KR102506110B1 - Resist composition and patterning process - Google Patents

Abstract

(식 중, W₁은 탄소수 4∼12의 헤테로 원자를 포함하는 환형의 2가 탄화수소기를 나타낸다. W₂는 탄소수 4∼14의 헤테로 원자를 포함하지 않는 환형의 1가 탄화수소기를 나타낸다. Rf는 상기 일반식으로 표시되는 2가의 유기기이다. M⁺는 오늄 양이온을 나타낸다.)[Problem] A resist composition showing particularly good mask dimension dependence (mask error factor: MEF) and dimensional uniformity (CDU) in photolithography using high-energy rays such as KrF excimer laser light, electron beams, and extreme ultraviolet rays as a light source, and A pattern formation method using the resist composition is provided.
[Solution] (A) a resin containing a repeating unit having an acid labile group and at least one repeating unit having an aromatic substituent, (B) a photoacid generator represented by the general formula (B-1), and ( C) A resist composition comprising a solvent.

(In the formula, W ₁ represents a cyclic divalent hydrocarbon group containing a hetero atom of 4 to 12 carbon atoms. W ₂ represents a cyclic monovalent hydrocarbon group having 4 to 14 carbon atoms and not containing a hetero atom. Rf is It is a divalent organic group represented by the general formula. M ⁺ represents an onium cation.)

Description

Resist composition and pattern formation method {RESIST COMPOSITION AND PATTERNING PROCESS}

The present invention relates to a resist composition and a method for forming a pattern.

Miniaturization is rapidly progressing according to high integration and high speed of LSI. As a state-of-the-art miniaturization technology, mass production by ArF immersion lithography in which exposure is performed by inserting a liquid such as water between a projection lens and a substrate is performed, multiple exposure (multi-patterning) of ArF lithography, and extreme ultraviolet (EUV) with a wavelength of 13.5 nm. Lithography and the like are being reviewed.

Among the chemically amplified resist materials used in the above lithography, a compound that generates an acid by decomposition by exposure (hereinafter referred to as an "acid generator") is used, but acid diffusion can be suppressed by optimizing the structure in the acid generator. This makes it possible to form high-resolution patterns. As such acid generators, for example, those disclosed in Patent Literatures 1 to 4 have been studied.

[Patent Document 1] Japanese Patent Publication 2008-07484 [Patent Document 2] Japanese Patent Publication 2009-191054 [Patent Document 3] Japanese Patent Publication 2011-126869 [Patent Document 4] Japanese Patent Publication 2012-072108

In advancing further miniaturization, acid generators that have been studied in the past have not always been sufficient from the viewpoint of various performances including resolution and resist pattern shape.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a resist composition and pattern formation method showing good mask dimension dependence (mask error factor: MEF) and dimensional uniformity (CDU) in photolithography. .

In order to solve the above problems, in the present invention, (A) a resin containing a repeating unit having an acid labile group and at least one repeating unit having an aromatic substituent, (B) a general formula (B-1) A resist composition characterized by comprising the photo-acid generator shown above and (C) a solvent is provided.

(In the formula, W ₁ represents a cyclic divalent hydrocarbon group containing a hetero atom of 4 to 12 carbon atoms. W ₂ represents a cyclic monovalent hydrocarbon group having 4 to 14 carbon atoms and not containing a hetero atom. Rf is It is a divalent organic group represented by the general formula, A ₁ and A ₂ each independently represent a hydrogen atom or a trifluoromethyl group, and B ₁ and B ₂ each independently represent a hydrogen atom, a fluorine atom or a trifluoromethyl group. and * represents the number of bonds with the carbonyloxy group. m represents an integer of 0 to 4 and n represents an integer of 0 to 1. M ⁺ represents an onium cation.)

Such a resist composition of the present invention exhibits good mask dimension dependence (mask error factor: MEF) and dimensional uniformity (CDU) in photolithography.

In this case, it is preferable that _W1 in the said general formula (B-1) is a cyclic divalent hydrocarbon group containing a lactone ring structure of 6-12 carbon atoms.

With such a resist composition, acid diffusion can be further suppressed by disposing the lactone ring at a position close to the sulfonic acid group during acid generation after exposure, so that better mask dimensional dependence and dimensional uniformity can be exhibited.

Further, it is preferable that W ₂ in the above general formula (B-1) is a polycyclic monovalent hydrocarbon group having 7 to 14 carbon atoms and not containing a hetero atom.

With such a resist composition, appropriate solubility can be imparted by disposing a highly condensed hydrocarbon group at the terminal, and thus better mask dimensional dependence and dimensional uniformity can be exhibited.

Further, the Rf group in the general formula (B-1) is preferably selected from groups represented by the following formulas (Rf-1) to (Rf-6).

(* represents the number of bonds with the carbonyloxy group.)

With such a resist composition, since solubility is improved by the effect of fluorine atoms in Rf and sulfonic acid generated after exposure has an appropriate acid strength, better mask dimensional dependence, LWR, and dimensional uniformity can be exhibited.

Moreover, it is preferable that 1 type of the repeating unit which has the said aromatic substituent in resin of the said component (A) is a repeating unit represented by the following formula (A-1).

(Wherein, R ^A represents a hydrogen atom or a methyl group. R ₆₁ represents a hydrogen atom or a straight-chain, branched or cyclic hydrocarbon group which may be interposed with a hetero atom having 1 to 10 carbon atoms. R ₆₂ represents a hetero atom intervening. Represents an optional straight-chain, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms, t is an integer from 1 to 3, u is an integer satisfying u≤5+2s-t, s is 0 or 1 .L ₁ represents either a single bond or -C(=O)O-, -C(=O)NH-.)

The resist composition of the present invention can exhibit better mask dimensional dependence and dimensional uniformity by combining the component (A) with the component (B).

It is preferable that one of the repeating units having an aromatic substituent in the resin of the component (A) is a repeating unit represented by the following general formulas (A-2) to (A-4).

(In the formula, R ^A is each independently a hydrogen atom or a methyl group, R ²⁰¹ is a single bond, a phenylene group, -OR ²¹⁰ - or -C(=O)-Z ² -R ²¹⁰ -. Z ² is an oxygen atom or NH, R ²¹⁰ is a straight-chain, branched or cyclic alkylene group having 1 to 6 carbon atoms, an alkenylene group or a phenylene group, and a carbonyl group (-CO-), an ester group (-COO-), an ether group (- L ₂ represents a single bond or -Z ³ -C(=O)-O-, and Z ³ is a straight-chain or branched chain which may be substituted with a heteroatom having 1 to 20 carbon atoms. represents a monovalent or cyclic divalent hydrocarbon group, Z ¹ is a single bond, methylene group, ethylene group, phenylene group, fluorinated phenylene group, -OR ²¹¹ - or -C(=O)-Z ⁴ -R ²¹¹ -. Z ⁴ is an oxygen atom or NH, R ²¹¹ is a straight-chain, branched or cyclic alkylene group, alkenylene group or phenylene group having 1 to 6 carbon atoms, which may contain a carbonyl group, ester group, ether group or hydroxyl group. ^{and M - represents a non - nucleophilic} counter ion ^. Represents a preferably straight-chain or branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ²⁰² and R ²⁰³ may combine with each other to form a ring with the sulfur atom in the formula; Alternatively, any two or more of R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ or any two or more of R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ may be bonded to each other to form a ring together with the sulfur atom in the formula. The repeating units represented by -2) to (A-4) have one or more aromatic substituents.)

The resist composition of the present invention can exhibit better mask dimensional dependence and dimensional uniformity by using such component (A).

The resist composition, as component (D), is a resin different from the resin of component (A) and is selected from repeating units represented by the following formulas (D-1), (D-2) and (D-3): It is preferable to further contain at least one fluorine-containing resin.

(In the formula, R ^A is each independently a hydrogen atom or a methyl group. R ₅₁ and R ₅₂ are each independently a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. R ₅₃ is a single bond or a linear or branched divalent hydrocarbon group having 1 to 5 carbon atoms R ₅₄ , R ₅₅ and R ₅₆ are each independently a hydrogen atom or a linear, branched or cyclic carbon atom having 1 to 15 carbon atoms , is a monovalent hydrocarbon group, a fluorinated monovalent hydrocarbon group or an acyl group, or an acid labile group When R ₅₄ , R ₅₅ and R ₅₆ are a monovalent hydrocarbon group or a fluorinated monovalent hydrocarbon group, some of these carbon atoms are ether groups Alternatively, it may be substituted with a carbonyl group. R ₅₇ is a straight-chain, branched or cyclic hydrocarbon group having a (v+1) valency of 1 to 20 carbon atoms or a fluorinated hydrocarbon group. v is an integer of 1 to 3.)

