exemplified in paragraphs [0029] to [0031] of JP-A-2012-252124.

(Content of onium salt)
The content of the onium salt in the composition for forming an upper layer film is preferably 0.5% by mass or more, more preferably 1% by mass or more, and more preferably 2.5% by mass or more based on the solid content of the composition for forming an upper layer film. Is more preferred.
On the other hand, the upper limit of the onium salt content is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and more preferably 8% by mass, based on the solid content of the composition for forming an upper layer film. The following are particularly preferred.

<(A4) Compound having a radical trap group>
(A4) The compound having a radical trap group is also referred to as compound (A4).
The radical trap group is a group that traps an active radical and stops a radical reaction. Examples of such a radical trapping group include a group that reacts with an active radical and is converted into a stable free radical, and a group having a stable free radical. Specific examples of the non-basic radical trap group include, for example, at least one member selected from the group consisting of a hindered phenol group, a hydroquinone group, an N-oxyl free radical group, a nitroso group, and a nitrone group. The group of is preferably mentioned.

  The number of radical trap groups in the compound (A4) is not particularly limited. When the compound (A4) is a compound other than the above-mentioned polymer compound, the number of radical trap groups is preferably 1 to 10 in one molecule, and preferably 1 to 10. -5 are more preferable, and 1-3 are still more preferable.

  On the other hand, when the compound (A4) is a polymer compound having a repeating unit, the repeating unit having a radical trapping group preferably has 1 to 5 radical trapping groups, and has 1 to 3 radical trapping groups. Is more preferable. Further, the composition ratio of the repeating unit having a radical trap group in the polymer compound is preferably 1 to 100 mol%, more preferably 10 to 100 mol%, and further preferably 30 to 100 mol%.

  As the compound having a radical trapping group, a compound having a nitrogen-oxygen bond is preferable because the effects of the present invention are more excellent, and the compounds represented by the following general formulas (1) to (3) because the effects of the present invention are more excellent. A compound represented by any of the above is more preferred.

  In addition, the compound represented by the following general formula (1) corresponds to a compound having an N-oxyl free radical group, the compound represented by the following general formula (2) corresponds to a compound having a nitroso group, The compound represented by the following general formula (3) corresponds to a compound having a nitrone group.

In the general formulas (1) to (3), R _{1 to} R ₆ each independently represent an alkyl group, a cycloalkyl group, or an aryl group. In Formula (1), R ₁ and R ₂ may combine to form a ring, and in Formula (3), at least two of R _{4 to} R ₆ may combine to form a ring.
An alkyl group, a cycloalkyl group, and an aryl group represented by R _{1 to} R ₆ , a ring which may be formed by bonding R ₁ and R _2, and at least two of R _{4 to} R ₆ bonded to each other; The ring which may be formed may have a substituent.

In addition, the compound represented by any of the general formulas (1) to (3) may be in the form of a resin. In this case, at least one of R _{1 to} R ₆ has a main chain or a side chain of the resin. May be bonded to

  Hereinafter, specific examples of the compound having a radical trap group are shown, but the present invention is not limited thereto.

  Further, as described above, the compound (A4) may be a polymer compound having a repeating unit. Specific examples of the repeating unit of the polymer compound (A4) are shown below, but the invention is not limited thereto.

The molecular weight of the compound having a radical trap group (low molecular weight compound) is not particularly limited, but is preferably 100 to 5,000, more preferably 100 to 2,000, even more preferably 100 to 1,000.
When the compound having a radical trapping group is a polymer compound having a repeating unit, the weight average molecular weight is preferably from 5,000 to 20,000, more preferably from 5,000 to 10,000.

  As the compound having a radical trap group, a commercially available compound may be used, or a compound synthesized by a known method may be used. Compound A is synthesized by reacting a commercially available low molecular weight compound having a radical trap group with a high molecular weight compound having a reactive group such as an epoxy group, a halogenated alkyl group, an acid halide group, a carboxyl group, and an isocyanate group. May be.

  The content of the compound having a radical trap group is usually from 0.001 to 10% by mass, and preferably from 0.01 to 5% by mass, based on the total solid content of the composition for forming an upper layer film.

The composition for forming an upper layer film may include a plurality of one compound among the compounds represented by (A1) to (A4). For example, it may contain two or more compounds (A1) that are distinguished from each other.
Further, the composition for forming an upper layer film may contain two or more compounds represented by (A1) to (A4). For example, both the compound (A1) and the compound (A2) may be contained.
When the composition for forming an upper layer film contains a plurality of compounds represented by (A1) to (A4), the total content of these compounds is based on the total solid content of the composition for forming an upper layer film of the present invention. Usually, it is 0.001 to 20% by mass, preferably 0.01 to 10% by mass, more preferably 1 to 8% by mass.

<Surfactant>
The composition for forming an upper layer film may further contain a surfactant.
There is no particular limitation on the surfactant, as long as the composition for forming the upper layer film can be uniformly formed and can be dissolved in the solvent of the composition for forming the upper layer film, an anionic surfactant, a cation Both a nonionic surfactant and a nonionic surfactant can be used.
The amount of the surfactant added is preferably 0.001 to 20% by mass, and more preferably 0.01 to 10% by mass.
One type of surfactant may be used alone, or two or more types may be used in combination.

Examples of the surfactant include an alkyl cation surfactant, an amide quaternary cation surfactant, an ester quaternary cation surfactant, an amine oxide surfactant, a betaine surfactant, and an alkoxylate. Surfactants, fatty acid ester surfactants, amide surfactants, alcohol surfactants, ethylenediamine surfactants, and fluorine and / or silicon surfactants (fluorine surfactants, silicon Surfactants and surfactants having both a fluorine atom and a silicon atom) can be suitably used.
Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenol ether, polyoxyethylene Polyoxyethylene alkyl allyl ethers such as nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene Nso sorbitan mono palmitate - DOO, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, surfactants such as polyoxyethylene sorbitan tristearate; commercial surfactants listed below; and the like.
Commercially available surfactants that can be used include, for example, F-Top EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florado FC430, 431 and 4430 (manufactured by Sumitomo 3M Limited), and Megafac F171, F173, and F176. , F189, F113, F110, F177, F120, R08 (manufactured by Dainippon Ink and Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troysol S -366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (manufactured by Toagosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-Top EF121, EF122A, EF122B, RF122C , EF125M, EF135M, EF351, 352, EF801, E 802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204D, 208G, 218G, 230G, 204D, 208D, 212D, 218, 222D (manufactured by Neos) And the like, and a fluorine-based surfactant or a silicon-based surfactant. Further, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as the silicon-based surfactant.

  The composition for forming an upper layer film may contain a crosslinking agent. Examples of the cross-linking agent include those similar to those described as the cross-linking agent which may be contained in the actinic ray-sensitive or radiation-sensitive resin composition.

