JP2010175859A - Actinic ray-sensitive or radiation-sensitive resin composition and pattern formation method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an actinic ray-sensitive or radiation-sensitive resin composition, capable of forming a pattern which simultaneously satisfies high sensitivity, high resolution, proper pattern profile and satisfactory line edge roughness, particularly in an electron beam, X-ray or EUV lithography in an ultrafine region, and to provide a pattern formation method that uses the composition. <P>SOLUTION: The actinic ray-sensitive or radiation-sensitive resin composition comprises (A) a resin which decomposes under the action of an acid and exhibits an increased dissolution rate in an aqueous alkali solution; (B) a compound which generates an acid upon irradiation with actinic rays or radiation; and (C) a compound which is unevenly distributed unevenly in a film surface, upon formation of film. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in an ultramicrolithography process such as the manufacture of VLSI and high-capacity microchips and other photofabrication processes, and a pattern forming method using the same More particularly, the present invention relates to a positive resist composition for electron beam, X-ray or EUV light, a pattern forming method using the same, and a resin used for the positive resist composition.

  In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation.

  Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this, there is a tendency to shorten the exposure wavelength from g-line to i-line and further to KrF excimer laser light. Furthermore, at present, in addition to excimer laser light, lithography using electron beams, X-rays, or EUV light is also being developed.

  In particular, lithography using an electron beam or EUV is positioned as a next-generation or next-generation pattern formation technology, and a positive resist with high sensitivity and high resolution is desired. In particular, high sensitivity is a very important issue for shortening the wafer processing time. However, when using chemically amplified resists, especially in lithography using electron beams or EUV, the sensitivity decreases and the shape of the resist pattern deteriorates. There is a problem that problems such as a decrease in resolution occur.

  One of the causes of such problems is contamination (environmental influence) on the resist layer of a basic substance such as amine existing in the environment. That is, in the chemically amplified resist, due to the reaction mechanism of utilizing the action of acid, the acid is deactivated by the contamination of the basic substance, and its performance (sensitivity, shape, resolution, etc.) is affected. In addition, such environmental influence is also caused by the length of the process delay, for example, the time from the application of the resist to the exposure and the time from the exposure to the post-exposure heating (PEB). The degree differs, and this causes a difference in performance between lots, and changes in sensitivity, shape, resolution, and the like. In particular, in lithography using an electron beam or EUV, since exposure is usually performed in a reduced pressure environment, it is necessary to perform a reduced pressure operation, a purge operation, or the like, so that the process delay is long and the environmental influence becomes a serious problem. With respect to such a problem, a protective film forming material for a resist layer used in electron beam or EUV lithography has been disclosed (Patent Document 1). That is, after forming a resist layer on a substrate, a protective film is formed on the resist layer using a protective film forming material, and the resist layer is selectively exposed with an electron beam or EUV through the protective film. Then, after performing PEB (post-exposure heating), the protective film is removed, and the resist layer is developed to form a resist pattern. However, a method of forming a protective film using such a protective film forming material requires a longer process, and a simpler and lower cost method is required.

  One of the other causes of the above-mentioned problems is the volatilization of basic substances and acids from the resist film. In ultrafine pattern formation of several tens of nanometers or less, volatilization of a very small amount of basic substance or acid in the process before exposure, during exposure, or after exposure causes a decrease in sensitivity, shape deterioration of the resist pattern, and resolution. This has a major impact on the decline of the product, and its improvement is an issue.

  Furthermore, the volatilization of the compound from the resist film causes contamination of the exposure apparatus which is very expensive as outgas, and the reduction of outgas from the resist film is also a very important issue. A solution is needed. Since both the electron beam and EUV lithography are required to be in a vacuum state, it is essential to solve this problem.

  In order to solve such a problem, it is disclosed that an EUV transmissive protective film (topcoat) having a EUV radiation transmittance higher than 50% made of a polymer including a group including boron is provided on a resist layer. (Patent Document 2). However, the method of forming a protective film using such a protective film forming material requires a longer process as described above, and a simpler and lower cost method is required.

JP 2006-58739 A Patent No. 4036849

  The object of the present invention is to provide an activity that simultaneously satisfies high sensitivity, high resolution, good pattern shape, and good line edge roughness in an ultrafine region, particularly in electron beam, X-ray or EUV light lithography. The object is to provide a light or radiation sensitive resin composition and a pattern forming method using the same.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention shown below.
(1) (A) a resin that is decomposed by the action of an acid to increase the dissolution rate in an alkaline aqueous solution;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(C) a compound that is unevenly distributed on the film surface by film formation;
An actinic ray-sensitive or radiation-sensitive resin composition comprising:

  (2) The active sensitivity according to (1), wherein the compound (C) unevenly distributed on the film surface is a resin having a fluorine atom and / or a silicon atom and / or a hydrocarbon group in a side chain. Light or radiation sensitive resin composition.

(3) The compound (B) that generates an acid upon irradiation with actinic rays or radiation contains at least a compound represented by the following general formula (I), (1) or (2) An actinic ray-sensitive or radiation-sensitive resin composition.

In general formula (I),
R ^{1 to} R ¹³ each independently represents a hydrogen atom or a substituent.
Z represents a single bond or a divalent linking group.
X ⁻ represents a counter anion.

(4) The resin (A) that decomposes by the action of an acid and increases the dissolution rate in an alkaline aqueous solution has a repeating unit represented by the general formula (II) and a repeating unit represented by the general formula (III) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (3).

In general formulas (II) and (III):
R ₀₁ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a halogen atom, a cyano group, or a substituted or unsubstituted alkoxycarbonyl group.
L1 and L2 may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group. To express.
M represents a single bond or a divalent linking group.
Q represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted alicyclic group or aromatic ring group which may contain a hetero atom.
At least two of Q, M, and L1 may combine to form a 5-membered or 6-membered ring.
When there are a plurality of A, each independently represents a halogen atom, a cyano group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted acyloxy group, or A substituted or unsubstituted alkoxycarbonyl group is represented.
m and n each independently represents an integer of 0 to 4.

  (5) The actinic ray-sensitive or radiation-sensitive resin composition contains (E) an organic solvent, and 50% by mass or more of the organic solvent (E) is propylene glycol monomethyl ether, (1) ) -Actinic light-sensitive or radiation-sensitive resin composition according to any one of (4).

  (6) including a step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (5), and exposing and developing with an electron beam, X-ray or EUV. A pattern forming method characterized by the above.

  According to the present invention, an actinic ray that simultaneously satisfies high sensitivity, high resolution, good pattern shape, and good line edge roughness in an ultrafine region, particularly in electron beam, X-ray or EUV light lithography. A radiation-sensitive resin composition and a pattern forming method using the composition can be provided.

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

[1] Resin (A) which decomposes by the action of an acid and increases the solubility in an aqueous alkali solution
A resin that is decomposed by an acid used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and has increased solubility in an alkaline aqueous solution (hereinafter also referred to as “acid-decomposable resin” or “resin (A)”) is a resin. It is a resin having a group (acid-decomposable group) that is decomposed by the action of an acid to generate an alkali-soluble group in the main chain or side chain, or in both the main chain and side chain. Among these, a resin having an acid-decomposable group in the side chain is more preferable.