By further including the component (D), the resist composition of the present invention improves the contact angle between the surface of the resist film and water, and suppresses defects due to residual immersion water and elution of the acid generator or quencher. In addition, the solubility of the surface of the resist film can be adjusted, and good dimensional uniformity can be achieved.

In addition, the present invention includes a step of applying the resist composition on a substrate and subjecting it to heat treatment to form a resist film, a step of exposing the resist film to high energy rays, and a step of developing the exposed resist film using a developing solution. It provides a pattern forming method characterized in that it comprises.

With this pattern formation method, good mask dimension dependence and dimensional uniformity can be achieved in photolithography.

In the pattern forming method of the present invention, the high energy ray may be an ArF excimer laser with a wavelength of 193 nm or a KrF excimer laser with a wavelength of 248 nm.

In addition, the exposure is performed by immersion exposure with a liquid having a refractive index of 1.0 or more interposed between the resist film and the projection lens, or by forming an additional protective film on the resist film and interposing the liquid between the protective film and the projection lens. It is also possible to form a pattern by performing liquid immersion exposure.

With such a pattern formation method, better mask dimension dependence and dimensional uniformity can be achieved in photolithography.

In the pattern formation method of the present invention, the high energy ray may be an electron beam or an extreme ultraviolet ray having a wavelength of 3 to 15 nm.

With such a pattern formation method, a pattern with excellent MEF and CDU can be formed with good sensitivity.

The resist composition of the present invention makes it possible to form a resist pattern with excellent mask dimension dependence (mask error factor: MEF) and LWR, in particular.

The present invention is a resist composition exhibiting good mask dimension dependence (mask error factor: MEF) and dimensional uniformity (CDU) in photolithography using high-energy rays such as KrF excimer laser light, electron beams, and extreme ultraviolet rays as a light source. and a pattern forming method.

1 is a diagram showing a ¹ HNMR spectrum of PAG1 obtained in Example 1-1.
Fig. 2 is a diagram showing the ¹⁹ FNMR spectrum of PAG1 obtained in Example 1-1.
Fig. 3 is a diagram showing the ¹ HNMR spectrum of PAG2 obtained in Example 1-2.
4 is a diagram showing the ¹⁹ FNMR spectrum of PAG2 obtained in Example 1-2.

As described above, in advancing further miniaturization, conventionally studied acid generators are not necessarily sufficient from the viewpoints of various performances including resolution and resist pattern shape.

As a result of intensive studies to achieve the above object, the present inventors have found that a resist composition using an acid generator represented by the following formula (B-1) has good mask dimension dependence (mask error factor: MEF) and dimensional uniformity. (CDU), and found that it is very effective for precise microfabrication.

That is, the present invention provides (A) a resin containing a repeating unit having an acid labile group and at least one repeating unit having an aromatic substituent, (B) a photoacid generator represented by the general formula (B-1) and (C) a solvent.

(In the formula, W ₁ represents a cyclic divalent hydrocarbon group containing a hetero atom of 4 to 12 carbon atoms. W ₂ represents a cyclic monovalent hydrocarbon group having 4 to 14 carbon atoms and not containing a hetero atom. Rf is It is a divalent organic group represented by the general formula, A ₁ and A ₂ each independently represent a hydrogen atom or a trifluoromethyl group, and B ₁ and B ₂ each independently represent a hydrogen atom, a fluorine atom or a trifluoromethyl group. and * represents the number of bonds with the carbonyloxy group. m represents an integer of 0 to 4, n represents an integer of 0 to 1. M ⁺ represents an onium cation.)

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto. In addition, in the following chemical formulas, there are a number of chemical structures in which enantiomers or diastereomers may exist, but in any case, unless otherwise specified, each chemical formula represents all of these stereoisomers. . In addition, these stereoisomers may be used alone or as a mixture.

[resist composition]

The resist composition of the present invention comprises: (A) a resin (base resin) containing a repeating unit having an acid labile group and at least one repeating unit having an aromatic substituent; (B) the general formula (B-1) It includes the photoacid generator and (C) solvent indicated. You may further contain other components, such as a specific fluororesin different from the resin of (A) component as component (D), a quencher, and surfactant, as needed. Hereinafter, each component is demonstrated.

[(A) base resin]

In the resist composition of the present invention, the base resin (resin A) of component (A) is a resin containing a repeating unit having an acid labile group and at least one repeating unit having an aromatic substituent.

Among the base resins of component (A), examples of repeating units having an aromatic substituent include the following general formula (A-1).

(Wherein, R ^A represents a hydrogen atom or a methyl group. R ₆₁ represents a hydrogen atom or a straight-chain, branched or cyclic hydrocarbon group which may be interposed with a hetero atom having 1 to 10 carbon atoms. R ₆₂ represents a hetero atom intervening. Represents an optional straight-chain, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms, t is an integer from 1 to 3, u is an integer satisfying u≤5+2s-t, s is 0 or 1 .L ₁ represents either a single bond or -C(=O)O-, -C(=O)NH-.)

In the above formula, examples of the straight-chain, branched, or cyclic hydrocarbon group represented by R ₆₁ having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, which may be interposed by a hetero atom, include a methyl group, an ethyl group, a propyl group, and an isopropyl group. , n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 1-methyl-cyclohexyl group Although an actual machine etc. are mentioned, it is not limited to these.

In the above formula, examples of the straight-chain, branched, or cyclic hydrocarbon group represented by R ₆₂ having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, which may be interposed by a heteroatom, include a methyl group, an ethyl group, a propyl group, and an isopropyl group. , n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, etc. can be specifically exemplified, not limited to these

Here, the broken line represents the number of bonds (the same applies hereinafter).

Specific examples of the repeating unit represented by the general formula (A-1) include the following, but are not limited thereto.

(In the formula, R ^A is the same as above)

(In the formula, R ^A is the same as above)

Among the base resins of the component (A), further examples of the repeating unit having an aromatic substituent include the following general formulas (A-2) to (A-4).

(In the formula, R ^A is each independently a hydrogen atom or a methyl group, R ²⁰¹ is a single bond, a phenylene group, -OR ²¹⁰ - or -C(=O)-Z ² -R ²¹⁰ -. Z ² is an oxygen atom or NH, R ²¹⁰ is a straight-chain, branched or cyclic alkylene group having 1 to 6 carbon atoms, an alkenylene group or a phenylene group, and a carbonyl group (-CO-), an ester group (-COO-), an ether group (- L ₂ represents a single bond or -Z ³ -C(=O)-O-, and Z ³ is a straight-chain or branched chain which may be substituted with a heteroatom having 1 to 20 carbon atoms. represents a monovalent or cyclic divalent hydrocarbon group, Z ¹ is a single bond, methylene group, ethylene group, phenylene group, fluorinated phenylene group, -OR ²¹¹ - or -C(=O)-Z ⁴ -R ²¹¹ -. Z ⁴ is an oxygen atom or NH, R ²¹¹ is a straight-chain, branched or cyclic alkylene group, alkenylene group or phenylene group having 1 to 6 carbon atoms, which may contain a carbonyl group, ester group, ether group or hydroxyl group. M ^- represents a non-nucleophilic counter ion M ^- is a hydroxyl ion, a carboxylic acid ion, a halogen ion, a nitrate ion, a nitrite ion, a chlorate ion, a bromate ion, a methanesulfonate ion, a p-toluenesulfonate ion, monomethyl sulfate ion, carbonate ion, sulfate ion, etc. R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , and R ²⁰⁹ may each independently be substituted with a hetero atom, and the hetero atom intervenes. Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, straight chain, or branched or cyclic having 3 to 20 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert -Alkyl groups such as butyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group, vinyl group, allyl group, propenyl group , butenyl group, hexenyl group, time alkenyl groups such as chlorhexenyl groups; aryl groups such as phenyl, naphthyl and thienyl groups; aralkyl groups such as benzyl, 1-phenylethyl and 2-phenylethyl groups; and the like, preferably aryl groups. In addition, some of the hydrogen atoms in these groups may be substituted with heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms, or may be interposed with heteroatoms such as oxygen, sulfur, and nitrogen, resulting in a hydroxyl group , cyano group, carbonyl group, ether linkage, ester linkage, sulfonic acid ester linkage, carbonate linkage, lactone ring, sultone ring, carboxylic acid anhydride, haloalkyl group, etc. may be formed or intervened. Further, R ²⁰² and R ²⁰³ may combine with each other to form a ring together with the sulfur atom in the formula, or any two or more of R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ or any two or more of R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ may combine with each other to form a ring together with the sulfur atom in the formula. However, the repeating units represented by the general formulas (A-2) to (A-4) have one or more aromatic substituents.)