<Preparation method of composition for forming upper layer film>
It is preferable that each component of the composition for forming an upper layer film is dissolved in a solvent, and the solution is filtered. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. Note that a plurality of types of filters may be connected in series or in parallel. Further, the composition may be filtered a plurality of times, and the step of filtering the composition a plurality of times may be a circulation filtration step. Further, the composition may be subjected to a degassing treatment before and after the filtration. The composition for forming an upper layer film of the present invention preferably does not contain impurities such as metals. The content of the metal component contained in these materials is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 1 ppm or less, and it is particularly preferred that they are substantially not contained (below the detection limit of the measuring device). .

When the exposure in step (c) is immersion exposure, the upper layer film is disposed between the actinic ray-sensitive or radiation-sensitive film and the immersion liquid, and the actinic ray-sensitive or radiation-sensitive film is directly It also functions as a layer that does not come into contact with the immersion liquid. In this case, it is preferable that the upper layer film (composition for forming the upper layer film) has properties such as suitability for application to an actinic ray-sensitive or radiation-sensitive film, transparency to radiation, particularly to 193 nm, and immersion liquid (preferably Water). Further, it is preferable that the upper layer film is not mixed with the actinic ray-sensitive or radiation-sensitive film and can be uniformly applied to the surface of the actinic ray-sensitive or radiation-sensitive film.
In order to uniformly apply the composition for forming an upper layer film to the surface of the actinic ray-sensitive or radiation-sensitive film without dissolving the actinic ray-sensitive or radiation-sensitive film, the composition for forming an upper layer film is used. Preferably contains a solvent that does not dissolve the actinic ray-sensitive or radiation-sensitive film. As the solvent that does not dissolve the actinic ray-sensitive or radiation-sensitive film, it is more preferable to use a solvent having a component different from that of the developer.

  The method for applying the composition for forming an upper layer film is not particularly limited, and a conventionally known spin coating method, spray method, roller coating method, dipping method, or the like can be used.

The thickness of the upper layer film is not particularly limited, but is usually 5 nm to 100 nm, preferably 10 nm to 80 nm, more preferably 10 nm to 60 nm, and still more preferably 10 nm to 50 nm, from the viewpoint of transparency to an exposure light source. .
The composition for forming an upper layer film is applied on the actinic ray-sensitive or radiation-sensitive film, and then heated (prebaked (PB: Prebake)) to form an upper layer on the actinic ray-sensitive or radiation-sensitive film. Preferably, a film is formed. Thereby, the diffusion of the cross-linking agent in the upper layer film is promoted, and the film loss can be further reduced. The temperature of the prebaking is not particularly limited, but is preferably from 80C to 160C, more preferably from 100C to 140C.
The refractive index of the upper layer film is preferably close to the refractive index of the actinic ray-sensitive or radiation-sensitive film from the viewpoint of resolution.

  When peeling the upper layer film, a developer (alkali developer and / or organic developer) may be used, or a separate peeling agent may be used. As the release agent, a solvent having low penetration into the actinic ray-sensitive or radiation-sensitive film is preferable. From the viewpoint that the upper layer film can be peeled off simultaneously with the development of the actinic ray-sensitive or radiation-sensitive film, the upper layer film is preferably peelable with an organic developer. The organic developer used for peeling is not particularly limited as long as it can dissolve and remove the low-exposed portion of the actinic ray-sensitive or radiation-sensitive film.

From the viewpoint of peeling with an organic developer, the dissolution rate of the upper layer film in the organic developer is preferably from 1 to 300 nm / sec, more preferably from 10 to 100 nm / sec.
Here, the dissolution rate of the upper layer film in the organic developer is the rate of decrease in the film thickness when the upper layer film is exposed to the developer after the film is formed. In the present invention, the film was immersed in butyl acetate at 23 ° C. Speed.
By setting the dissolution rate of the upper layer film in the organic developer to 1 / sec second or more, preferably 10 nm / sec or more, the effect of reducing the occurrence of development defects after developing the actinic ray-sensitive or radiation-sensitive film is reduced. is there. The line edge of the pattern after developing the actinic ray-sensitive or radiation-sensitive film may be set to 300 nm / sec or less, preferably 100 nm / sec, possibly due to reduced exposure unevenness during immersion exposure. There is an effect that the roughness becomes better.
The upper layer film may be removed using another known developer, for example, an alkaline aqueous solution. Specific examples of the alkaline aqueous solution that can be used include an aqueous solution of tetramethylammonium hydroxide.

Between step (a) and step (b), a step of applying a pre-wet solvent on the actinic ray-sensitive or radiation-sensitive film may be included. Thereby, the coatability of the composition for forming an upper layer film is improved, and liquid saving can be achieved.
The pre-wet solvent is not particularly limited as long as it has low solubility in the actinic ray-sensitive or radiation-sensitive film, but is not limited to alcohol-based solvents, fluorine-based solvents, ether-based solvents, hydrocarbon-based solvents, and ester-based solvents. A pre-wet solvent for the upper layer film containing at least one compound selected from the group consisting of:
As the alcohol-based solvent, a monohydric alcohol is preferable from the viewpoint of applicability, and more preferably a monohydric alcohol having 4 to 8 carbon atoms. As the monohydric alcohol having 4 to 8 carbon atoms, a linear, branched or cyclic alcohol can be used, but a linear or branched alcohol is preferable. Such alcohol solvents include, for example, 1-butanol, 2-butanol, 3-methyl-1-butanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, isobutyl alcohol, tert- Butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4 Alcohols such as octanol; glycols such as ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether Glycol ethers such as triethylene glycol monoethyl ether and methoxymethyl butanol; and the like, among which alcohols and glycol ethers are preferable, and 1-butanol, 1-hexanol, 1-pentanol, and 3-methyl-1 are preferable. -Butanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, propylene glycol monomethyl ether are more preferred.
Examples of ether solvents include dipropyl ether, diisopropyl ether, butyl methyl ether, butyl ethyl ether, butyl propyl ether, dibutyl ether, diisobutyl ether, tert-butyl-methyl ether, tert-butyl ethyl ether, tert-butyl propyl ether, -Tert-butyl ether, dipentyl ether, diisoamyl ether, cyclopentyl methyl ether, cyclohexyl methyl ether, cyclopentyl ethyl ether, cyclohexyl ethyl ether, cyclopentyl propyl ether, cyclopentyl-2-propyl ether, cyclohexyl propyl ether, cyclohexyl -2-propyl ether, cyclopentyl butyl ether, cyclopentyl-tert- Butyl ether, cyclohexyl butyl ether, cyclohexyl-tert-butyl ether and the like.
Examples of the fluorinated solvent include 2,2,3,3,4,4-hexafluoro-1-butanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol 2,2,3,3,4,4,5,5,6,6-decafluoro-1-hexanol, 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4,4,5,5,6,6,7,7- Dodecafluoro-1,8-octanediol, 2-fluoroanisole, 2,3-difluoroanisole, perfluorohexane, perfluoroheptane, perfluoro-2-pentanone, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, perflu B tributylamine, include perfluoro tetrapentyl amine or the like, and among this, can be preferably used a fluorinated alcohol or fluorinated hydrocarbon solvent.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene, xylene, and anisole; n-heptane, n-nonane, n-octane, n-decane, 2-methylheptane, 3-methylheptane, 3 And aliphatic hydrocarbon solvents such as 2,3-dimethylhexane and 2,3,4-trimethylpentane.
Examples of the ester solvent include methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate (n-butyl acetate), pentyl acetate, hexyl acetate, isoamyl acetate, butyl propionate (n-butyl propionate), butyl butyrate, and butyric acid. Isobutyl, butyl butanoate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3- Methoxy butyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, methyl 2-hydroxyisobutyrate, 2- Dorokishiiso butyric acid methyl, isobutyl isobutyrate, and butyl propionate.