A preferable group as the acid-decomposable group is a group in which a hydrogen atom of an alkali-soluble group such as a —COOH group or a —OH group is substituted with a group capable of leaving with an acid.
In the present invention, the acid-decomposable group is preferably an acetal group or a tertiary ester group.

  The base resin (A) in the case where these acid-decomposable groups are bonded as side chains is preferably an alkali-soluble resin having —OH or —COOH groups in the side chains.

  When formed as a resist film, the alkali dissolution rate of these alkali-soluble resins is preferably 80 to 8 nm / second or more as measured with 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, it is 160 to 16 nm / second or more.

  The acid-decomposable resin preferably contains a repeating unit having an aromatic group, and is particularly preferably an acid-decomposable resin having a hydroxystyrene-based repeating unit (hereinafter also referred to as “resin (A1)”). . More preferred are a hydroxystyrene copolymer protected with a group capable of leaving with hydroxystyrene / acid, and a hydroxystyrene / (meth) acrylic acid tertiary alkyl ester copolymer.

The content of the repeating unit having an acid-decomposable group is determined by the number of acid-decomposable groups in the resin (B) and the number of alkali-soluble groups not protected by an acid-eliminating group (S). B + S). The content of the repeating unit having an acid-decomposable group in the resin (A1) is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, still more preferably 0.05 to 0.40. It is.
As the resin (A1), a resin having a repeating unit represented by the following general formula (II) and a repeating unit represented by the general formula (III) is particularly preferable.

In general formulas (II) and (III):
R ₀₁ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a halogen atom, a cyano group, or a substituted or unsubstituted alkoxycarbonyl group.
L ₁ and L ₂ may be the same or different and are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl Represents a group.
M represents a single bond or a divalent linking group.
Q represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted alicyclic group or aromatic ring group which may contain a hetero atom.
At least two of Q, M, and L1 may combine to form a 5-membered or 6-membered ring.
When there are a plurality of A, each independently represents a halogen atom, a cyano group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted acyloxy group, or A substituted or unsubstituted alkoxycarbonyl group is represented.
m and n each independently represents an integer of 0 to 4. However, m and n are preferably not 0 at the same time.

The resin (A1) is a resin having a repeating unit represented by the general formula (II), a repeating unit represented by the general formula (III), and a repeating unit represented by the general formula (IV). Also good. In this case, m = n = 0 may be used.

In general formula (IV),
R ₀₁ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a halogen atom, a cyano group, or a substituted or unsubstituted alkoxycarbonyl group.
When there are a plurality of B, each independently represents a halogen atom, a cyano group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted acyloxy group or a substituted group. Alternatively, it represents an unsubstituted alkoxycarbonyl group.
p represents an integer of 0 to 5.

  In the repeating unit represented by the general formula (II), the substituent as —OC (L 1) (L 2) OMQ possessed by the benzene ring is decomposed by the action of an acid to form a hydroxyl group (alkali-soluble group). It is a generated group (acid-decomposable group), which is decomposed by an acid to produce a hydroxystyrene unit, which is used as a resin having increased solubility in an alkaline developer.

In the general formulas (II) and (III), R ₀₁ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group, preferably 20 or less carbon atoms. It is.

The alkyl group or cycloalkyl group in R ₀₁ preferably has 20 or less carbon atoms, and is a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, cyclopentyl group. Hexyl group, cyclohexyl group, octyl group, dodecyl group and the like. These groups may have a substituent, for example, alkoxy group, hydroxyl group, halogen atom, nitro group, acyl group, acyloxy group, acylamino group, sulfonylamino group, alkylthio group, arylthio group, aralkylthio group, thiophene. Examples include carbonyloxy groups, thiophenemethylcarbonyloxy groups, and heterocyclic residues such as pyrrolidone residues, and those having 8 or less carbon atoms are preferred. As for the cycloalkyl group, examples of the substituent further include an alkyl group. As the alkyl group or cycloalkyl group in R ₀₁ , a CF ₃ group, an alkoxycarbonylmethyl group, an alkylcarbonyloxymethyl group, a hydroxymethyl group, an alkoxymethyl group, and the like are more preferable.

Examples of the halogen atom for R ₀₁ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.
As the alkyl group contained in the alkoxycarbonyl group in R _01, the same alkyl groups represented by R ₀₁ are preferred.

The alkyl group as L ₁ and L ₂ is, for example, an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Preferred examples include a group and an octyl group.
The cycloalkyl group as L ₁ and L ₂ is, for example, a cycloalkyl group having 3 to 15 carbon atoms, and specifically, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group can be preferably exemplified.
The aryl group as L ₁ and L ₂ is, for example, an aryl group having 6 to 15 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a naphthyl group, and an anthryl group.
The aralkyl group as L ₁ and L ₂ has, for example, 6 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.
Further, it is preferable that either one of L _1, L ₂ is a hydrogen atom.

The divalent linking group as M contains, for example, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, —OCO—, —COO—, or —CON (R ₀ ) —, and a plurality thereof. A linking group. R ₀ is a hydrogen atom or an alkyl group.

The alkyl group and cycloalkyl group as Q are the same as the above groups as L ₁ and L ₂ .
Examples of the aryloxy group as Q include a phenoxy group, a naphthoxy group, and a terphenyloxy group.
Examples of the alicyclic group or aromatic ring group which may contain a hetero atom as Q include the cycloalkyl group and aryl group as L ₁ and L ₂ described above, preferably 3 to 15 carbon atoms. It is.

  Examples of the alicyclic group or aromatic ring group containing a hetero atom include thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, pyrrolidone, and the like. Is a structure generally called a heterocycle (a ring formed from carbon and a heteroatom, or a ring formed from a heteroatom).

As a 5-membered or 6-membered ring that may be formed by combining at least two of Q, M, and L ₁ , at least two of Q, M, and L ₁ are combined to form, for example, a propylene group and a butylene group In this case, a 5-membered or 6-membered ring containing an oxygen atom is formed.
As the group represented by -M-Q, 1 to 30 carbon atoms, more preferably from 5 to 20 carbon atoms, for _{example, -OC (L 1) (L} 2) a group represented by O-M-Q The following may be mentioned.

The acyl group as A is, for example, an acyl group having 2 to 8 carbon atoms. Specifically, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, a benzoyl group and the like can be preferably exemplified. .
The alkyl group as A is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group. Can be preferably mentioned.
The alkoxy group as A is, for example, the above alkoxy group having 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyloxy group. .
Examples of the acyloxy group or alkoxycarbonyl group as A include groups corresponding to the above acyl group and alkoxy group.

  Each of the above groups may have a substituent, and preferred substituents include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkoxy group (methoxy group, Ethoxy group, propoxy group, butoxy group, etc.). As for the cyclic structure, examples of the substituent further include an alkyl group (preferably having 1 to 8 carbon atoms).

m and n independently represent an integer of 0 to 4. m and n are each preferably 0 to 2, and more preferably 1.
Specific examples of the repeating unit represented by the general formula (II) are shown below, but are not limited thereto.

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

R ₀₁ in the general formula (IV) independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group, preferably having 20 or less carbon atoms, The same as R ₀₁ in (II) or (III).