In the above formula, when L ₂ is -Z ³ -C(=O)-O-, a straight-chain, branched or cyclic divalent hydrocarbon group represented by Z ³ which may be substituted with a hetero atom having 1 to 20 carbon atoms. As examples, the following can be specifically exemplified, but are not limited thereto.

(In the formula, the broken line represents the number of bonds.)

In the above formula, R ²⁰² and R ²⁰³ may combine with each other to form a ring together with the sulfur atom in the formula, or any two or more of R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ or any of R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ Two or more may be bonded to each other to form a ring together with the sulfur atom in the formula, and in that case, groups represented by the following formulas are exemplified.

(In the formula, R ²¹² represents R ²⁰¹ or the same group exemplified as R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , and R ²⁰⁹ .)

Specific structures of the sulfonium cations represented in the general formulas (A-3) to (A-4) include those shown below. However, the present invention is not limited to these.

Examples of the repeating unit having an acid labile group in the base resin of component (A) include the following general formula (a1).

(In the formula, R ¹ is a hydrogen atom or a methyl group. X represents an acid labile group.)

The repeating unit represented by the general formula (a1) is decomposed by the action of an acid to generate a carboxylic acid, giving an alkali-soluble polymer. Although various acid labile groups X can be used, specifically, groups represented by the general formulas (L1) to (L9) below, tertiary alkyl groups having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, and each alkyl group having carbon atoms, respectively. A trialkylsilyl group of 1-6, an oxoalkyl group of 4-20 carbon atoms, etc. are mentioned.

In formula (L1), R ^L01 and R ^L02 represent a hydrogen atom or a straight-chain, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, specifically methyl, ethyl, propyl, iso Propyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, norbornyl group, tricyclodecanyl group, tetracyclododeca A yl group, an adamantyl group, etc. can be illustrated. R ^L03 represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, which may have a hetero atom such as an oxygen atom, and is a linear, branched or cyclic alkyl group, a part of these hydrogen atoms being a hydroxyl group or an alkoxy group groups, oxo groups, amino groups, and those substituted with alkylamino groups and the like, and specifically, the following substituted alkyl groups and the like can be exemplified.

R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 may be mutually bonded to form a ring together with the carbon atom or oxygen atom to which they are bonded, and in the case of forming a ring, R ^L01 , R ^L02 , R ^L03 each represents a straight-chain or branched alkylene group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.

In the formula (L2), R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the above general formula The group represented by (L1) is shown, and examples of the tertiary alkyl group include tert-butyl group, tert-amyl group, 1,1-diethylpropyl group, 2-cyclopentylpropan-2-yl group, and 2-cyclohexyl group. Propan-2-yl group, 2-(bicyclo[2.2.1]heptan-2-yl)propan-2-yl group, 2-(adamantan-1-yl)propan-2-yl group, 1-ethylcyclophene ethyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl-2- An adamantyl group, a 2-ethyl-2-adamantyl group, etc. can be exemplified, and as the trialkylsilyl group, specifically, a trimethylsilyl group, a triethylsilyl group, a dimethyl-tert-butylsilyl group, etc. can be exemplified. Examples of the oxoalkyl group include 3-oxocyclohexyl group, 4-methyl-2-oxoxan-4-yl group, and 5-methyl-2-oxoxolan-5-yl group. l is an integer from 0 to 6;

In formula (L3), R ^L05 represents an optionally substituted straight-chain, branched or cyclic alkyl group of 1 to 8 carbon atoms or an optionally substituted aryl group of 6 to 20 carbon atoms, and the optionally substituted alkyl group is specifically is a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. A straight-chain, branched or cyclic alkyl group, some of these hydrogen atoms are hydroxyl group, alkoxy group, carboxy group, alkoxycarbonyl group, oxo group, amino group, alkylamino group, cyano group, mercapto group, alkylthio group, sulfo group, etc. Substituted ones can be exemplified, and examples of aryl groups which may be substituted include phenyl groups, methylphenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, pyrenyl groups and the like. In Formula (L3), m is 0 or 1, n is any one of 0, 1, 2, and 3, and is a number satisfying 2m+n=2 or 3.

In the formula (L4), R ^L06 represents an optionally substituted straight-chain, branched or cyclic alkyl group having 1 to 8 carbon atoms or an aryl group which may be substituted with 6 to 20 carbon atoms, and is specifically the same as R ^L05 . can be exemplified. R ^L07 to R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 15 carbon atoms, specifically methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclopentyl group Straight-chain, branched or cyclic alkyl groups such as butyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, etc., some of these hydrogen atoms are hydroxyl group, alkoxy group, carboxy group, alkoxycarbonyl group, oxo group, amino group, alkyl Those substituted with an amino group, a cyano group, a mercapto group, an alkylthio group, a sulfo group, and the like can be exemplified. R ^L07 to ^{R L16} may be bonded to each other to form a ring (for example, R ^L07 and R ^L08 , R ^L07 and R ^L09 , R L08 and R ^L10 , R ^L09 and ^{R L10} , R ^L11 and R ^L12 , R ^L13 and R ^L14, etc.), in which case it represents a divalent hydrocarbon group having 1 to 15 carbon atoms, and specifically, those exemplified in the above monovalent hydrocarbon group except for one hydrogen atom can be exemplified. In addition, R ^L07 to ^{R L16} may be bonded to adjacent carbon atoms without passing through each other to form a double bond (for example, R ^L07 and R ^L09 , R ^L09 and R ^L15 , R ^L13 and R ^L15 , etc.) .

In formula (L5), R ^L17 , R ^L18 , and R ^L19 each independently represent a straight-chain, branched or cyclic alkyl group having 1 to 15 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, 1- An adamantyl group, a 2-adamantyl group, etc. can be illustrated.

In formula (L6), R ^L20 represents an optionally substituted straight-chain, branched or cyclic alkyl group of 1 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms which may be substituted, and is specifically the same as R ^L05 . can be exemplified.

In formula (L7), R ^L21 represents an optionally substituted straight-chain, branched or cyclic alkyl group of 1 to 10 carbon atoms or an optionally substituted aryl group of 6 to 20 carbon atoms, specifically R ^L05 , etc. can be exemplified.

R ^L24 represents a divalent group that forms a substituted or unsubstituted cyclopentane ring, cyclohexane ring or norbornane ring together with the carbon atom to which it is bonded. R ^L22 and R ^L23 each independently represent a hydrogen atom or a straight-chain, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. R ^L22 and R ^L23 may be bonded to each other to form a ring together with the carbon atom to which they are bonded, and in that case represent a divalent group forming a substituted or unsubstituted cyclopentane ring or cyclohexane ring. p represents 1 or 2;

In the formula (L8), R ^L25 represents an optionally substituted straight-chain, branched or cyclic alkyl group of 1 to 10 carbon atoms or an optionally substituted aryl group of 6 to 20 carbon atoms, and is specifically the same as R ^L05 . can be exemplified.

R ^L28 represents a divalent group that forms a substituted or unsubstituted cyclopentane ring, cyclohexane ring or norbornane ring together with the carbon atom to which it is bonded. R ^L26 and R ^L27 each independently represent a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. R ^L26 and R ^L27 may be bonded to each other to form a ring together with the carbon atom to which they are bonded, and in that case represent a divalent group forming a substituted or unsubstituted cyclopentane ring or cyclohexane ring. q represents 1 or 2;

In the formula (L9), R ^L29 represents an optionally substituted straight-chain, branched or cyclic alkyl group of 1 to 10 carbon atoms or an optionally substituted aryl group of 6 to 20 carbon atoms, specifically R ^L05 , etc. can be exemplified.

R ^L32 represents a divalent group that forms a substituted or unsubstituted cyclopentane ring, cyclohexane ring or norbornane ring together with the carbon atom to which it is bonded. R ^L30 and R ^L31 each independently represent a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. R ^L30 and R ^L31 may be bonded to each other to form a ring together with the carbon atom to which they are bonded, and in that case represent a divalent group forming a substituted or unsubstituted cyclopentane ring or cyclohexane ring.

Among the acid labile groups represented by the above formula (L1), examples of straight-chain or branched groups are specifically exemplified by the following groups.