  These solvents may be used alone or in combination of two or more. By mixing a solvent other than the above, the solubility in the actinic ray-sensitive or radiation-sensitive film, the solubility of the resin in the composition for forming the upper layer film, the elution characteristics from the actinic ray-sensitive or radiation-sensitive film, Can be appropriately adjusted.

<Step (c)>
Step (c) of the pattern forming method of the present invention is a step of exposing the actinic ray-sensitive or radiation-sensitive film, and can be performed, for example, by the following method.
The actinic ray-sensitive or radiation-sensitive film having the upper layer film formed as described above is irradiated with actinic ray or radiation through a predetermined mask. In electron beam irradiation, drawing (direct drawing) without using a mask is generally performed.
The actinic ray or radiation is not particularly limited. Examples thereof include a KrF excimer laser, an ArF excimer laser, extreme ultraviolet (EUV light, Extreme Ultra Violet), and an electron beam (EB, Electron Beam). preferable. The exposure may be immersion exposure.

<Post exposure bake (PEB: Post Exposure Bake)>
In the pattern forming method of the present invention, it is preferable to perform baking (heating) after exposure and before development. The baking promotes the reaction in the exposed part, and the sensitivity and pattern shape are further improved.
The heating temperature is not particularly limited as long as a good pattern is obtained, and is usually 40 ° C to 160 ° C. The number of times of performing the PEB may be one or more.
The heating time is preferably from 30 to 1000 seconds, more preferably from 60 to 800 seconds, even more preferably from 60 to 600 seconds.
Heating can be carried out by means provided in a usual exposure / developing machine, and may be carried out using a hot plate or the like.

<Step (d)>
Step (d) of the pattern forming method of the present invention is a step of developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer containing an organic solvent.

<Developer>
The developer used in the developing step (d) is preferably an alkali developer or a developer containing an organic solvent. The developer containing an organic solvent can also be referred to as an organic developer.

(Alkali developer)
Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as ammonia water, ethylamine, primary amines such as n-propylamine, diethylamine, Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrapropylammonium Hydoxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyl Tetraalkylammonium hydroxide such as methylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, trimethylphenylammonium hydroxide, trimethyl Quaternary ammonium salts such as benzylammonium hydroxide and triethylbenzylammonium hydroxide, and alkaline aqueous solutions such as cyclic amines such as pyrrole and pyrhelidine can be used.
Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkaline developer is usually from 10.0 to 15.0.
As the alkali developer, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is particularly desirable.

(Organic developer)
Next, the organic solvent contained in the organic developer will be described.
The vapor pressure of the organic solvent (in the case of a mixed solvent, the overall vapor pressure) at 20 ° C. is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. By reducing the vapor pressure of the organic solvent to 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, the temperature uniformity on the wafer surface is improved, and as a result, the dimensional uniformity on the wafer surface is improved. Improve.
As the organic solvent used in the organic developer, various organic solvents are widely used, and examples thereof include an ester solvent, a ketone solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent. Solvent can be used.

An ester solvent is a solvent having an ester bond in the molecule, a ketone solvent is a solvent having a ketone group in the molecule, and an alcohol solvent is a solvent having an alcoholic hydroxyl group in the molecule. The amide-based solvent is a solvent having an amide group in the molecule, and the ether-based solvent is a solvent having an ether bond in the molecule. Among these, there are also solvents having a plurality of the above-mentioned functional groups in one molecule. In such a case, the solvent corresponds to any solvent containing the functional group of the solvent. For example, diethylene glycol monomethyl ether corresponds to both alcohol solvents and ether solvents in the above classification. The hydrocarbon solvent is a hydrocarbon solvent having no substituent.
In particular, an organic developer containing at least one solvent selected from an ester solvent, a ketone solvent, an ether solvent, and a hydrocarbon solvent is preferable, and an organic developer containing an ester solvent is preferred. More preferably, it is a liquid.

  Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, propyl acetate, isopropyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (isopentyl acetate, 3-methylbutyl acetate), acetic acid 2 -Methylbutyl, 1-methylbutyl acetate, hexyl acetate, heptyl acetate, octyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, butyl butyrate, methyl 2-hydroxyisobutyrate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2- Acetoxypropane), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl -Tel acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4- Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-pu Poxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl Acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate , Ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, propionic acid Pentyl, hexyl propionate, heptyl propionate, butyl butanoate, isobutyl butanoate, pentyl butanoate, hexyl butanoate, isobutyl isobutanoate, propyl pentanoate, isopropyl pentanoate, butyl pentanoate, pentyl pentanoate, ethyl hexanoate, Propyl hexanoate, butyl hexanoate, isobutyl hexanoate, methyl heptanoate, ethyl heptanoate, propyl heptanoate, cyclohexyl acetate, cycloheptyl acetate, 2-ethylhexyl acetate, cyclopentyl propionate, methyl 2-hydroxypropionate, 2-hydroxy Ethyl propionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropione Mention may be made of a door or the like. Among these, butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, butyl butanoate are preferably used, and isoamyl acetate is particularly preferred. It is preferably used.

  Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, Phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetenyl alcohol, acetylcarboninol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, γ-butyrolactone, etc. Heptanone is preferred.

  Examples of alcohol solvents include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, -Hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, 3-methyl-3-pen Tanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2- Pentanol, 3-methyl-3-pentanol, 4-methyl-2 Pentanol, 4-methyl-3-pentanol, cyclohexanol, 5-methyl-2-hexanol, 4-methyl-2-hexanol, 4,5-dityl-2-hexal, 6-methyl-2-heptanol, 7 Alcohols (monohydric alcohols) such as -methyl-2-octanol, 8-methyl-2-nonal, 9-methyl-2-decanol and 3-methoxy-1-butanol, and ethylene glycol, diethylene glycol, triethylene glycol and the like Glycol-based solvents, ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, and ethylene. Glycol ether solvents having a hydroxyl group such as glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and propylene glycol monophenyl ether; Can be mentioned. Among these, it is preferable to use a glycol ether-based solvent.