Examples of the acyl group, alkyl group, alkoxy group, acyloxy group or alkoxycarbonyl group as B in the general formula (IV) include the same groups as A in the general formula (II). An acyloxy group and an alkoxycarbonyl group are preferable, and an acyloxy group is more preferable. Among acyloxy groups (represented by the general formula —O—CO—R _A , where R _A is an alkyl group), those having 1 to 6 carbon atoms in _RA are preferred, and those having 1 to 3 carbon atoms in _RA. Are more preferable, and those in which R _A has 1 carbon atom (that is, an acetoxy group) are particularly preferable.
p represents an integer of 0 to 5, preferably 0 to 2, more preferably 1 to 2, and still more preferably 1.

Each of the above groups may have a substituent, and preferred substituents include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkoxy group (methoxy group, Ethoxy group, propoxy group, butoxy group, etc.). As for the cyclic structure, examples of the substituent further include an alkyl group (preferably having 1 to 8 carbon atoms).
Specific examples of the repeating unit represented by the general formula (IV) are shown below, but are not limited thereto.

The resin (A1) may have a repeating unit represented by the following general formula (V).

In general formula (V),
R _{a to} R _c each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group.
X ₁ represents a hydrogen atom or an organic group.

In general formula (V), the alkyl group as R _{a to} R _c is preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. .

The organic group as X ₁ preferably has 1 to 40 carbon atoms and may be an acid-decomposable group or a non-acid-decomposable group.
Examples of the non-acid-decomposable group represented by X ₁ include an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group. However, an alkyl group and a cycloalkyl group are excluded when the portion bonded to the oxygen atom of the ester bond is a tertiary carbon.

  In the non-acid-decomposable group, the alkyl group is preferably a group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group or a sec-butyl group. Those having 3 to 10 carbon atoms such as propyl group, cyclobutyl group, cyclohexyl group and adamantyl group are preferred, and the alkenyl group has 2 to 4 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Those having 6 to 14 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthracenyl group are preferable as the aryl group.

Examples of the organic group of the acid-decomposable group represented by X ₁ include —C (R _11a ) (R _12a ) (R _13a ), —C (R _14a ) (R _15a ) (OR _16a ), —CO -OC (R _11a ) (R _12a ) (R _13a ) can be mentioned.
R _{11a to} R _13a each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group. R _14a and R _15a each independently represents a hydrogen atom or an alkyl group. R _16a represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group. Two of R _11a , R _12a and R _13a , or two of R _14a , R _15a and R _16a may be bonded to form a ring.

Note that a group having an acid-decomposable group can be introduced into X ₁ by modification. In this way, X ₁ introduced with the acid decomposable group is, for example, as follows.
-[C ( _R17a ) ( _R18a )] _p- CO-OC ( _R11a ) ( _R12a ) ( _R13a )
R _17a and R _18a each independently represents a hydrogen atom or an alkyl group. p is an integer of 1 to 4.

The organic group as X ₁ is preferably an acid-decomposable group having at least one cyclic structure selected from alicyclic, aromatic and bridged alicyclic, and an aromatic group (particularly a phenyl group). Or a structure containing an alicyclic or bridged alicyclic structure represented by the following general formulas (pI) to (pVI).

In the formula, R ₁₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R _{12 to} R ₁₄ , or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group.

R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R _{17 to} R ₂₁ Represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ Represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In the general formulas (pI) to (pVI), the alkyl group in R _{11 to} R ₂₅ may be either substituted or unsubstituted, and a linear or branched alkyl group having 1 to 4 carbon atoms. Represents. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.

  Further, the further substituent of the alkyl group includes an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, A carboxy group, an alkoxycarbonyl group, a nitro group, etc. can be mentioned.

The alicyclic hydrocarbon group in R _{12 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and a carbon atom 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 carbon number is preferably 6-30, and particularly preferably 7-25. These alicyclic hydrocarbon groups may have a substituent.

  In the present invention, preferable examples of the alicyclic structure include an adamantyl structure, a noradamantyl structure, a decalin structure, a tricyclodecanyl structure, a tetracyclododecanyl structure, a norbornyl structure, a cedrol structure, a cyclopentane structure, and a cyclohexyl structure. , Cycloheptyl structure, cyclooctyl group structure, cyclodecanyl structure, and cyclododecanyl structure. More preferred are an adamantyl structure, a decalin structure, a norbornyl structure, a cedrol structure, a cyclohexyl structure, a cycloheptyl structure, a cyclooctyl structure, a cyclodecanyl structure, and a cyclododecanyl structure.

  Examples of the substituent that the alicyclic hydrocarbon group may have include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, more preferably a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group, and an isopropyl group. Can be mentioned. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  The alkyl group, alkoxy group, and alkoxycarbonyl group may further have a substituent. Examples of such a substituent include an alkoxy group having 1 to 4 carbon atoms (methoxy group, ethoxy group, butoxy group). Group), hydroxy group, oxo group, alkylcarbonyl group (preferably 2 to 5 carbon atoms), alkylcarbonyloxy group group (preferably 2 to 5 carbon atoms), alkoxycarbonyl group (preferably 2 to 5 carbon atoms) And halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.).

As the acid-decomposable group for X ₁ , an atomic group represented by —CH (Rn) —AR described in JP-A-2008-096951 is also preferable. Here, Rn represents an alkyl group or an aryl group, and AR represents an aryl group.

The resin (A1) has an alkali-soluble group such as a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a hexafluoroisopropanol group (—C (CF ₃ ) ₂ ) in order to maintain good developability with respect to an alkaline developer. Other suitable polymerizable monomers may be copolymerized so that (OH) can be introduced, and other hydrophobic polymerizable monomers such as alkyl acrylates and alkyl methacrylates may be copolymerized to improve film quality. May be.

The content of the repeating unit represented by the general formula (II) is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, particularly preferably 10 to 10 mol% in all repeating units constituting the resin (A1). 40 mol%.
The content of the repeating unit represented by the general formula (III) is preferably 40 to 90 mol%, more preferably 45 to 80 mol%, particularly preferably 50 to 50% in all repeating units constituting the resin (A1). 75 mol%.

The content of the repeating unit represented by the general formula (IV) is preferably 0 to 50 mol%, more preferably 10 to 40 mol%, particularly preferably 15 to the total repeating units constituting the resin (A1). 30 mol%.
The content of the repeating unit represented by the general formula (V) is preferably 0 to 30 mol%, more preferably 0 to 20 mol%, particularly preferably 0 to 0 in all repeating units constituting the resin (A1). 10 mol%.