Among the cyclic acid labile groups represented by the formula (L1), specifically, tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, 2-methyltetra A hydropyran-2-yl group etc. can be illustrated.

Examples of the acid labile group of the formula (L2) include tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tert-amyloxycarbonyl, tert-amyloxycarbonylmethyl, and 1,1-diethylpropyloxycarbonyl. , 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2-cyclo Pentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group, etc. can be illustrated.

Examples of acid labile groups of the formula (L3) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1- sec-butylcyclopentyl, 1-tert-butylcyclopentyl, 1-cyclohexylcyclopentyl, 1-(4-methoxy-n-butyl)cyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3 -Methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopenten-3-yl, 3-methyl-1-cyclohexen-3-yl, 3-ethyl-1-cyclohexen-3-yl etc. can be exemplified.

As the acid labile group of the formula (L4), groups represented by the following formulas (L4-1) to (L4-4) are particularly preferred.

In the general formulas (L4-1) to (L4-4), the broken line indicates the bonding position and bonding direction. R ^L41 each independently represents a monovalent hydrocarbon group such as a straight-chain, branched or cyclic alkyl group having 1 to 10 carbon atoms, specifically methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. can be illustrated.

The general formulas (L4-1) to (L4-4) may have enantiomers or diastereomers. Shown representative of all isomers. These stereoisomers may be used alone or as a mixture.

For example, the general formula (L4-3) represents one type or a mixture of two types selected from groups represented by the following general formulas (L4-3-1) and (L4-3-2). .

In addition, the formula (L4-4) represents one type or a mixture of two or more types selected from groups represented by the following general formulas (L4-4-1) to (L4-4-4).

The general formulas (L4-1) to (L4-4), (L4-3-1), (L4-3-2) and (L4-4-1) to (L4-4-4) are Enantiomers and enantiomeric mixtures are also meant to be representative.

In addition, the bonding directions of (L4-1) to (L4-4), (L4-3-1), (L4-3-2) and (L4-4-1) to (L4-4-4) are respectively By being on the exo side with respect to the bicyclo[2.2.1]heptane ring, high reactivity in the acid-catalyzed elimination reaction is realized (see Japanese Patent Laid-Open No. 2000-336121). In the production of monomers having a tertiary exo-alkyl group having a bicyclo[2.2.1]heptane skeleton as a substituent, endo- represented by the following general formulas (L4-1-endo) to (L4-4-endo) It may contain a monomer substituted with an alkyl group, but in order to realize good reactivity, the exo ratio is preferably 50% or more, and the exo ratio is more preferably 80% or more.

(Refer to Japanese Unexamined Patent Publication No. 2000-336121)

Specific examples of the acid labile group in the formula (L4) include the following groups.

Further, examples of the tertiary alkyl group having 4 to 20 carbon atoms, the trialkylsilyl group having each alkyl group having 1 to 6 carbon atoms, and the oxoalkyl group having 4 to 20 carbon atoms include those specifically exemplified by R ^L04 . there is.

Specific examples of the acid labile group of the formula (L5) include a tert-butyl group, a tert-amyl group and the following groups.

Specific examples of the acid labile group of the formula (L6) include the following groups.

Specific examples of the acid labile group of the formula (L7) include the following groups.

Specific examples of the acid labile group in the formula (L8) include the following groups.

Specific examples of the acid labile group of the formula (L9) include the following groups.

Specific examples of the monomer represented by the general formula (a1) include the following, but are not limited thereto.

(In the formula, R ¹ represents a hydrogen atom or a methyl group)

(In the formula, R ¹ represents a hydrogen atom or a methyl group)

(In the formula, R ¹ represents a hydrogen atom or a methyl group)

(In the formula, R ¹ represents a hydrogen atom or a methyl group)

In addition to the units represented by the general formula (a1), among the base resins of the component (A), it is preferable to use monomers represented by the following general formulas (a2) to (a4) as needed.

(In the formula, R ¹ is the same as above. R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydroxyl group. Y represents a substituent having a lactone structure or a substituent having a sultone structure. Z is a hydrogen atom or carbon number Represents a fluorinated hydrocarbon group of 1 to 15 or a substituent containing fluoroalcohol of 1 to 15 carbon atoms.)

As the unit represented by the general formula (a2), specifically, the following units can be exemplified, but are not limited thereto.

Specific examples of the monomer represented by the general formula (a3) include the following, but are not limited thereto.

(In the formula, R ¹ represents a hydrogen atom or a methyl group)

(In the formula, R ¹ represents a hydrogen atom or a methyl group)

(In the formula, R ¹ represents a hydrogen atom or a methyl group)

(In the formula, R ¹ represents a hydrogen atom or a methyl group)

Specific examples of the repeating unit represented by the general formula (a4) include the following, but are not limited thereto.

In the resist composition of the present invention, monomers containing carbon-carbon double bonds other than those described above, such as substituted acrylic acid esters such as methyl methacrylate, methyl crotonic acid, dimethyl maleate, dimethyl itaconate, maleic acid, and fumaric acid , unsaturated carboxylic acids such as itaconic acid, norbornene, norbornene derivatives, cyclic olefins such as tetracyclo[4.4.0.1 ^{2,5.17 7,10} ] dodecene derivatives, unsaturated acids such as itaconic acid anhydride Anhydrides, α-methylene-γ-butyrolactones, α-methylstyrenes, and other monomers may be used.

1,000-500,000 are preferable and, as for the weight average molecular weight (Mw) of resin A (base resin of (A) component), 3,000-100,000 are more preferable. If it is the said range, there is no fear that etching resistance will fall or resolution before and after exposure cannot be ensured, and resolution will fall. In the present invention, Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or dimethylacetamide (DMF) as a solvent.

Furthermore, in the resin A, when the molecular weight distribution (Mw/Mn) is wide, low molecular weight or high molecular weight polymers are present, so there is a possibility that foreign matter may be seen on the pattern after exposure or the shape of the pattern may be deteriorated. Therefore, as the pattern rule becomes finer, the influence of such molecular weight and molecular weight distribution tends to increase. Therefore, in order to obtain a resist composition suitable for fine pattern dimensions, the molecular weight distribution of Resin A is set to 1.0 to 2.0, particularly 1.0 to 1.5. Narrow dispersion is preferred.

As a method for synthesizing Resin A, for example, a monomer having an unsaturated bond to obtain a repeating unit represented by formula (a1) and optionally a repeating unit represented by formulas (a2) to (a4) or other repeating units is organically Among the solvents, a method of adding a radical initiator to heat polymerization is exemplified. Examples of the organic solvent used during polymerization include toluene, benzene, THF, diethyl ether, dioxane, methyl ethyl ketone, γ-butyrolactone, and propylene glycol monomethyl ether acetate (PGMEA). As the polymerization initiator, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropio nate), benzoyl peroxide, lauroyl peroxide and the like. The reaction temperature is preferably 50 to 150°C, more preferably 60 to 100°C. The reaction time is preferably 2 to 24 hours. As the acid labile group, those introduced into the monomer may be used as they are, or may be protected or partially protected after polymerization. In addition, polymerization may be performed using a known chain transfer agent such as dodecylmercaptan or 2-mercaptoethanol to adjust the molecular weight. In this case, the added amount of the chain transfer agent is preferably 0.01 to 10 in terms of molar ratio with respect to all the monomers to be polymerized.

In the resin A, the preferable content ratio of each repeating unit obtained from each monomer can be set to, for example, the range shown below, but is not limited thereto.

(I) contains preferably 1 to 99 mol%, more preferably 20 to 95 mol%, and even more preferably 30 to 90 mol% of the repeating unit represented by formula (a1), as necessary;

(II) contains preferably 1 to 70 mol%, more preferably 5 to 60 mol%, still more preferably 10 to 60 mol% of the repeating unit represented by formula (A-1);

(III) at least one selected from repeating units represented by formulas (A-2) to (A-4), preferably 1 to 40 mol%, more preferably 3 to 35 mol%, still more preferably contains 5 to 30 mol%,

(IV) preferably 0 to 99 mol%, more preferably 0 to 90 mol%, still more preferably 0 to 70 mol% of at least one selected from repeating units represented by formulas (a2) to (a4) contains mol %,

(V) other repeating units, preferably 0 to 99 mol%, more preferably 0 to 70 mol%, still more preferably 0 to 50 mol%.