  Examples of the ether-based solvent include, in addition to the glycol ether-based solvent containing a hydroxyl group, glycol ether-based solvents not containing a hydroxyl group such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, anisole, phenetole, and the like. Aromatic ether solvents, dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane and the like. Preferably, a glycol ether solvent or an aromatic ether solvent such as anisole is used.

  Examples of the amide solvent 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 pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, and perfluoroheptane Aliphatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, dipropylbenzene, etc. And unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, and hexadecene.
The unsaturated hydrocarbon solvent may have a plurality of double bonds and triple bonds, and may have it at any position in the hydrocarbon chain. Cis and trans forms having a double bond may be mixed.
The hydrocarbon-based solvent may be a mixture of compounds having the same carbon number and different structures. For example, when decane is used as an aliphatic hydrocarbon solvent, compounds having the same carbon number and different structures, such as 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isodecane, are used as aliphatic hydrocarbon solvents. May be included.
The compounds having the same carbon number and different structures may contain only one kind or a plurality of kinds as described above.

The organic solvent contained in the organic developer has a carbon atom number of 7 or more (7 to 7) in that when the EUV light and EB are used in the exposure step, the swelling of the actinic ray-sensitive or radiation-sensitive film can be suppressed. To 14, more preferably 7 to 12, and even more preferably 7 to 10), and it is preferable to use an ester solvent having 2 or less heteroatoms.
The hetero atom of the ester solvent is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of hetero atoms is preferably 2 or less.

  Preferred examples of the ester solvent having 7 or more carbon atoms and 2 or less hetero atoms are amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, Examples thereof include butyl propionate, isobutyl isobutyrate, heptyl propionate, and butyl butanoate. It is particularly preferable to use isoamyl acetate.

When the EUV light and EB are used in the exposure step, the organic solvent contained in the organic developer is replaced with the ester solvent having 7 or more carbon atoms and 2 or less hetero atoms, You may use the mixed solvent of the said hydrocarbon solvent, or the mixed solvent of the said ketone solvent and the said hydrocarbon solvent. Also in this case, it is effective in suppressing swelling of the actinic ray-sensitive or radiation-sensitive film.
When an ester solvent and a hydrocarbon solvent are used in combination, it is preferable to use isoamyl acetate as the ester solvent. As the hydrocarbon solvent, a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) is used from the viewpoint of adjusting the solubility of the actinic ray-sensitive or radiation-sensitive film. Is preferred.
When a ketone-based solvent and a hydrocarbon-based solvent are used in combination, it is preferable to use 2-heptanone as the ketone-based solvent. As the hydrocarbon solvent, a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) is used from the viewpoint of adjusting the solubility of the actinic ray-sensitive or radiation-sensitive film. Is preferred.
In the case of using the above-mentioned mixed solvent, the content of the hydrocarbon-based solvent depends on the solvent solubility of the actinic ray-sensitive or radiation-sensitive film, and is not particularly limited. I just need.

  A plurality of the above organic solvents may be mixed, or a mixture of a solvent other than the above and water may be used. However, in order to sufficiently exhibit the effects of the present invention, the water content of the entire developer is preferably less than 10% by mass, and more preferably substantially no water content. The concentration of the organic solvent (total in the case of a mixture of a plurality) in the developer is preferably 50% by mass or more, more preferably 50 to 100% by mass, still more preferably 85 to 100% by mass, and still more preferably 90 to 100% by mass. %, Particularly preferably 95 to 100% by mass. Most preferably, it consists essentially of only an organic solvent. In addition, the case of substantially consisting only of an organic solvent includes the case of containing a trace amount of a surfactant, an antioxidant, a stabilizer, an antifoaming agent, and the like.

  The developer also preferably contains an antioxidant. Thereby, generation of the oxidizing agent over time can be suppressed, and the content of the oxidizing agent can be further reduced. As the antioxidant, known ones can be used, but when used for semiconductor applications, amine-based antioxidants and phenol-based antioxidants are preferably used.

  Although the content of the antioxidant is not particularly limited, it is preferably 0.0001 to 1% by mass, more preferably 0.0001 to 0.1% by mass, and 0.0001 to 0% by mass based on the total mass of the developer. 0.01% by mass is more preferred. When the content is 0.0001% by mass or more, a more excellent antioxidant effect is obtained, and when the content is 1% by mass or less, development residues tend to be suppressed.

  The developer may contain a basic compound, and specific examples thereof include those similar to the basic compound that the actinic ray-sensitive or radiation-sensitive composition may contain.

The developer may contain a surfactant. When the developer contains a surfactant, the wettability to the actinic ray-sensitive or radiation-sensitive film is improved, and the development proceeds more effectively.
As the surfactant, those similar to the surfactant which the actinic ray-sensitive or radiation-sensitive resin composition can contain can be used.
When the developer contains a surfactant, the content of the surfactant is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, based on the total mass of the developer. %, More preferably 0.01 to 0.5% by mass.

As a developing method, for example, a method of dipping a substrate in a bath filled with a developing solution for a certain period of time (dip method), a method of raising the developing solution on the substrate surface by surface tension and stopping for a certain period of time (paddle) Method), a method of spraying a developing solution onto a substrate surface (spray method), and a method of continuously discharging a developing solution while scanning a developing solution discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispense method). Etc. can be applied.
Further, after the step of performing development, a step of stopping development while replacing the solvent with another solvent may be performed.
The development time is not particularly limited and is usually 10 to 300 seconds, preferably 20 to 120 seconds.
The temperature of the developer is preferably from 0 to 50 ° C, more preferably from 15 to 35 ° C.

  As the developer used in the development step, both development using a developer containing an organic solvent and development using an alkali developer may be performed (so-called double development may be performed).

<Step (e)>
The pattern forming method of the present invention preferably has a step (e) of rinsing (washing) the developed actinic ray-sensitive or radiation-sensitive film using a rinsing liquid after the step (d).

<Rinse liquid>
As the rinsing liquid in the rinsing treatment performed after the alkali development, pure water is used, and an appropriate amount of a surfactant may be added.
Further, after the development process or the rinsing process, a process of removing the developing solution or the rinsing solution attached to the pattern with a supercritical fluid can be performed.

  It is preferable to use a rinsing liquid containing an organic solvent (organic rinsing liquid) as the rinsing liquid in the rinsing treatment performed after the organic solvent development.

  The vapor pressure of the rinsing liquid (in the case of a mixed solvent, the vapor pressure as a whole) at 20 ° C. is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and 0.12 kPa or more. And 3 kPa or less is most preferable. By making the vapor pressure of the rinsing liquid 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and the swelling due to the penetration of the rinsing liquid is suppressed, and the dimensional uniformity in the wafer surface is reduced. Is improved.

(Organic solvent)
As the organic solvent contained in the organic rinsing liquid, various organic solvents are used, and are selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. It is preferable to use at least one organic solvent selected. In particular, the rinsing liquid preferably contains a hydrocarbon solvent.
Specific examples of these organic solvents are the same as the organic solvents described for the developer.