The content of the repeating unit having an alkali-soluble group such as a carboxy group or a sulfonic acid group other than a hydroxyl group is preferably 0 to 10 mol%, more preferably 1 to 8 mol%, in all repeating units constituting the resin. Most preferably, it is 2-6 mol%.
The resin (A1) can be synthesized by any method of radical polymerization, anionic polymerization, and cationic polymerization. A radical polymerization method is preferred from the viewpoint of controlling the copolymerization reaction. The living radical polymerization method is preferred from the viewpoint of molecular weight and molecular weight distribution control. Specific examples include a method in which a compound selected from a nitroxide compound, an atom transfer polymerization method, and an RAFT agent and a radical polymerization initiator (azo-based or peroxide-based) are used in combination. The acid-decomposable protecting group can be introduced by either copolymerizing a monomer having an acid-decomposable protecting group or by introducing a protecting group to a resin having an alkali-soluble hydroxyl group such as a phenolic hydroxyl group or a carboxyl group. It is. Further, a group that can be decomposed with an acid into an alkali-soluble resin as described in European Patent No. 254853, JP-A-2-258500, JP-A-3-223860, and JP-A-4-251259. It can be synthesized by a known synthesis method such as a method of reacting a precursor or a method of copolymerizing a monomer having a group capable of decomposing with an acid with various monomers.

  The synthesized resin is usually used in a resist composition after purifying impurities such as unreacted monomers that may adversely affect the desired performance by a method such as reprecipitation and washing generally used in polymer synthesis.

The weight average molecular weight of the resin (A1) is preferably 15000 or less, more preferably 1,000 to 10,000, still more preferably 3,000 to 8,000, and particularly preferably, as a polystyrene conversion value by the GPC method. 4,000 to 6,000.
The dispersity (Mw / Mn) of the resin (A1) is preferably 1.0 to 3.0, more preferably 1.05 to 2.0, and even more preferably 1.1 to 1.7. .
Moreover, you may use resin (A1) in combination of 2 or more types.
Specific examples of the resin (A1) are shown below, but are not limited thereto.

In the composition of the present invention, the blending amount of the acid-decomposable resin in the composition is preferably 45 to 90% by mass, more preferably 55 to 85% by mass, and still more preferably 60% in the total solid content of the composition. -80 mass%.
In the above description, the resin having the repeating units represented by the general formulas (II) and (III) has been mainly described. However, the acid-decomposable resin of the present invention does not exclude other resins.

[2] Compound that generates acid upon irradiation with actinic ray or radiation (acid generator) (B)
As a compound (hereinafter also referred to as “acid generator”) that decomposes upon irradiation with actinic rays or radiation and contained in the actinic ray- or radiation-sensitive resin composition of the present invention, photocationic polymerization Photoinitiators, radical photopolymerization photoinitiators, dyes photodecolorants, photochromic agents, known compounds that generate acids upon irradiation with actinic rays or radiations used in microresists, and the like These mixtures can be appropriately selected and used.

  Examples of the acid generator include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

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

Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712, etc. can also be used.
Among the compounds that generate an acid upon irradiation with actinic rays or radiation, compounds represented by the following general formulas (ZI), (ZII), and (ZIII) can be exemplified.

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Z ⁻ represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion as Z ⁻ include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methide anion.
A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist.

Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.
Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.

The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, and preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms. Alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl , Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, etc. Can be mentioned.
The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group , Hydroxyl group, amino group, cyano group, alkyl group (preferably having 1 to 5 carbon atoms), alkoxy group (preferably having 1 to 5 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), aryl group (preferably C6-14), alkoxycarbonyl group (preferably C2-7), acyl group (preferably C2-12), alkoxycarbonyloxy group (preferably C2-7), etc. Can do. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylmethyl group. These groups may further have a substituent. Examples thereof include a substituent which the alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have. Groups.
Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, An isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, and the like can be given. Examples of the substituent of these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, and an alkylthio group, and an alkyl group substituted with a fluorine atom is preferable.
Examples of other non-nucleophilic anions include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.

Examples of the non-nucleophilic anion of Z ⁻ include an aliphatic sulfonate anion in which the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group. A bis (alkylsulfonyl) imide anion substituted with a fluorine atom and a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms, a benzenesulfonic acid anion having a fluorine atom, still more preferably a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, It is a pentafluorobenzenesulfonic acid anion and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

Examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the corresponding groups in the compounds (ZI-1), (ZI-2) and (ZI-3) described later.
In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI) is, at least one bond with structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

More preferable (ZI) components include compounds (ZI-1), (ZI-2), and (ZI-3) described below.
The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compounds, namely, compounds containing an arylsulfonium as a cation.

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group with the remaining being an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

  The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples thereof include an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms) , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, more preferably carbon. These are an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (ZI-2) will be described.
Compound (ZI-2) is a compound in which R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.

The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.

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 (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.

The 2-oxoalkyl group may be either linear or branched, and a group having> C = O at the 2-position of the above alkyl group is preferable.
The 2-oxocycloalkyl group is preferably a group having> C═O at the 2-position of the cycloalkyl group.

The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

In general formula (ZI-3),
R _1c to R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
R _x and R _y independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.

Any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom and a sulfur atom. , An ester bond and an amide bond may be included. Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
Zc ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ^{− in} formula (ZI).

  As specific examples of the compound represented by the general formula (ZI-3), as preferable specific examples of the compound (ZI-3), paragraphs 0047 and 0048 of JP-A No. 2004-233661 and JP-A No. 2003-2003 Examples thereof include compounds exemplified in paragraphs [0040] to [0046] of Japanese Patent No. 35948.

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group. With respect to specific examples of these aryl groups, alkyl groups, or cycloalkyl groups, and specific examples of substituents that these groups may further have, R _{201 to} R _{203 in} the above-described general formula (ZI-1) The same as the aryl group, alkyl group, and cycloalkyl group.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).
Examples of the compound that generates an acid upon irradiation with actinic rays or radiation that can be used further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.

  Of the compounds that generate an acid upon irradiation with actinic rays or radiation, compounds represented by general formulas (ZI) to (ZIII) are more preferable.

Further, as a compound that generates an acid by radiation of actinic rays or radiation, a compound that generates an acid having one sulfonic acid group or imide group is preferable, and a compound that generates monovalent perfluoroalkanesulfonic acid, more preferably, Or a compound generating an aromatic sulfonic acid substituted with a monovalent fluorine atom or a group containing a fluorine atom, or a compound generating an imido acid substituted with a monovalent fluorine atom or a group containing a fluorine atom Even more preferably, it is a sulfonium salt of fluorinated substituted alkane sulfonic acid, fluorine substituted benzene sulfonic acid or fluorine substituted imido acid. The acid generator that can be used is particularly preferably a fluorinated substituted alkane sulfonic acid, a fluorinated substituted benzene sulfonic acid or a fluorinated substituted imido acid whose pKa of the generated acid is pKa = -1 or less, and the sensitivity is improved. .
Among the compounds that generate an acid upon irradiation with actinic rays or radiation, particularly preferred examples are given below.

As the acid generator, a compound represented by the general formula (I) (acid generator A1) is particularly preferable.

In general formula (I),
R ^{1 to} R ¹³ each independently represents a hydrogen atom or a substituent.
Z is a single bond or a divalent linking group.
X ⁻ represents a counter anion.

In the general formula (I), at least one of R ^{1 to} R ¹³ is preferably a substituent containing an alcoholic hydroxyl group. Here, the alcoholic hydroxyl group represents a hydroxyl group bonded to a carbon atom of an alkyl group. If at least one of R ¹ to R ¹³ is a substituent containing an alcoholic hydroxyl group, R ¹ to R ¹³ is represented by -W-Y. Y is an alkyl group substituted with a hydroxyl group, and W is a single bond or a divalent linking group.