In addition, the base resin of component (A) may contain two or more types of resins having different composition ratios, molecular weights or molecular weight distributions, and, if necessary, in addition to resins having repeating units having acid labile groups, formula (a1) A resin not containing the repeating unit represented by may be included.

[(B) Photoacid Generator]

The resist composition of the present invention contains a photoacid generator represented by the following formula (B-1) as component (B).

(In the formula, W ₁ represents a cyclic divalent hydrocarbon group containing a hetero atom of 4 to 12 carbon atoms. W ₂ represents a cyclic monovalent hydrocarbon group having 4 to 14 carbon atoms and not containing a hetero atom. Rf is It is a divalent organic group represented by the general formula, A ₁ and A ₂ each independently represent a hydrogen atom or a trifluoromethyl group, and B ₁ and B ₂ each independently represent a hydrogen atom, a fluorine atom or a trifluoromethyl group. and * represents the number of bonds with the carbonyloxy group. m represents an integer of 0 to 4 and n represents an integer of 0 to 1. M ⁺ represents an onium cation.)

Specific examples of the cyclic divalent hydrocarbon group represented by W ₁ containing a heteroatom of 4 to 12 carbon atoms include the following.

(* represents the number of bonds with the oxycarbonyl group.)

Particularly preferable as W ₁ is a cyclic divalent hydrocarbon group containing a lactone ring structure, and particularly preferably a cyclic divalent hydrocarbon group containing a lactone ring structure of 6 to 12 carbon atoms. When acid is generated after exposure, by arranging the lactone ring at a position close to the sulfonic acid group, acid diffusion can be further suppressed.

Specific examples of the cyclic monovalent hydrocarbon group represented by W ₂ having 4 to 14 carbon atoms and not containing a hetero atom include the following ones.

(The dashed line represents the number of bonds.)

W ₂ is preferably a polycyclic monovalent hydrocarbon group having 7 to 14 carbon atoms and not containing a hetero atom. A particularly preferable example of W ₂ is an adamantyl group. Appropriate solubility can be imparted by arranging a highly condensed hydrocarbon group at the terminal.

Rf is a divalent organic group represented by the above general formula. Here, A ₁ and A ₂ each independently represent a hydrogen atom or a trifluoromethyl group, B ₁ and B ₂ each independently represent a hydrogen atom, a fluorine atom or a trifluoromethyl group, and * represents a carbonyloxy group indicates the number of bonds. m represents an integer of 0 to 4, and n represents an integer of 0 to 1. It is preferable that m+n>0.

In particular, it is preferable that the Rf group is selected from groups represented by the following formulas (Rf-1) to (Rf-6).

(* represents the number of bonds with the carbonyloxy group.)

If the photoacid generator represented by the formula (B-1) has such an Rf, the solubility is improved by the effect of the fluorine atom, and the sulfonic acid generated after exposure has an appropriate acid strength, so it is preferable.

Although the specific example of the structure of the anion part of the photo-acid generator represented by Formula (B-1) is shown below, it is not limited to these.

In the formula (B-1), the onium cation represented by M ⁺ is preferably at least one selected from cations represented by the following formula (b1) and formula (b2).

In formulas (b1) and (b2), R ⁴¹ to R ⁴⁵ are each independently a straight-chain, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. Also, any two of R ⁴¹ , R ⁴² and R ⁴³ may be mutually bonded to form a ring together with the sulfur atom in the formula.

Examples of the monovalent hydrocarbon group represented by R ⁴¹ to ^{R 45} include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclo alkyl groups such as propylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, and adamantyl group; Alkenyl groups, such as a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group; Aryl groups, such as a phenyl group, a naphthyl group, and a thienyl group; Aralkyl groups, such as a benzyl group, 1-phenylethyl group, and 2-phenylethyl group, etc. are mentioned. Among these, an aryl group is preferable. In addition, some of the hydrogen atoms of the monovalent hydrocarbon group may be substituted with heteroatom-containing groups such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and some of the carbon atoms in these groups are oxygen atoms, sulfur atoms, and nitrogen atoms. may be substituted with a group containing a hetero atom such as an atom, and as a result, a hydroxyl group, a cyano group, a carbonyl group, an ether group, an ester group, a sulfonic acid ester group, a carbonate group, a lactone ring, a sultone ring, a carboxylic acid anhydride, a haloalkyl group, etc. may contain

Examples of the sulfonium cation represented by the formula (b1) include those shown below, but are not limited thereto.

Although what is shown below is mentioned as an iodonium cation represented by Formula (b2), It is not limited to these.

In addition, the resist composition of the present invention may further contain other photoacid generators other than the photoacid generator described above in order to fine-tune the lithography performance. As the other photoacid generator, any compound that generates an acid when irradiated with high energy rays may be used, and any known photoacid generator used in conventional resist compositions, particularly chemically amplified resist compositions may be used. Other suitable photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate type acid generators, which are used alone or in combination of two or more. Can be used in combination. As acids generated from other photoacid generators, strong acids such as sulfonic acid, (bisperfluoroalkanesulfonyl)imide, and (trisperfluoromethanesulfonyl)methide or weak acids such as carboxylic acid are preferable.

Specific examples of other photoacid generators include the following formulas (B-2), formulas (B-3) and formulas (B-4).

In Formula (B-2), A ¹ is a hydrogen atom or a trifluoromethyl group. R ²¹ is a linear, branched or cyclic monovalent hydrocarbon group having 1 to 35 carbon atoms, a nitrogen-containing heterocyclic group, or a group represented by the following formula (i), which may contain an oxygen atom. M ⁺ is an onium cation.

In formula (i), R ³¹ and R ³² are each independently a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. R ³¹ and R ³² may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded. R ³³ is a straight-chain, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.

Examples of the monovalent hydrocarbon group that may contain an oxygen atom represented by R ²¹ include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, Heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, 1-adamantyl group, 1-adamantylmethyl group, etc. Alkyl group of; a group containing a steroid structure; 2-oxocyclopentyl group, 2-oxocyclohexyl group, 4-oxocyclohexyl group, 2-oxopropyl group, 2-oxoethyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxo Ethyl group, 2-(4-methylcyclohexyl)-2-oxoethyl group, 4-oxa-tricyclo[4.2.1.0 ^3,7 ]nonan-5-one-9-yl group, 4-oxo-1-adamantyl group oxoalkyl groups such as; Phenyl group, 1-naphthyl group, 2-naphthyl group, anthranyl group, thienyl group, 4-hydroxyphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 4- Alkoxyphenyl groups such as tert-butoxyphenyl group and 3-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4-n-butyl Alkyl phenyl groups such as phenyl group and 2,4-dimethylphenyl group, alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dimethyl naphthyl group, diethyl naphthyl group, etc. Aryl groups, such as a dialkoxy naphthyl group, such as a dialkyl naphthyl group, a dimethoxy naphthyl group, and a diethoxy naphthyl group of; Aralkyl groups, such as a benzyl group, 1-phenylethyl group, and 2-phenylethyl group; Aryloxo, such as 2-aryl-2-oxoethyl group, such as 2-phenyl-2-oxoethyl group, 2-(1-naphthyl)-2-oxoethyl group, and 2-(2-naphthyl)-2-oxoethyl group An alkyl group etc. are mentioned. In addition, a vinyl group, an isopropenyl group, etc. are mentioned.

Examples of the nitrogen-containing heterocyclic group represented by R ²¹ include aziridine, pyrrolidine, piperidine, morpholine, pyrrole, pyridine, azetine, oxazole, isoxazole, thiazole, isothiazole, imidazole, and pyra. Sol, pyridazine, pyrimidine, pyrazine, pyrroline, 2-imidazoline, imidazolidine, 3-pyrazoline, pyrazolidine, piperazine, triazine, oxadiazine, dithiazine, indole, isoindole , quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, 1,8-naphthyridine, purine, pteridine, indolizine, carbazole, acridine, phenazine, phenanthridine, 1 , 10-phenanthroline, phenoxazine, indoline, isoindoline, quinuclidine, benzo[e]indole, benzo[cd]indole and the like.

Particularly preferred examples of R ²¹ include tert-butyl group, cyclohexyl group, 1-adamantyl group, 1-adamantylmethyl group, 4-oxa-tricyclo[4.2.1.0 ^3,7 ]nonan-5-one- 9-yl group, 4-oxo-1-adamantyl group, steroid structure-containing alkyl group, etc. are mentioned.