As the organic solvent contained in the organic rinsing liquid, when EUV light or EB is used in the exposure step, it is preferable to use a hydrocarbon solvent among the above organic solvents, and to use an aliphatic hydrocarbon solvent. Is more preferred. As the aliphatic hydrocarbon solvent used for the rinsing liquid, from the viewpoint that the effect is further improved, an aliphatic hydrocarbon solvent having 5 or more carbon atoms (for example, pentane, hexane, octane, decane, undecane, dodecane, Hexadecane, etc.) are preferred, aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferred, and aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferred.
The upper limit of the number of carbon atoms in the aliphatic hydrocarbon solvent is not particularly limited, but is, for example, 16 or less, preferably 14 or less, and more preferably 12 or less.
Among the above-mentioned fatty hydrocarbon solvents, decane, undecane and dodecane are particularly preferred, and undecane is most preferred.
By using a hydrocarbon-based solvent (especially an aliphatic hydrocarbon-based solvent) as the organic solvent contained in the rinsing liquid, the developer slightly permeated into the actinic ray-sensitive or radiation-sensitive film after development is washed away. As a result, the effect of further suppressing swelling and suppressing pattern collapse is further exhibited.
In addition, examples of the hydrocarbon-based solvent include unsaturated hydrocarbon-based solvents such as octene, nonene, decene, undecene, dodecene, and hexadecene.
The unsaturated hydrocarbon solvent may have a plurality of double bonds and triple bonds, and may have it at any position in the hydrocarbon chain. Cis and trans forms having a double bond may be mixed.
The hydrocarbon-based solvent may be a mixture of compounds having the same carbon number and different structures. For example, when decane is used as an aliphatic hydrocarbon solvent, compounds having the same carbon number and different structures, such as 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isodecane, are used as aliphatic hydrocarbon solvents. May be included.
The compounds having the same carbon number and different structures may contain only one kind or a plurality of kinds as described above.

  A plurality of organic solvents may be mixed, or a mixture of organic solvents other than those described above may be used. The solvent may be mixed with water, but the water content in the rinsing liquid is usually 60% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less. is there. By setting the water content to 60% by mass or less, good rinsing characteristics can be obtained.

The rinsing liquid preferably contains a surfactant. Thereby, the wettability to the actinic ray-sensitive or radiation-sensitive film is improved, and the cleaning effect tends to be further improved.
As the surfactant, those similar to the surfactant used in the actinic ray-sensitive or radiation-sensitive resin composition can be used.
The content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass based on the total mass of the rinsing liquid. .

  The rinse liquid preferably contains an antioxidant. Thereby, generation of the oxidizing agent over time can be suppressed, and the content of the oxidizing agent can be further reduced. Specific examples and contents of the antioxidant are as described in the developer.

  In the rinsing step, the developed wafer is washed using the above-mentioned rinsing liquid. The method of the cleaning treatment is not particularly limited. For example, a method of continuously discharging a rinsing liquid onto a substrate rotating at a constant speed (rotation coating method), or immersing the substrate in a bath filled with the rinsing liquid for a predetermined time A method (dip method) and a method of spraying a rinsing liquid on the substrate surface (spray method) are exemplified. Among these, it is preferable to remove the rinsing liquid from the substrate by rotating the substrate at a rotation speed of 2000 rpm to 4000 rpm after performing the cleaning treatment by the spin coating method.

  Generally, the developing solution and the rinsing solution are stored in a waste liquid tank through a pipe after use. In this case, when a hydrocarbon solvent is used as the rinsing liquid, in order to prevent the resist dissolved in the developing solution from depositing and adhering to the back surface of the wafer or the side surface of the pipe, the solvent in which the resist is dissolved again is used. Through a pipe. As a method of passing through a pipe, a method in which the back and side surfaces of the substrate are washed and rinsed with a solvent that dissolves the resist after washing with a rinsing liquid, or a solvent in which the resist dissolves without contacting the resist can be passed through the pipe. Method.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention and various materials used in the pattern forming method of the present invention (for example, a resist solvent, a developing solution, a rinsing solution, a composition for forming an antireflection film, an upper layer) The film-forming composition) preferably does not contain impurities such as a metal, a metal salt containing a halogen, an acid, and an alkali (excluding an alkali in an alkali developer). The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free of them (below the detection limit of the measuring device). Is most preferred.
Examples of a method for removing impurities such as metals from various materials include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be a composite material combining these materials and an ion exchange medium. The filter may be one that has been washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore sizes and / or materials may be used in combination. Further, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step.
Further, as a method for reducing impurities such as metals contained in various materials, a material having a low metal content is selected as a material constituting various materials, and a filter filtration is performed on the materials constituting various materials. A method in which the inside is lined with Teflon (registered trademark) or the like and distillation is performed under the condition where contamination is suppressed as much as possible. Preferred conditions for filter filtration performed on raw materials constituting various materials are the same as those described above.
In addition to filter filtration, impurities may be removed by an adsorbent, or a combination of filter filtration and an adsorbent may be used. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel and zeolite, and an organic adsorbent such as activated carbon can be used.

<Container>
When the developing solution and the rinsing solution are organic solvents, the organic solvent (organic processing solution) that can be used for the developing solution and the rinsing solution is a storage of an organic processing solution for patterning a chemically amplified resist film having a storage section. It is preferable to use one stored in a container. As the storage container, for example, the inner wall of the storage portion that is in contact with the organic treatment liquid is made of a resin different from polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin, or is subjected to rust prevention and metal elution prevention treatment. It is preferable that the container is a container for an organic treatment liquid for patterning a chemically amplified resist film formed from the metal thus formed. An organic solvent to be used as an organic treatment liquid for patterning a chemically amplified resist film is stored in the storage section of the storage container, and is discharged from the storage section during patterning of the chemically amplified resist film. Can be used.

When the storage container further has a seal portion for sealing the storage portion, the seal portion is also a polyethylene resin, a polypropylene resin, and a resin different from the polyethylene-polypropylene resin, or It is preferably formed from a metal that has been subjected to rust prevention and metal elution prevention treatment.
Here, the seal portion means a member capable of shutting off the housing portion and the outside air, and preferably includes a packing, an O-ring, and the like.

  The resin different from the polyethylene resin, the polypropylene resin, and the polyethylene-polypropylene resin is preferably a perfluoro resin.

As the perfluoro resin, tetrafluoroethylene resin (PTFE), ethylene tetrafluoride / perfluoroalkyl vinyl ether copolymer (PFA), ethylene tetrafluoride-propylene hexafluoride copolymer resin (FEP), tetrafluoride Ethylene-ethylene copolymer resin (ETFE), ethylene trifluoride ethylene-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), ethylene trifluoride ethylene copolymer resin (PCTFE), vinyl fluoride resin ( PVF) and the like.
Particularly preferred perfluoro resins include ethylene tetrafluoride resin, ethylene tetrafluoride / perfluoroalkyl vinyl ether copolymer, and ethylene tetrafluoride-propylene hexafluoride copolymer resin.