The alkyl group of Y is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl Group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group Preferably ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl group, more preferably ethyl group, propyl group and isopropyl group. Y particularly preferably contains a —CH ₂ CH ₂ OH structure.

  The divalent linking group represented by W is not particularly limited, and examples thereof include an alkoxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an acylamino group, an aminocarbonylamino group, Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxy Examples thereof include a divalent group in which an arbitrary hydrogen atom in a monovalent group such as a carbonyl group, an alkoxycarbonyl group, or a carbamoyl group is replaced with a single bond.

  W is preferably a single bond, an alkoxy group, an acyloxy group, an acylamino group, an alkyl and arylsulfonylamino group, an alkylthio group, an alkylsulfonyl group, an acyl group, an alkoxycarbonyl group, and any hydrogen atom in the carbamoyl group replaced with a single bond. It is a divalent group, more preferably a divalent group in which any hydrogen atom in a single bond, acyloxy group, alkylsulfonyl group, acyl group or alkoxycarbonyl group is replaced with a single bond.

When R ^{1 to} R ¹³ are substituents containing an alcoholic hydroxyl group, the number of carbon atoms contained is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4. .
The substituent containing an alcoholic hydroxyl group as R ^{1 to} R ¹³ may have two or more alcoholic hydroxyl groups. The number of alcoholic hydroxyl groups having a substituent containing an alcoholic hydroxyl group as R ^{1 to} R ¹³ is 1 to 6, preferably 1 to 3, and more preferably 1.
The number of alcoholic hydroxyl groups possessed by the compound represented by the general formula (I) is preferably 1 to 10, more preferably 1 to 6, and even more preferably all R ^{1 to} R ^{13 in} total. Is 1 to 3.

As the substituent other than the substituent containing an alcoholic hydroxyl group in R ^{1 to} R ¹³ , any substituent may be used without any particular limitation. For example, a halogen atom, an alkyl group (a cycloalkyl group, a bicycloalkyl group, a trialkyl group) Cycloalkyl groups), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups (also referred to as heterocyclic groups), cyano groups, nitro groups, carboxyl groups, Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonyl An amino group, an alkoxycarbonylamino group, Reeloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group , Acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, Examples include hydrazino group, ureido group, boronic acid group (—B (OH) ₂ ), phosphato group (—OPO (OH) ₂ ), sulfato group (—OSO ₃ H), and other known substituents. .

In addition, two adjacent R ^{1 to} R ¹³ may be combined to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These may be further combined to form a polycyclic fused ring. For example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine Ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, Phenanthridine ring, acridine ring, Ntororin ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring and a phenazine ring.) May also be formed.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are preferably a hydrogen atom or a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group ( Cycloalkenyl group, bicycloalkenyl group), alkynyl group, aryl group, cyano group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, Aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group, sulfamoyl group, alkyl and arylsulfonyl group, aryloxycarbonyl group, alkoxycarbonyl group A carbamoyl group, an imido group, a silyl group, a ureido group.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are more preferably a hydrogen atom or a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), a cyano group. , Alkoxy group, acyloxy group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkyl and arylsulfonylamino group, alkylthio group, sulfamoyl group, alkyl and arylsulfonyl group, alkoxycarbonyl group and carbamoyl group.

Further, when R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are particularly preferably a hydrogen atom or an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), a halogen atom, An alkoxy group;
In general formula (I), preferably at least one of R ^{1 to} R ¹³ contains an alcoholic hydroxyl group, and more preferably at least one of R ^{9 to} R ¹³ contains an alcoholic hydroxyl group.

Z represents a single bond or a divalent linking group, and examples of the divalent linking group include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether group, and a thioether. Group, amino group, disulfide group, acyl group, alkylsulfonyl group, -CH = CH-, aminocarbonylamino group, aminosulfonylamino group, and the like, and may have a substituent. These substituents are the same as the substituents shown for R ^{1 to} R ¹³ above. Z is preferably a single bond, an alkylene group, an arylene group, an ether group, a thioether group, an amino group, —CH═CH—, an aminocarbonylamino group, an aminosulfonylamino group, or the like, which has no electron withdrawing property, More preferred are a single bond, an ether group and a thioether group, and particularly preferred is a single bond.

The compound represented by the general formula (I) has a counter anion X ⁻ . Examples of the counter anion X ⁻ include those similar to the anion described as Z− in the general formula (ZI).

The counter anion X ⁻ of the compound represented by the general formula (I) is preferably a sulfonate anion, and more preferably an aryl sulfonate anion.
Specific examples of the counter anion X ⁻ include methanesulfonate anion, trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate anion, perfluorobutanesulfonate anion, perfluorohexanesulfonate anion, Perfluorooctanesulfonate anion, pentafluorobenzenesulfonate anion, 3,5-bistrifluoromethylbenzenesulfonate anion, 2,4,6-triisopropylbenzenesulfonate anion, perfluoroethoxyethanesulfonate anion, 2,3 , 5,6-tetrafluoro-4-dodecyloxybenzenesulfonate anion, p-toluenesulfonate anion, 2,4,6-trimethylbenzenesulfonate anion, and the like.

200-2000 are preferable and, as for the molecular weight of the compound represented by general formula (I), 400-1000 are especially preferable.
For the synthesis method of the compound represented by the general formula (I), see, for example, the synthesis method described in paragraph [0090] on page 5 of US Patent Publication: US2007 / 0184384A.

Although the specific example of a compound represented by general formula (I) below is shown, it is not limited to these.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
In the present invention, the content of the acid generator is preferably 10% by mass or more based on the total solid content of the composition. Furthermore, 10-50 mass% is preferable, More preferably, it is 20-50 mass%, More preferably, it is 22-50 mass%, Most preferably, it is 25-50 mass%, Most preferably, it is 25-40 mass%. This concentration range is a concentration range that is concerned from the viewpoint of light transmittance and the like in conventional resists for ArF and KrF. On the other hand, electron beams and EUVs are different in the mechanism of radiation irradiation to acid generation, and thus can be put to practical use even in such a concentration range.

[3] Compound (C) unevenly distributed on the film surface
In the present invention, the compound (C) unevenly distributed on the film surface refers to a compound capable of forming a protective layer unevenly distributed on the film surface by being added to the composition. Whether or not the protective layer is formed is determined by, for example, comparing the surface static contact angle (contact angle with pure water) of the film to which the compound (C) is not added with the surface static contact angle of the film to which the compound (C) is added. If the contact angle increases, it can be considered that a protective layer has been formed.

  The compound (C) is ubiquitous at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule, and the polar / nonpolar substance is uniformly mixed. You don't have to contribute to

  Although it does not specifically limit as a compound (C) as long as the above characteristics are satisfy | filled, It is preferable that it is a resin, It is preferable that a weight average molecular weight is a resin of the range of 1000-100000, The range of 1500-30000 More preferably, the resin is in the range of 1500 to 30000, and particularly preferably in the range of 3000 to 10,000 (hereinafter, when the compound (C) is a resin, the compound (C ').

  Further, from the viewpoint of uneven distribution on the film surface, the compound (C ′) has (i) a fluorine atom in the main chain or side chain of the resin, and (ii) a silicon atom in the main chain or side chain of the resin. Or (iii) having at least one feature of having a hydrocarbon group in the side chain of the resin.