In formula (i), examples of the monovalent hydrocarbon group represented by R ³¹ and R ³² include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and hex. alkyl groups such as a real group, a heptyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopropylmethyl group, a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, and an adamantyl group; Alkenyl groups, such as a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group; Aralkyl groups, such as aryl groups, such as a phenyl group, a naphthyl group, and a thienyl group, and a benzyl group, 1-phenylethyl group, and 2-phenylethyl group, are mentioned. Furthermore, in the hydrocarbon group, some of the hydrogen atoms may be substituted with the monovalent hydrocarbon group or a heteroatom-containing group such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, or a part of the carbon atoms of these groups may be substituted with a heteroatom-containing group such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result, a hydroxy group, a cyano group, a carbonyl group, an ether group, an ester group, a sulfonic acid ester group, a carbonate group, a lactone ring, a sultone ring, A boxylic acid anhydride, a haloalkyl group, etc. may be included.

When R ³¹ and R ³² are mutually bonded to form a ring together with the nitrogen atom to which they are bonded, specific ring types include aziridine, pyrrolidine, piperidine, morpholine, pyrrole, pyridine, azetine, and oxazole. , isoxazole, thiazole, isothiazole, imidazole, pyrazole, pyridazine, pyrimidine, pyrazine, pyrroline, 2-imidazoline, imidazolidine, 3-pyrazoline, pyrazolidine, pipe Razine, triazine, oxadiazine, dithiazine, indole, isoindole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, 1,8-naphthyridine, purine, pteridine, indolizine , carbazole, acridine, phenazine, phenanthridine, 1,10-phenanthroline, phenoxazine, indoline, isoindoline, quinuclidine, benzo[e]indole, benzo[cd]indole, etc. can be heard In addition, some of the hydrogen atoms of these rings may be substituted with the above hydrocarbon groups or heteroatom-containing groups such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, or some of the carbon atoms of these rings may be substituted with oxygen atoms or sulfur atoms. may be substituted with a heteroatom-containing group such as atom or nitrogen atom, and as a result, a hydroxyl group, a cyano group, a carbonyl group, an ether group, an ester group, a sulfonic acid ester group, a carbonate group, a lactone ring, a sultone ring, a carboxylic anhydride, a halo It may contain an alkyl group etc.

Examples of the divalent hydrocarbon group represented by R ³³ in formula (i) include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, Hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1, 11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1, straight-chain alkanediyl groups such as 16-diyl group and heptadecane-1,17-diyl group; a branched alkanediyl group obtained by adding a side chain such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, or a tert-butyl group to the straight-chain alkanediyl group; saturated cyclic hydrocarbon groups such as cyclopentanediyl group, cyclohexanediyl group, norbornandiyl group, and adamantanediyl group; Unsaturated cyclic divalent hydrocarbon groups, such as a phenylene group and a naphthylene group, are mentioned. In addition, some of the hydrogen atoms of these groups may be substituted with hetero atom-containing groups such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, or some of the carbon atoms of these groups may be oxygen atoms, sulfur atoms, nitrogen atoms, etc. may be interposed with a heteroatom-containing group of, and as a result, a hydroxyl group, a cyano group, a carbonyl group, an ether group, an ester group, a sulfonic acid ester group, a carbonate group, a lactone ring, a sultone ring, a carboxylic acid anhydride, a haloalkyl group, etc. may be

Although the specific example of the structure of the anion part of the photo-acid generator represented by Formula (B-2) is shown below, it is not limited to these. In addition, in the following formula, A ¹ is the same as above.

In the formula (B-2), the onium cation represented by M ⁺ is preferably at least one selected from cations represented by the formulas (b1) and (b2).

In formula (B-3), A ² is a hydrogen atom or a trifluoromethyl group. R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom or a straight-chain, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. p and q are each independently an integer of 0 to 5; r is an integer from 0 to 4; L is a straight-chain, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a single bond, an ether group or a hetero atom.

Examples of the monovalent hydrocarbon group represented by R ²² , R ²³ and R ²⁴ include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, n- A pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group, and alkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, norbornyl group, oxanorbornyl group, tricyclo[5.2.1.0 ^2,6 ]decanyl group, and adamantyl group. In addition, some of the hydrogen atoms of these groups may be substituted with hetero atom-containing groups such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, or some of the carbon atoms of these groups may be oxygen atoms, sulfur atoms, nitrogen atoms, etc. may be substituted with a group containing a hetero atom of, and as a result, a hydroxyl group, a cyano group, a carbonyl group, an ether group, an ester group, a sulfonic acid ester group, a carbonate group, a lactone ring, a sultone ring, a carboxylic acid anhydride, a haloalkyl group, etc. may be As R ²² , R ²³ and R ²⁴ , a methyl group, a methoxy group, a tert-butyl group, a tert-butoxy group and the like are preferable.

Examples of the divalent hydrocarbon group represented by L in the formula (B-3) include those exemplified as R ³³ , and two or more of these groups may be combined. In addition, some of the hydrogen atoms of these groups may be substituted with hetero atom-containing groups such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, or some of the carbon atoms of these groups may be oxygen atoms, sulfur atoms, nitrogen atoms, etc. may be substituted with a group containing a hetero atom of, and as a result, a hydroxyl group, a cyano group, a carbonyl group, an ether group, an ester group, a sulfonic acid ester group, a carbonate group, a lactone ring, a sultone ring, a carboxylic acid anhydride, a haloalkyl group, etc. may be

Although what is shown below is mentioned as a photo-acid generator represented by Formula (B-3), It is not limited to these. In addition, in the following formula, A ² is the same as above.

(B) The photoacid generator may further contain a compound represented by the formula (B-4). In Formula (B-4), A ³ and A ⁴ are each independently a hydrogen atom or a trifluoromethyl group, and do not become a hydrogen atom at the same time. R ²⁵ is a linear, branched or cyclic monovalent hydrocarbon group having 1 to 35 carbon atoms, a nitrogen-containing heterocyclic group, or a group represented by the formula (i), which may contain an oxygen atom. M ⁺ is the same as the above onium cation.

Although the specific example of the structure of the anion part of the photo-acid generator represented by Formula (B-4) is shown below, it is not limited to these.

Among the other photoacid generators described above, a compound having a trifluoromethyl group or other fluorine atom-containing structure in the anion structural portion has high hydrophobicity and little elution into immersion water. In addition, since it has a fluorine atom-containing structure, solvent solubility is high, and it is possible to reduce residues after development in organic solvent development. As a result, defects after development can be reduced, and it is suitable as a resist composition for ArF immersion lithography.

Specific examples other than the photoacid generator described above include compounds described in paragraphs [0122] to [0142] of Japanese Patent Laid-Open No. 2008-111103, and particularly preferred are compounds described in Japanese Patent Laid-Open No. 2014-001259 [ 0088] to [0092], compounds described in paragraphs [0015] to [0017] of Japanese Patent Laid-Open No. 2012-41320, and paragraphs [0015] to [0029] of Japanese Patent Laid-Open No. 2012-106986 A compound etc. are mentioned. The partially fluorinated sulfonic acid-generating type photo-acid generator described in the above publication can be suitably used, especially in ArF lithography, because the strength and diffusion length of the generated acid are suitable.

The content of the photoacid generator in component (B) is preferably from 0.1 to 50 parts by mass, more preferably from 0.2 to 40 parts by mass, still more preferably from 0.3 to 35 parts by mass, based on 100 parts by mass of the base resin of component (A). Within the above range, the resolution is not deteriorated, and there is no fear of causing a problem of foreign matter after development or during peeling of the resist film. Moreover, as for content in the case of adding the compound represented by Formula (B-4), 0-50 mass % is preferable in the photo-acid generator of component (B).

[(C) Solvent]

The resist composition of the present invention contains a solvent as component (C). As the solvent, ketones such as cyclohexanone and methyl-2-n-pentyl ketone, 3-methoxybutanol, and 3-methyl- Alcohols such as 3-methoxybutanol, 1-methoxy-2-propanol and 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethylene glycol monoethyl Ethers such as ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, PGMEA, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, 3-methoxymethylpropionate, 3-ethoxyethylpropionate, acetic acid esters such as tert-butyl, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; lactones such as γ-butyrolactone; keto alcohols such as diacetone alcohol; and mixed solvents thereof. When an acetal acid labile group is used, a high-boiling alcohol solvent, specifically diethylene glycol, propylene glycol, glycerin, 1,4-butanediol, 1,3-butanediol, etc., is used to accelerate the deprotection reaction of acetal. may be added.

The content of the solvent of component (C) is preferably 100 to 10,000 parts by mass, and more preferably 300 to 8,000 parts by mass with respect to 100 parts by mass of the base resin of component (A).