Examples of the metal which has been subjected to the rust prevention / metal elution prevention treatment include carbon steel, alloy steel, nickel chromium steel, nickel chromium molybdenum steel, chromium steel, chromium molybdenum steel, and manganese steel.
As the rust prevention / metal elution prevention treatment, it is preferable to apply a coating technique.
The coating technology is roughly divided into three types: metal coating (various plating), inorganic coating (various chemical treatment, glass, concrete, ceramics, etc.) and organic coating (rust preventive oil, paint, rubber, plastics). .
Preferred coating techniques include surface treatment with rust inhibitor oil, rust inhibitors, corrosion inhibitors, chelating compounds, strippable plastics, and lining agents.
Among them, various chromates, nitrites, silicates, phosphates, carboxylic acids such as oleic acid, dimer acid, naphthenic acid, carboxylic acid metal soaps, sulfonates, amine salts, esters (glycerin esters of higher fatty acids) And phosphoric acid esters), chelating compounds such as ethylenediantetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethylethylenediamine triic acid, and diethylenetriaminepentaic acid, and fluororesin linings are preferred. Particularly preferred are phosphating and fluororesin lining.
Also, compared to direct coating treatment, it does not directly prevent rust, but as a treatment method that extends the rust prevention period due to coating treatment, it is a stage before rust prevention treatment, "pre-treatment" It is also preferable to employ
As a specific example of such a pretreatment, a treatment for removing various corrosion factors such as chlorides and sulfates present on the metal surface by washing or polishing can be preferably mentioned.

Specific examples of the storage container include the following.
-FluoroPure PFA composite drum manufactured by Entegris (inner surface of liquid: PFA resin lining)
・ Steel drum by JFE (in contact with liquid; zinc phosphate coating)

  In addition, examples of the storage container that can be used in the present invention include the containers described in JP-A-11-021393 [0013] to [0030] and JP-A-10-45961 [0012] to [0024]. be able to.

  The organic processing solution of the present invention may be added with a conductive compound in order to prevent failure of chemical solution piping and various parts (filters, O-rings, tubes, etc.) due to static electricity charging and subsequent electrostatic discharge. good. The conductive compound is not particularly limited, but includes, for example, methanol. The amount of addition is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining preferable development characteristics. Regarding the member of the chemical solution piping, various types of piping coated with SUS (stainless steel) or polyethylene, polypropylene or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment may be used. it can. Similarly, for the filter and the O-ring, polyethylene, polypropylene, or a fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, or the like) subjected to an antistatic treatment can be used.

  The pattern obtained by the pattern forming method of the present invention is generally suitably used as an etching mask of a semiconductor device, but can be used for other purposes. As other uses, for example, guide pattern formation in DSA (Directed Self-Assembly) (for example, see ACS Nano Vol. 4 No. 8 Page 4815-4823), use as a so-called spacer process core (for example) JP-A-3-270227 and JP-A-2013-164509).

[Electronic device manufacturing method]
The present invention also relates to a method for manufacturing an electronic device, including the pattern forming method of the present invention described above.
An electronic device manufactured by the method for manufacturing an electronic device according to the present invention is suitably mounted in the manufacture of electrical and electronic equipment (home appliances, office equipment (OA) / media-related equipment, optical equipment, communication equipment, and the like). It is.

[Laminate]
The present invention is a laminate comprising an actinic ray-sensitive or radiation-sensitive film and an upper layer film, wherein the actinic ray-sensitive or radiation-sensitive film contains a resin containing a repeating unit having an aromatic ring, and the upper layer The film also relates to a laminate including a compound (Q) having a molecular weight of 5,000 or less, which does not generate an acid by actinic rays or radiation, in an amount of 1% by mass to 40% by mass based on the total mass of the upper layer film.
The laminate of the present invention is preferably a laminate having an actinic ray-sensitive or radiation-sensitive film on a substrate and the above-mentioned upper layer film in this order, and is suitable as a resist material for pattern formation included in a semiconductor device or the like. Can be used.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

The following resin was used as the resin (A).
The composition ratio of the following repeating units is a molar ratio. Mw is the weight average molecular weight, Mw / Mn is the degree of dispersion, and Mn is the number average molecular weight.

  The following were used as the photoacid generator.

P-5

  The following were used as the acid diffusion controller.

  The following were used as the crosslinking agent.

  The following were used as the hydrophobic resin.

  The following were used as basic compounds.

The following were used as the resist solvent.
C-1: Propylene glycol monomethyl ether acetate (PGMEA)
C-2: Propylene glycol monomethyl ether (PGME)
C-3: Ethyl lactate (EL)
C-4: cyclohexanone

  The following resin was used as the resin for the upper layer film. The structure of the resin, the composition ratio of each repeating unit (molar ratio, corresponding to the order from the left), the weight average molecular weight (Mw), and the degree of dispersion (Mw / Mn) are shown below.

T-1: Polyacrylic acid Jurimer AC-10L (manufactured by Nippon Pure Chemical Industries, Ltd.)
T-2: Poly (N-vinylpyrrolidone) Luviskol K90 (manufactured by BASF Japan Ltd.)
T-3: (vinyl alcohol 60 / vinyl acetate 40) copolymer SMR-8M (manufactured by Shin-Etsu Chemical Co., Ltd.)
T-4: Pullulan PI-20 (manufactured by Hayashibara)

  As the additive, those described above as the compound (Q) were used.

The following were used as the topcoat solvent.
Y1: 4-methyl-2-pentanol (MIBC)
Y2: Decane Y3: Diisoamyl ether Y4: 1-butanol Y5: Isobutyl isobutyrate Y6: Isobutyl alcohol Y7: Water

<Examples 1 to 14, Comparative Examples 1 to 4>
[Preparation of resist composition]
The components shown in Table 2 are dissolved in a solvent (mixing ratio is mass ratio), and a solution having a solid content concentration of 1.5% by mass is prepared for each, and the solution is further filtered through a polyethylene filter having a pore size of 0.03 μm. And a resist composition was prepared.

[Preparation of composition for forming upper layer film]
The components shown in Table 3 below were dissolved in a solvent, and a solution having a solid content concentration of 2.0% by mass was prepared for each. The solution was filtered through a polyethylene filter having a pore size of 0.04 μm to prepare a composition for forming an upper layer film.

[Formation of resist film]
A resist composition shown in Table 4 below was applied on a 4-inch silicon wafer that had been subjected to HMDS (hexamethyldisilazane) treatment, and baked (PB: Prebake) at 120 ° C. for 60 seconds to obtain a film thickness. Formed a resist film having a thickness of 40 nm. One inch is 25.4 mm.

(Formation of upper layer film)
The composition for forming an upper layer film shown in Table 4 below was applied on the resist film to form an upper layer film having a thickness of 30 nm.