When the compound (C ′) has a fluorine atom in the main chain or side chain of the resin (i), as the partial structure having a fluorine atom, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or a fluorine atom It is preferable that it is resin which has an aryl group which has.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, It may have a substituent.

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

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

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{57 to} R ₆₁ , R _{62 to} R ₆₄ and R _{65 to} R ₆₈ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably having a carbon number of 1 ~ 4). R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 1,3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.

Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH (CF ₃₎ OH and the like, -C (CF _{3) 2} OH is preferred.
Preferred examples of the repeating unit having a fluorine atom include those shown below.

In the formula, R ₁₀ and R ₁₁ are each independently a hydrogen atom, a fluorine atom, or an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and particularly as an alkyl group having a substituent, Fluorinated alkyl group can be mentioned).
W _{3 to} W ₆ each independently represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).
Besides these, resins having units as shown below are also applicable.

In the formula, R _{4 to} R ₇ are each independently a hydrogen atom, a fluorine atom, or an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and the alkyl group having a substituent is In particular, a fluorinated alkyl group can be mentioned).
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.
W ₂ each independently represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).

L ₂ represents a single bond or a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R )-Or a divalent linking group in which a plurality of these are combined.

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

When the compound (C ′) has a silicon atom in the main chain or side chain of the resin (ii), a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure as a partial structure having a silicon atom It is preferable that
Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represents a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. As the divalent linking group, an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a urea group is used alone or in combination of two or more groups. A combination is mentioned.

  n represents an integer of 1 to 5.

Examples of the repeating unit having a silicon atom include the repeating units shown in the above (C-Ia) to (C-Id) and (C-III). (However, W _{3 to} W ₆ are represented as “an atomic group containing at least one silicon atom, specifically, an atomic group represented by (CS-1) to (CS-3)”) To read)
Hereinafter, although the specific example of the repeating unit which has group represented by general formula (CS-1)-(CS-3) is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

When the compound (C ′) has a hydrocarbon group in the side chain of (iii) resin, it preferably has a hydrocarbon group having 4 or more carbon atoms in the side chain, and a hydrocarbon group having 6 or more carbon atoms in the side chain. More preferably, it has.
Further, in another aspect, preferably has a hydrocarbon group having a -CH ₃ structure at one or more side chains, and more preferably has a hydrocarbon group having a -CH ₃ structure two or more side chains. In this respect, the hydrocarbon group is preferably a branched alkyl group.
Specific examples of the repeating unit include the repeating units represented by the general formulas (C-Ia) to (C-Id). (However, W _{3 to} W ₆ are read as “represents a hydrocarbon group”)
Examples of the side chain hydrocarbon group include an alkyl group, an alkyloxy group, an alkyl-substituted cycloalkyl group, an alkenyl group, an alkyl-substituted alkenyl group, an alkyl-substituted cycloalkenyl group, an alkyl-substituted aryl group, and an alkyl-substituted aralkyl group. Group, an alkyl-substituted cycloalkyl group is preferred.

As the alkyl group, a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms is preferable. Specific examples of preferable branched alkyl groups include isopropyl, isobutyl, t-butyl, 3-pentyl, 2-methyl-3-butyl, 3-hexyl, and 2-methyl-3-pentyl. 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 preferable linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl groups.

Examples of the alkyloxy group include a group in which an ether group is bonded to the above-described alkyl group.
The cycloalkyl group 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 carbon number is preferably 6-30, and particularly preferably 7-25. Preferred cycloalkyl groups include adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, A cyclodecanyl group and a cyclododecanyl group can be mentioned. More preferable examples include an adamantyl group, norbornyl group, cyclohexyl group, cyclopentyl group, tetracyclododecanyl group, and tricyclodecanyl group. More preferably, they are a norbornyl group, a cyclopentyl group, and a cyclohexyl group.

  The cycloalkyl group may be substituted with an alkyl group, and examples thereof include 3,5-dimethylcyclohexyl group, 4-isopropylcyclohexyl group, 4-tbutylcyclohexyl group and the like.

As the alkenyl group, a linear or branched alkenyl group having 1 to 20 carbon atoms is preferable, and a branched alkenyl group is more preferable.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The aralkyl group 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.

(iii) Preferred specific examples of the repeating unit having a hydrocarbon group in the side chain of the resin are given below. In addition, this invention is not limited to these. In specific examples, Rx represents a hydrogen atom or a methyl group, and Rxa to Rxc each represents an alkyl group having 1 to 4 carbon atoms.

  The total content of the repeating units having any of the characteristics (i) to (iii) is preferably 50 to 100 mol%, more preferably 80 to 100 mol%, based on all repeating units in the compound (C ′). More preferably, it is 90-100 mol%.

  The compound (C ′) may further have at least one group selected from the following groups (x) to (z).

(X) an alkali-soluble group,
(Y) a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer;
(Z) A group that decomposes by the action of an acid.

(X) Alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (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) ) And a methylene group.
Preferred alkali-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (carbonyl) methylene groups.

Examples of the repeating unit having an alkali-soluble group (x) include a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a main group of the resin via a linking group. Examples include repeating units in which an alkali-soluble group is bonded to the chain. Furthermore, a polymerization initiator or a chain transfer agent having an alkali-soluble group can be used at the time of polymerization to be introduced at the end of the polymer chain. Is also preferable.
The content of the repeating unit having an alkali-soluble group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 20 mol%, based on all repeating units in the polymer.
Specific examples of the repeating unit having an alkali-soluble group (x) are shown below, but the present invention is not limited thereto.

  (Y) Examples of the group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer include a group having a lactone structure, an acid anhydride group, an acid imide group, and the like, and preferably a lactone A group having a structure.

  As the repeating unit having a group (y) that is decomposed by the action of an alkali developer and increases the solubility in the alkali developer, an alkali is added to the main chain of the resin, such as a repeating unit of an acrylate ester or a methacrylate ester. A polymerization initiator having a repeating unit to which a group (y) that decomposes by the action of the developer and increases the solubility in an alkali developer is bonded, or a group (y) that increases the solubility in an alkali developer And a chain transfer agent used at the time of polymerization are preferably introduced at the end of the polymer chain.

The content of the repeating unit having a group (y) whose solubility in an alkali developer is increased is preferably 1 to 40 mol%, more preferably 3 to 30 mol%, still more preferably based on all repeating units in the polymer. 5 to 15 mol%.
Specific examples of the group (y) that increases the solubility in an alkali developer are shown below, but are not limited thereto.

  Examples of the repeating unit having a group (z) that can be decomposed by the action of an acid include the same repeating units having an acid-decomposable group as mentioned for the resin (A). In the compound (C), the content of the repeating unit having a group (z) that decomposes by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all repeating units in the polymer. Preferably it is 20-60 mol%.

  The weight average molecular weight of the compound (C ′) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000. .

  As in the case of the resin of the component (A), the compound (C ′) preferably has 0 to 10% by mass of the residual monomer or oligomer component, and more preferably has few impurities such as metals. 0-5 mass% and 0-1 mass% are still more preferable. Thereby, a resist having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is the range of 1-2.