[(D) fluorine-containing resin]

The resist composition of the present invention is a resin different from the resin A, and contains fluorine containing at least one repeating unit selected from the following formulas (D-1), (D-2) and (D-3): You may contain resin.

In the formula, R ^A is a hydrogen atom or a methyl group. R ₅₁ and R ₅₂ are each independently a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. R ₅₃ is a single bond or a linear or branched divalent hydrocarbon group having 1 to 5 carbon atoms. R ₅₄ , R ₅₅ and R ₅₆ are each independently a hydrogen atom, a linear, branched or cyclic monovalent hydrocarbon group having 1 to 15 carbon atoms, a fluorinated monovalent hydrocarbon group or an acyl group, or an acid labile group. When R ₅₄ , R ₅₅ and R ₅₆ are monovalent hydrocarbon groups or fluorinated monovalent hydrocarbon groups, some of these carbon atoms may be substituted with ether groups or carbonyl groups. R ₅₇ is a straight-chain, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms and a (v+1) valency, or a fluorinated hydrocarbon group. v is an integer from 1 to 3;

Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ₅₁ and R ₅₂ include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl group, cyclobutyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, adamantyl group , and an alkyl group such as a norbornyl group. Among these, a straight-chain, branched or cyclic monovalent hydrocarbon group having 1 to 6 carbon atoms is preferable.

Specific examples of the divalent hydrocarbon group having 1 to 5 carbon atoms represented by R ₅₃ include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, and a pentamethylene group.

Examples of the monovalent hydrocarbon group having 1 to 15 carbon atoms represented by R ₅₄ , R ₅₅ and R ₅₆ include an alkyl group, an alkenyl group and an alkynyl group, and an alkyl group is preferable. Examples of the alkyl group include n-undecyl group, n-dodecyl group, tridecyl group, tetradecyl group, and pentadecyl group in addition to those described above. Examples of the fluorinated monovalent hydrocarbon group having 1 to 15 carbon atoms include groups in which some or all of the hydrogen atoms bonded to carbon atoms of the monovalent hydrocarbon group described above are substituted with fluorine atoms. As described above, some of these carbon atoms may be substituted with ether groups or carbonyl groups.

When R ₅₄ , R ₅₅ and R ₅₆ are acid labile groups, specific examples thereof include groups represented by formulas (L1) to (L9), tertiary alkyl groups having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, and each alkyl group. are trialkylsilyl groups each having 1 to 6 carbon atoms, oxoalkyl groups having 4 to 20 carbon atoms, and the like.

As the (v+1) valent hydrocarbon group or fluorinated hydrocarbon group of 1 to 20 carbon atoms represented by R ₅₇ , a group obtained by excluding the necessary number of hydrogen atoms from the aforementioned monovalent hydrocarbon group or fluorinated monovalent hydrocarbon group is exemplified.

Although what is shown below is mentioned as a repeating unit represented by Formula (D-1), It is not limited to these. In addition, in the following formula, R ^A is the same as above.

Examples of the repeating unit represented by the formula (D-2) include those shown below, but are not limited thereto. In addition, in the following formula, R ^A is the same as above.

Although what is shown below is mentioned as a repeating unit represented by Formula (D-3), It is not limited to these. In addition, in the following formula, R ^A is the same as above.

(D) 1,000-100,000 are preferable and, as for Mw of the fluorine-containing resin of component, 3,000-15,000 are more preferable. Mw/Mn is preferably 1.0 to 2.0, and more preferably 1.0 to 1.6.

In order to synthesize the fluorine-containing resin of component (D), as one method, repeating units represented by formulas (D-1) to (D-3), and optionally unsaturated bonds to obtain other repeating units A method of heat polymerization by adding a radical initiator to the monomer in an organic solvent is exemplified. Examples of the organic solvent used during polymerization include toluene, benzene, THF, diethyl ether, dioxane, methyl ethyl ketone, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. As the polymerization initiator, AIBN, 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate), benzoyl peroxide, lauroyl peroxide, etc. can be heard The reaction temperature is preferably 50 to 100°C. The reaction time is preferably 4 to 24 hours. As the acid labile group, those introduced into the monomer may be used as they are, or may be protected or partially protected after polymerization. In addition, polymerization may be performed using a known chain transfer agent such as dodecylmercaptan or 2-mercaptoethanol to adjust the molecular weight. In this case, the added amount of the chain transfer agent is preferably 0.01 to 10 in terms of molar ratio with respect to all the monomers to be polymerized.

When the resist composition of the present invention contains the fluorine-containing resin as component (D), the content thereof is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the base resin of component (A). do. When the content is within the above range, the contact angle between the surface of the resist film and water is sufficiently improved, and defects due to residual immersion water and elution of an acid generator or quencher can be suppressed. Moreover, it becomes possible to adjust the solubility of the surface of the resist film, and good dimensional uniformity can be achieved.

[Other Ingredients]

The resist composition of the present invention may contain an amine compound, a sulfonic acid salt or a carboxylate salt as a quencher, if necessary. In this specification, the quencher means a compound capable of suppressing the diffusion rate when an acid generated from a photoacid generator diffuses into a resist film.

Examples of the amine compound in such a quencher include the primary, secondary or tertiary amine compounds described in paragraphs [0146] to [0164] of Japanese Patent Laid-Open No. 2008-111103, particularly hydroxy groups, ether groups, ester groups, lactone rings, and cyanates. An amine compound having either a no group, a sulfonic acid ester group, or the like is exemplified as a preferable one. Further, compounds in which a primary or secondary amine is protected as a carbamate group, such as the compound described in Japanese Patent No. 3790649, are also exemplified. Such a protected amine compound is effective when there is a base-labile component in the resist composition.

As said sulfonic acid salt, the compound represented by the following formula (Z1) is mentioned. Moreover, as said carboxylate, the compound represented by the following formula (Z2) is mentioned.

R ¹⁰¹ is a hydrogen atom or a hydrocarbyl group having 1 to 40 carbon atoms which may contain a hetero atom, except those in which the hydrogen atom bonded to the carbon atom at the α position of the sulfo group is substituted with a fluorine atom or a fluoroalkyl group. . M ⁺ is each independently an onium cation, and the same ones as those exemplified above are exemplified.

The hydrocarbyl group may be either saturated or unsaturated, and may be straight-chain, branched or cyclic. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-pentyl group, n-pentyl group, n-hexyl group, n-octyl group, 2 - Alkyl groups, such as an ethylhexyl group, n-nonyl group, and n-decyl group; Cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, norbornyl group, tricyclo[5.2.1.0 ^2,6 ]decanyl group , cyclic saturated hydrocarbyl groups such as adamantyl group and adamantylmethyl group; As an alkenyl group, Alkenyl groups, such as a vinyl group, an allyl group, a propenyl group, a butenyl group, and a hexenyl group; Unsaturated aliphatic cyclic hydrocarbyl groups, such as a cyclohexenyl group; Phenyl group, naphthyl group, alkylphenyl group (2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4-n-butylphenyl group, etc.), dialkylphenyl group (2, Aryl such as 4-dimethylphenyl group, 2,4,6-triisopropylphenyl group, etc.), alkyl naphthyl group (methyl naphthyl group, ethyl naphthyl group, etc.), dialkyl naphthyl group (dimethyl naphthyl group, diethyl naphthyl group, etc.) energy; heteroaryl groups such as thienyl groups; Aralkyl groups, such as a benzyl group, 1-phenylethyl group, and 2-phenylethyl group, etc. are mentioned.

In addition, some of the hydrogen atoms of these groups may be substituted with hetero atom-containing groups such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and some of the carbon atoms of these groups may be replaced by oxygen atoms, sulfur atoms, nitrogen atoms, etc. It may be substituted with a hetero atom-containing group, and as a result, even if it contains a hydroxyl group, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride, a haloalkyl group, etc. good night. As a hydrocarbyl group containing a hetero atom, 4-hydroxyphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 4-tert-butoxyphenyl group, 3- alkoxyphenyl groups such as tert-butoxyphenyl groups; Alkoxy naphthyl groups, such as a methoxy naphthyl group, an ethoxy naphthyl group, n-propoxy naphthyl group, and n-butoxy naphthyl group; Dialkoxy naphthyl groups, such as a dimethoxy naphthyl group and a diethoxy naphthyl group; Aryloxo, such as 2-aryl-2-oxoethyl group, such as 2-phenyl-2-oxoethyl group, 2-(1-naphthyl)-2-oxoethyl group, and 2-(2-naphthyl)-2-oxoethyl group An alkyl group etc. are mentioned.