[EUV exposure]
The wafer prepared as described above was subjected to EUV exposure using NA (lens numerical aperture, Numerical Aperture) 0.3 and Annular illumination. Specifically, in order to obtain a dot pattern after the negative development, EUV exposure was performed by changing the exposure amount through a dark mask including a hole pattern having a pitch of 100 nm and a diameter of 20 nm. However, in Examples and Comparative Examples in which development was performed using SG-4 as a developing solution, EUV exposure was performed by changing the exposure amount through a bright mask including a dot pattern having a pitch of 100 nm and a diameter of 20 nm.

[Bake after exposure (PEB: Post Exposure Bake)]
After the irradiation, after being taken out of the EUV exposure apparatus, it was immediately baked for 60 seconds under the temperature conditions shown in Table 4 below.

〔developing〕
Thereafter, using a shower type developing device (ADE3000S manufactured by ACTES Corp.), the developer (23 ° C.) shown in Table 4 was supplied at a flow rate of 200 mL / min while rotating the wafer at 50 rotations (rpm). Development was performed by spraying for a time.

〔rinse〕
Thereafter, a rinsing treatment was performed by spraying a rinsing liquid (23 ° C.) shown in Table 4 below at a flow rate of 200 mL / min for a predetermined time while rotating the wafer at 50 rotations (rpm). Finally, the wafer was rotated at a high speed of 2500 rotations (rpm) for 120 seconds to dry the wafer.

(Evaluation of resist pattern EUV resolution)
Using a scanning electron microscope (S-9380II, manufactured by Hitachi, Ltd.), the dot diameter of the obtained resist pattern is measured, and the desired dot pattern is separated and resolved without occurrence of collapse or peeling. The minimum dimensions were calculated. The results are shown in Table 4 below as “EUV resolution”.

[EB exposure]
Using an electron beam irradiation apparatus (JBX6000 manufactured by JEOL; acceleration voltage 50 keV, Spot Beam method), a line pattern having a line width of 20 nm to 40 nm in 2.5 nm steps is formed on the resist film on which the upper layer film is formed. (0.5 mm in the length direction, 50 drawing lines) were exposed while changing the irradiation amount.

  Immediately after the irradiation, the substrate was baked (PEB: Post Exposure Bake) for 60 seconds on a hot plate under the conditions shown in Table 4 below.

  Subsequently, the developer (23 ° C.) shown in Table 4 was supplied at a flow rate of 200 mL / min while rotating the wafer at 50 rotations (rpm) using a shower-type developing device (ADE3000S manufactured by ACTES Corporation). The developer was sprayed on the wafer for 5 seconds to pour the developer on the wafer. Next, the rotation of the wafer was stopped, and the wafer was left standing for 60 seconds to perform development.

  Then, the wafer is rotated at 50 revolutions (rpm) using a rinsing liquid (23 ° C.) shown in Table 4 below at a flow rate of 200 mL / min and spray-discharged for 30 seconds to perform a rinsing process, so that the intervals are equal. Then, a line-and-space (L / S) resist pattern in which line patterns were lined up was obtained.

(Evaluation of resist pattern EB resolution)
The minimum line width for separating and resolving at a line-to-space ratio of 1: 1 was defined as the resolving power (nm). The results are shown in Table 4 below as “EB resolution”.

<Developer>
The following were used as the developer.
SG-1: methyl amyl ketone SG-2: isoamyl acetate SG-3: butyl acetate SG-4: 2.38 mass% aqueous solution of tetrabutylammonium SG-5: diisobutyl ketone

<Rinse liquid>
The following was used as the rinsing liquid.
RI-1: undecane RI-2: isodecane RI-3: decane RI-4: 4-methyl-2-pentanol RI-5: pure water RI-6: undecane / diisobutyl ketone = 30/70

<Examples 15 to 74, Comparative Examples 5 to 20>
[Preparation of resist composition]
The components shown in Tables 5 and 6 were dissolved in a solvent (mixing ratio is mass ratio), and a solution having a solid content concentration of 1.5% by mass was prepared for each. Thus, a resist composition was prepared.

[Preparation of composition for forming upper layer film]
The components shown in Table 7 below were dissolved in a solvent, and a solution having a solid content of 2.0% by mass was prepared for each, and the solution was filtered through a polyethylene filter having a pore size of 0.04 μm to prepare a composition for forming an upper layer film. .

(Formation of resist film)
The resist compositions described in Tables 8 to 11 were uniformly applied to a 6-inch silicon substrate that had been subjected to hexamethyldisilazane treatment using a spin coater. Next, baking was performed at 110 ° C. for 90 seconds using a hot plate. Thus, a resist film having a thickness of 30 nm was formed.

(Formation of upper layer film)
Compositions for forming an upper layer film shown in Tables 8 to 11 below were applied on the resist film to form an upper layer film having a thickness of 30 nm.

[EB exposure]
Using an electron beam irradiation apparatus (JBX6000 manufactured by JEOL; acceleration voltage 50 keV, Spot Beam method), a line pattern having a line width of 20 nm to 40 nm in 2.5 nm steps is formed on the resist film on which the upper layer film is formed. (0.5 mm in the length direction, 50 drawing lines) were exposed while changing the irradiation amount.

  Immediately after the irradiation, it was baked (Post Exposure Bake; PEB) on a hot plate at the temperature conditions shown in Tables 8 to 11 for 60 seconds.

  Subsequently, while rotating the wafer at 50 rotations (rpm) using a shower-type developing device (ADE3000S manufactured by ACTES Corporation), a 2.38% TMAH (tetramethylammonium hydroxide) developing solution (23 ° C.) was added at 200 mL / The developer was sprayed on the wafer at a flow rate of min for 5 seconds. Then, the rotation of the wafer was stopped, and the wafer was left standing for 60 seconds to perform development.

  Then, the wafer is rotated at 50 revolutions (rpm) while using pure water as a rinsing liquid (23 ° C.) and spraying at a flow rate of 200 mL / min for 30 seconds to perform a rinsing process, thereby forming line patterns at regular intervals. Were obtained as a line and space (L / S) resist pattern.

<Evaluation>
(Resolution)
The minimum line width for separating and resolving at a line-to-space ratio of 1: 1 was defined as the resolving power (nm). The results are shown in Tables 8 to 11 as "EB resolution".

  After the exposure and PEB in Examples 15 and Comparative Examples 5 and thereafter, the upper layer film was peeled off using a solvent of MIBC / decane = 90/10 (mass ratio), and then developed.

[EUV exposure]
EUV exposure was performed on a wafer having a resist film on which an upper layer film was formed as described above, using NA (lens numerical aperture, Numerical Aperture) 0.3 and Annular illumination. Specifically, in order to obtain a dot pattern after the negative development, EUV exposure was performed by changing the exposure amount through a dark mask including a hole pattern having a pitch of 100 nm and a diameter of 20 nm. However, in Examples and Comparative Examples in which TMAH development was performed, EUV exposure was performed by changing the exposure amount through a bright mask including a dot pattern having a pitch of 100 nm and a diameter of 20 nm.