  As the compound (C ′), various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the positive resist composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. The concentration of the reaction is 5 to 50% by mass, preferably 30 to 50% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.

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

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

  The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.

  The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.

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

The resin may be once deposited and separated, and then dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and dissolved again in the solvent. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).
Hereinafter, examples of preferred resins as the compound (C ′) will be shown, but the invention is not limited thereto.
(F, Si type)

(Hydrocarbon)

The compound (C) may be a low molecular compound having a triphenylene skeleton as shown below, for example. These compounds can be synthesized according to the method described in the liquid crystal manual.

A compound (C) may be used by 1 type and may be used in mixture of multiple types.
The content of the compound (C) is preferably 0.01 to 30% by mass, and 0.1 to 20% by mass based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. More preferably, 1-15 mass% is especially preferable.

<Other ingredients>
[4] Basic compound (D)
The composition of the present invention preferably contains a basic compound in order to reduce the change in performance over time from exposure to heating. The basic compound serves to quench the deprotection reaction by the acid generated by exposure, and its diffusibility and basicity affect the substantial acid diffusibility.

Preferable structures include basic compounds having structures represented by the following formulas (A) to (E).

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are each independently a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably carbon). Where R ²⁵⁰ and R ²⁵¹ may combine with each other to form a ring.

These may have a substituent. Examples of the alkyl group and cycloalkyl group having a substituent include an aminoalkyl group having 1 to 20 carbon atoms, an aminocycloalkyl group having 3 to 20 carbon atoms, and 1 to 1 carbon atoms. A 20 hydroxyalkyl group or a C 3-20 hydroxycycloalkyl group is preferred.
These may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.
In the formula, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represents an alkyl group (preferably having 1 to 6 carbon atoms) or a cycloalkyl group (preferably having 3 to 6 carbon atoms).

  Preferable compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine, and may have a substituent. More preferred compounds include compounds having an imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, hydroxyl groups and / or Or the aniline derivative which has an ether bond etc. can be mentioned.

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

  Further, at least one nitrogen-containing compound selected from an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group can be exemplified. .

The amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonate group, and the ammonium salt compound having a sulfonate group have at least one alkyl group bonded to a nitrogen atom. Is preferred. The alkyl chain preferably has an oxygen atom and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. -CH ₂ CH ₂ O Among the oxyalkylene group _{-, - CH (CH 3)} CH 2 O- or -CH ₂ CH ₂ CH ₂ O- structure is preferred.

  Specific examples of the amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group are exemplified in [0066] of US2007 / 0224539A. Examples thereof include, but are not limited to, compounds (C1-1) to (C3-3).

These basic compounds are used alone or in combination of two or more.
The molecular weight of the basic compound is preferably 250 to 1000, more preferably 250 to 800, and still more preferably 400 to 800.
The content of the basic compound is preferably 1.0 to 8.0% by mass, more preferably 1.5 to 5.0% by mass, and still more preferably based on the total solid content of the composition. It is 2.0-4.0 mass%.

[5] Solid content concentration and organic solvent (E)
The composition of the present invention is prepared by dissolving the above components in a solvent.
The resist composition is stored at refrigeration, room temperature, etc., and it is desired that there is no change in performance within the storage period. However, there is a problem that sensitivity fluctuation occurs after storage.
In the structure of this invention, it discovered that a sensitivity fluctuation | variation could be suppressed remarkably by adjusting the total solid content concentration in a composition to 1.0-4.5 mass%.
The total solid concentration in the composition of the present invention is preferably 2.0 to 4.0% by mass, more preferably 2.0 to 3.0% by mass.
The total solid content corresponds to the composition obtained by removing the solvent, and corresponds to the mass of the dried coating film formed from the composition.

Solvents for preparing the actinic ray-sensitive or radiation-sensitive resin composition of the present invention include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl. Ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate , Ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tet Organic solvents are preferred, such as such hydrofuran, more preferably cyclohexanone, .gamma.-butyrolactone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, and particularly preferably propylene glycol monomethyl ether.
The solvent may be a single solvent or a mixed solvent in which two or more are mixed.

Of the total amount of solvent, it is particularly preferable to contain 50% by mass or more of propylene glycol monomethyl ether, most preferably 50 to 80% by mass. As the solvent used in combination with propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone and ethyl lactate are preferable, and propylene glycol monomethyl ether acetate is most preferable.
In addition to the above components, the composition of the present invention may contain the following components.
[6] Surfactant (F)
The composition of the present invention preferably further contains a surfactant. As the surfactant, fluorine-based and / or silicon-based surfactants are preferable.
Surfactants corresponding to these include Megafac F176, Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656, PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical, Sumitomo 3M Examples include Fluorad FC430 manufactured by Co., Ltd., polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  Further, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. More specific examples include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

  In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include surfactants described in US 2008/0248425 A1 after [0273].

[7] Dissolution inhibiting compound (G) having a molecular weight of 3000 or less, which is decomposed by the action of an acid to increase the solubility in an alkaline developer.
The dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter also referred to as “(G) component” or “dissolution inhibiting compound”), which decomposes by the action of an acid and increases the solubility in an alkaline developer, is 220 nm or less. In order not to reduce the permeability, alicyclic or aliphatic compounds containing acid-decomposable groups such as cholic acid derivatives containing acid-decomposable groups described in Proceedings of SPIE, 2724, 355 (1996) preferable.

When the composition of the present invention is irradiated with an electron beam, it preferably contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. As a phenol compound, what contains 1-9 phenol frame | skeleton is preferable, More preferably, it contains 2-6 pieces.
The molecular weight of the dissolution inhibiting compound in the present invention is 3000 or less, preferably 300 to 3000, and more preferably 500 to 2500.
The addition amount of the dissolution inhibiting compound is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the total solid content of the composition of the present invention.
Specific examples of the dissolution inhibiting compound are shown below, but the present invention is not limited thereto.

[8] Other additives In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, if necessary, a dye, a plasticizer, a surfactant other than the component (E), a photosensitizer, and A compound or the like that promotes solubility in a developer can be contained.
The dissolution accelerating compound for the developer that can be used in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable.

A preferable addition amount of these dissolution promoting compounds is 2 to 50% by mass, and more preferably 5 to 30% by mass with respect to the resin of the component (A). 50 mass% or less is preferable at the point of development residue suppression and the pattern deformation prevention at the time of image development.
Such a phenol compound having a molecular weight of 1,000 or less can be obtained by, for example, the method described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, and the like. It can be easily synthesized by those skilled in the art with reference.

  Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

In the present invention, a surfactant other than the above (E) fluorine-based and / or silicon-based surfactant may be added. Specifically, nonionic interfaces such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan aliphatic esters, polyoxyethylene sorbitan aliphatic esters, etc. Mention may be made of activators.
These surfactants may be added alone or in some combination.

[8] Pattern Forming Method The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is applied on a support such as a substrate to form a film. The film thickness is preferably 0.02 to 0.1 μm.
As a method of coating on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.

For example, a resist composition is applied onto a substrate (eg, silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate application method such as a spinner or a coater, and dried to form a resist film. . In addition, a known antireflection film can be applied in advance.
The resist film is irradiated with an electron beam, X-rays or EUV, preferably baked (heated) and developed. Thereby, a good pattern can be obtained.