[Bake after exposure (PEB: Post Exposure Bake)]
After the irradiation, after being taken out of the EUV exposure apparatus, it was immediately baked for 60 seconds under the temperature conditions shown in Table 4 below.

〔developing〕
Then, while rotating the wafer at 50 rotations (rpm) using a shower type developing device (ADE3000S manufactured by ACTES Corporation), a 2.38% TMAH developing solution (23 ° C.) was supplied at a flow rate of 200 mL / min. Development was performed by spraying for a time.

〔rinse〕
Thereafter, while rotating the wafer at 50 rotations (rpm), a rinse treatment was performed by spraying pure water as a rinse liquid (23 ° C.) at a flow rate of 200 mL / min for a predetermined time. Finally, the wafer was rotated at a high speed of 2500 rotations (rpm) for 120 seconds to dry the wafer.

<Evaluation>
(Resolution)
Using a scanning electron microscope (S-9380II, manufactured by Hitachi, Ltd.), the dot diameter of the obtained resist pattern is measured, and the desired dot pattern is separated and resolved without occurrence of collapse or peeling. The minimum dimensions were calculated. The results are shown in Tables 8 to 11 as “EUV resolution”.

  As described above, the pattern forming method and the laminate according to the examples of the present invention showed better results in line and space and dot resolution than the comparative example.

The pattern forming method and the laminate of the present invention can provide the same effects as those of the above-described embodiment even by the multi-beam exposure as described below.
There is a multi-beam system (hereinafter, also referred to as “electron beam multi-beam exposure”) that increases efficiency by simultaneously irradiating a plurality of electron beams (for example, see Non-Patent Documents 2 and 3).
Non-Patent Document 2: Elmar Platzgummer, Stefan Cernusca, Christof Klein, Jan Klikovits, Samuel Kvasnica, Hans Loeschner, "eMET - 50 keV electron Mask Exposure Tool Development based on proven multi-beam projection technology", Proc. SPIE Vol. 7823, 782308 (2010).
Non-Patent Document 3: Christof Klein, Hans Loschner,
Elmar Platzgummer, "Performance of the Proof-of-Concept Multi-Beam Mask Writer", Proc. SPIE Vol. 8880, 88801E (2013).

  In Examples 29 to 42 and Examples 59 to 74, the same effects can be obtained by performing development and rinsing using an organic solvent to form a negative pattern.

  According to the present invention, particularly in the formation of an extremely fine pattern (for example, a dot or a line and space having a diameter of 30 nm or less), a pattern forming method capable of obtaining a high resolution with a small film loss and an electronic device including the pattern forming method A device manufacturing method and a laminate for forming the pattern can be provided.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on Sep. 30, 2015 (Japanese Patent Application No. 2015-195492), the contents of which are incorporated herein by reference.

Claims (14)

(A) forming an actinic ray-sensitive or radiation-sensitive film with the actinic ray-sensitive or radiation-sensitive resin composition;
(B) forming an upper layer film on the actinic ray-sensitive or radiation-sensitive film using the composition for forming an upper layer film;
(C) exposing the actinic ray-sensitive or radiation-sensitive film on which the upper layer film is formed; and (d) developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer. A pattern forming method comprising:
The actinic ray-sensitive or radiation-sensitive resin composition contains a resin containing a repeating unit having an aromatic ring, and a photoacid generator,
The resin containing a repeating unit having an aromatic ring is a resin containing a repeating unit having a phenolic hydroxyl group,
The compound for forming the upper layer film, which does not generate an acid by actinic rays or radiation and has a molecular weight of 5,000 or less, is used in an amount of 1% by mass to 40% by mass based on the total solid content of the composition for forming the upper layer film. Including
The compound (Q) is at least one compound selected from the following X1 to X6, TQ-1 to TQ-18, and A-1 to A-35;
The composition for forming an upper layer film contains a solvent, and the solvent is an alcohol solvent, an ether solvent, an ester solvent, a fluorine solvent, a hydrocarbon solvent, or an organic solvent obtained by mixing a plurality of these solvents. The solvent contained in the film-forming composition may or may not contain a solvent having a hydroxyl group, and when the solvent containing a hydroxyl group is contained, the content ratio of the solvent having a hydroxyl group to the total solvent. Is 50% by mass or less.

X3: tri-N-octylamine, X4: 1- (tert-butoxycarbonyl) -4-hydroxypiperidine, X5: tert-butyl 1-pyrrolidinecarboxylate, X6: triisopropanolamine





  The pattern forming method according to claim 1, wherein the compound (Q) has a molecular weight of 1500 or less.   3. The pattern forming method according to claim 1, wherein the content of the compound (Q) is 30% by mass or less based on the total solid content of the composition for forming an upper layer film. 4.   The pattern forming method according to claim 1 or 2, wherein the content of the compound (Q) is 20% by mass or less based on the total solid content of the composition for forming an upper layer film.   The pattern formation method according to claim 1, wherein the compound (Q) is at least one compound selected from the TQ-1 to TQ-18, A-22 to A-27, and A-33.   The pattern forming method according to any one of claims 1 to 5, wherein the content of the organic solvent is 50% by mass or more based on all solvents contained in the composition for forming an upper layer film.   The pattern forming method according to any one of claims 1 to 6, wherein the actinic ray-sensitive or radiation-sensitive resin composition contains a crosslinking agent.   The pattern forming method according to any one of claims 1 to 7, wherein the developer is a developer containing an organic solvent.   The pattern forming method according to claim 8, wherein the developer containing the organic solvent includes at least one solvent selected from an ester solvent, a ketone solvent, an ether solvent, and a hydrocarbon solvent.   The pattern forming method according to claim 9, wherein the developer containing the organic solvent contains an ester solvent. After the step (d),
(E) rinsing the developed actinic ray-sensitive or radiation-sensitive film with a rinsing liquid,
The pattern forming method according to claim 1, wherein the rinsing liquid includes a hydrocarbon-based solvent.   The pattern forming method according to claim 1, wherein the exposure is performed using an electron beam or extreme ultraviolet light.   An electronic device manufacturing method, comprising the pattern forming method according to claim 1. A laminate comprising an actinic ray-sensitive or radiation-sensitive film and an upper layer film,
The actinic ray-sensitive or radiation-sensitive film contains a resin containing a repeating unit having an aromatic ring, and a photoacid generator,
The resin containing a repeating unit having an aromatic ring is a resin containing a repeating unit having a phenolic hydroxyl group,
The upper layer film contains a compound (Q) having a molecular weight of 5,000 or less, which does not generate an acid by actinic rays or radiation, from 1% by mass to 40% by mass based on the total mass of the upper layer film,
The compound (Q) is at least one compound selected from the lower Symbol T Q-1~TQ-18, A -22~A-27 and A-33,, laminate.