  In the development step, an alkaline developer is used as follows. As an alkaline developer of the resist composition, inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like Alkaline aqueous solutions such as quaternary ammonium salts, cyclic amines such as pyrrole and pihelidine can be used.

Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline developer.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.
Synthesis Example 1 (Synthesis of Resin (R-1))
After anionic polymerization of p-tert-butoxystyrene, poly (p-hydroxystyrene) was obtained by deprotection with acid. The weight average molecular weight (Mw) determined from GPC (carrier: tetrahydrofuran, in terms of polystyrene) was Mw = 3300, and the dispersity (Pd) was 1.2.
Sufficiently dehydrated poly (p-hydroxystyrene) and propylene glycol monomethyl ether acetate (PGMEA) mixed solution (solid content 20.0% by mass) 50.0 parts by mass was added with cyclohexyl ethyl vinyl ether 3.21 parts by mass. . Subsequently, 1.58 parts by mass of a mixed solution of p-toluenesulfonic acid and PGMEA (solid content: 1.0% by mass) was added and reacted at room temperature with stirring for 1 hour.
After adding 0.99 parts by mass of pyridine, 0.85 parts by mass of acetic anhydride was added, and the mixture was further reacted at room temperature with stirring for 2 hours.
After completion of the reaction, washing with water and concentration were carried out, followed by reprecipitation with a large amount of hexane, filtration and drying to obtain 11.9 parts by mass of a polymer (R-1) powder. The weight average molecular weight of the obtained polymer was Mw = 5000 and Pd = 1.2.

Other resins were synthesized by the same method.
Hereinafter, the structure, composition ratio, weight average molecular weight (Mw), and dispersity (Pd) of the acid-decomposable resins (R-1) to (R-11) are shown.

[Examples 1 to 12 and Comparative Examples 1 and 2]
<Resist preparation>
The components shown in Table 3 below are dissolved in the mixed solvent shown in the table, and this is filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm, and the total solid content concentration (% by mass) shown in the table is given. The positive resist solution was prepared and evaluated as follows. The results are shown in Table 4 below.
The solid content concentration (mass%) of each component described in Table 3 is based on the total solid content.
The addition amount of the surfactant is 0.1% by mass in the total solid content of the resist composition.
The solid content concentration of the resin is an amount obtained by removing the photoacid generator, the basic compound, and the surfactant from the total solid content of the resist composition.

<Resist evaluation (EB)>
The prepared positive resist solution is uniformly coated on a silicon substrate that has been subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 120 ° C. for 90 seconds to form a resist having a film thickness of 100 nm. A film was formed.
This resist film was irradiated with an electron beam using an electron beam irradiation apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage: 50 keV). Immediately after the irradiation, it was heated on a hot plate at 110 ° C. for 90 seconds. Furthermore, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then dried to form a line and space pattern. Was evaluated by the following method.

〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). Sensitivity was defined as the minimum irradiation energy when resolving a 100 nm line (line: space = 1: 1).

[Resolution]
The resolving power was defined as the limiting resolving power (line and space were separated and resolving) at the irradiation dose showing the above sensitivity.

[Line edge roughness (LER)]
The distance from the reference line where there should be an edge, using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.) for any 30 points in the length direction 50 μm of the 100 nm line pattern at the irradiation amount showing the sensitivity described above. Was measured, the standard deviation was obtained, and 3σ was calculated.

[Pattern shape]
The cross-sectional shape of the 100 nm line pattern at the irradiation dose showing the above sensitivity is observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), and is divided into four stages: T-top, rectangular, slightly tapered, and tapered. Evaluation was performed.

<Measurement of surface static contact angle of resist film>
Each resist composition shown in Table 3 was applied onto a silicon wafer and baked at 110 degrees for 60 seconds to form a resist film having a thickness of 150 nm. After dropping one drop of pure water on the obtained resist film, the static contact angle when 5 seconds passed was measured using an automatic contact angle meter (CA-V type manufactured by Kyowa Interface Chemical Co., Ltd.), θ / 2. The static contact angle of the resist film was obtained by automatic measurement by the method. Next, except that the ubiquitous compound (C) is not included, the contact angle of the resist composition is measured in the same manner for other compositions to obtain the static contact angle of the resist film when the ubiquitous compound (C) is not added. It was. These differences were determined by subtracting the static contact angle of the resist film when no ubiquitous compound (C) was added from the static contact angle value of the obtained resist film.

The acid generator (B), ubiquitous compound (C), basic compound (D), organic solvent (E), and surfactant (F) used in Examples and Comparative Examples shown in Table 3 are as follows. It is.
[Acid generator (B)]
The acid generator corresponds to that exemplified above.

[Uniform compound (C)]

[Basic compound (D)]

[Solvent (E)]
A1: Propylene glycol monomethyl ether acetate B1: Propylene glycol monomethyl ether [Surfactant (F)]
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based)

  From the results shown in Table 4, it is clear that the positive resist composition of the present invention can provide a pattern that simultaneously satisfies high sensitivity, high resolution, good pattern shape, and good line edge roughness. It is.

  The same effects as described above can be obtained in EUV and X-ray lithography.

Claims (6)

(A) a resin that decomposes by the action of an acid and increases the dissolution rate in an aqueous alkali solution;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(C) a compound that is unevenly distributed on the film surface by film formation;
An actinic ray-sensitive or radiation-sensitive resin composition comprising:   The actinic ray or sensitization according to claim 1, wherein the compound (C) unevenly distributed on the film surface is a resin having a fluorine atom and / or a silicon atom and / or a hydrocarbon group in a side chain. Radiation resin composition. 3. The actinic ray or the active ray according to claim 1 or 2, which contains at least a compound represented by the following general formula (I) as the compound (B) that generates an acid upon irradiation with an actinic ray or radiation. Radiation sensitive resin composition.

In general formula (I),
R ^{1 to} R ¹³ each independently represents a hydrogen atom or a substituent.
Z represents a single bond or a divalent linking group.
X ⁻ represents a counter anion. The resin (A) that is decomposed by the action of an acid to increase the dissolution rate in an alkaline aqueous solution has a repeating unit represented by the general formula (II) and a repeating unit represented by the general formula (III). The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3.

In general formulas (II) and (III):
R ₀₁ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a halogen atom, a cyano group, or a substituted or unsubstituted alkoxycarbonyl group.
L1 and L2 may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group. To express.
M represents a single bond or a divalent linking group.
Q represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted alicyclic group or aromatic ring group which may contain a hetero atom.
At least two of Q, M, and L1 may combine to form a 5-membered or 6-membered ring.
When there are a plurality of A, each independently represents a halogen atom, a cyano group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted acyloxy group, or A substituted or unsubstituted alkoxycarbonyl group is represented.
m and n each independently represents an integer of 0 to 4.   The actinic ray-sensitive or radiation-sensitive resin composition contains (E) an organic solvent, and 50% by mass or more of the organic solvent (E) is propylene glycol monomethyl ether. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above.   A pattern comprising a step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, and exposing and developing with an electron beam, X-ray or EUV. Forming method.