R ¹⁰² is a hydrocarbyl group having 1 to 40 carbon atoms which may contain a hetero atom. Examples of the hydrocarbyl group represented by R ¹⁰² include those exemplified as the hydrocarbyl group represented by R ¹⁰¹ . In addition, as other specific examples, a trifluoromethyl group, a trifluoroethyl group, a 2,2,2-trifluoro-1-methyl-1-hydroxyethyl group, a 2,2,2-trifluoro-1-( fluorine-containing alkyl groups such as trifluoromethyl)-1-hydroxyethyl group; and fluorine-containing aryl groups such as a pentafluorophenyl group and a 4-trifluoromethylphenyl group.

Although what is shown below is mentioned as a sulfonic acid salt represented by Formula (Z1), It is not limited to these.

Although what is shown below is mentioned as a carboxylate represented by Formula (Z2), It is not limited to these.

When the resist composition of the present invention contains the quencher, its content is preferably 0.001 to 12 parts by mass, more preferably 0.01 to 8 parts by mass, based on 100 parts by mass of the base resin of component (A). The combination of the quencher makes it easy to adjust the resist sensitivity, suppresses the acid diffusion rate in the resist film, improves the resolution, suppresses the change in sensitivity after exposure, or reduces the dependency on the substrate or environment, An exposure margin or a pattern profile can be improved. In addition, substrate adhesion can be improved by adding these quenchers. These quenchers can be used alone or in combination of two or more.

[Surfactants]

The resist composition of the present invention may contain a surfactant component that is insoluble or sparingly soluble in water and soluble in an alkaline developer and/or insoluble or sparingly soluble in water and an alkaline developer. As such a surfactant, the component (S) defined in Unexamined-Japanese-Patent No. 2010-215608 or Unexamined-Japanese-Patent No. 2011-16746 can be referred.

As surfactants that are insoluble or poorly soluble in water and alkali developing solutions, among the surfactants described in the above publication, FC-4430 (manufactured by 3M), Saffron (registered trademark) S-381 (manufactured by AGC Semichemical Co., Ltd.), Sapphire Nol (registered trademark) E1004 (manufactured by Air Products), KH-20, KH-30 (manufactured by Asahi Glass Co., Ltd.) and oxetane ring-opening polymers represented by the following structural formula (surf-1) are suitable. These can be used individually by 1 type or in combination of 2 or more types.

However, Rf, R, M, A, B, C, and N in the formula above apply only to this formula.

In formula (surf-1), R is a 2 to 4 valent aliphatic group having 2 to 5 carbon atoms, specifically, it is divalent and is ethylene, tetramethylene, propylene, 2,2-dimethyl-1,3-propane A diyl group, a pentamethylene group, etc. are mentioned, What is shown below as a trivalent or tetravalent thing, etc. are mentioned.

(In the formula, the broken line indicates the number of bonds and is a partial structure derived from glycerol, trimethylolethane, trimethylolpropane and pentaerythritol, respectively.)

Among these, a tetramethylene group or a 2,2-dimethyl-1,3-propanediyl group is preferably used. Rf is a trifluoromethyl group or a pentafluoroethyl group, preferably a trifluoromethyl group. M is an integer of 0 to 3, N is an integer of 1 to 4, and the sum of M and N represents the valence of R and is an integer of 2 to 4. A is 1, B is an integer from 2 to 25, and C is an integer from 0 to 10. Preferably, B is an integer from 4 to 20, and C is 0 or 1. In addition, the arrangement|sequence of each structural unit of the said structure is not stipulated, and it may be combined blockwise or randomly. The preparation of a partially fluorinated oxetane ring-opening polymer-based surfactant is described in detail in the specification of US Patent No. 5650483 and the like.

[Pattern formation method]

The present invention also provides a pattern forming method using the resist composition described above. A known lithography technique can be employed to form a pattern using the resist composition of the present invention. Specifically, for example, substrates for manufacturing integrated circuits (Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflection films, etc.) or substrates for manufacturing mask circuits (Cr, CrO, CrON, MoSi ₂ , SiO _2, etc.) is coated with the resist composition of the present invention to a film thickness of 0.05 to 2 μm by a method such as spin coating, and this is applied on a hot plate at preferably 60 to 150° C. for 1 to 10 minutes, more preferably 80° C. A resist film is formed by prebaking at -140 DEG C for 1 to 5 minutes.

Next, a mask for forming a target pattern is covered on the resist film, and a KrF excimer laser, an ArF excimer laser, or a high-energy ray such as EUV or EB with a wavelength of 3 to 15 nm is applied at an exposure amount of preferably 1 to 15 nm. 200 mJ/cm 2 , more preferably 10 to 100 mJ/cm 2 , or preferably 0.1 to 100 μC/cm 2 , more preferably 0.5 to 50 μC/cm 2 . For exposure, in addition to the normal exposure method, an immersion method in which a liquid having a refractive index of 1.0 or more is interposed between a resist film and a projection lens may be used. The upper limit of the refractive index is not particularly limited, but can be set to 2.1. In that case, a water-insoluble protective film may be used. Subsequently, it is post-exposed baked (PEB) on a hot plate, preferably at 60 to 150°C for 1 to 5 minutes, more preferably at 80 to 140°C for 1 to 3 minutes. In addition, preferably 0.1 to 5% by mass, more preferably 2 to 3% by mass of an alkali aqueous solution developer such as tetramethylammonium hydroxide (TMAH) or an organic solvent developer such as butyl acetate, preferably is developed for 0.1 to 3 minutes, more preferably 0.5 to 2 minutes, by a conventional method such as a dip method, a puddle method, or a spray method to form a desired pattern on the substrate. do.

The water-insoluble protective film described above is used to block elution from the resist film and to increase the water slidability of the film surface, and there are two types broadly. One is an organic solvent stripping type that does not dissolve the resist film and requires stripping before alkali development with an organic solvent, and the other is an alkali soluble type that is soluble in an alkali developer and removes the protective film along with the removal of the resist film soluble portion. The latter is particularly insoluble in water and soluble in an alkali developer, and is based on a high molecular compound having a residue of 1,1,1,3,3,3-hexafluoro-2-propanol, an alcohol-based solvent having 4 or more carbon atoms, and 8 carbon atoms. Materials dissolved in the ether-based solvents of to 12 and mixed solvents thereof are preferred. It is also possible to use a material obtained by dissolving the aforementioned water-insoluble and alkaline developer-soluble surfactant in an alcohol-based solvent having 4 or more carbon atoms, an ether-based solvent having 8 to 12 carbon atoms, or a mixed solvent thereof.

Further, as a means of the pattern formation method, after forming the photoresist film, pure water rinsing (post-soak) may be performed to extract an acid generator or the like from the surface of the film or wash away particles, and water remaining on the film after exposure may be removed. You may perform a rinse (post-soak) to remove it.

As the developer for the pattern formation method of the present invention, as described above, preferably 0.1 to 5% by mass, more preferably 2 to 3% by mass of an aqueous alkali solution such as TMAH can be used, but an organic solvent can also be used. there is. In this case, negative tone development for developing/dissolving the unexposed portion can be performed.

In this organic solvent development, 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methyl Cyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, phenyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isoformate Pentyl, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, 2 -One selected from ethyl hydroxyisobutyrate, methyl benzoate, ethyl benzoate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, 3-phenylmethylpropionate, benzyl propionate, ethyl phenylacetate, 2-phenylethyl acetate, etc. more can be used.

Example

Examples and comparative examples are shown below to specifically explain the present invention, but the present invention is not limited to the following examples.

[1] Synthesis of photoacid generator (PAG)

[Example 1-1]

After mixing 100 g of ammonium salt 1, 68.7 g of cationic intermediate 1, 100 g of pure water, and 400 g of methylene chloride, the mixture was stirred and aged for 1 hour. After separating the organic layer, it was washed twice with a mixed solution of 5.7 g of the cationic intermediate 1 and 100 g of pure water, 5 times with 100 g of pure water, and twice with 100 g of 20 wt% methanol aqueous solution. The obtained organic layer was concentrated, and PGMEA was added and concentrated again to obtain a 20 wt% PGMEA solution. After stirring the obtained PGMEA solution at room temperature overnight to deposit solid, 500 g of hexane was further added and stirred for 2 hours. The obtained solid was separated by filtration, rinsed with 200 g of hexane, and finally heated and dried at 50°C under reduced pressure to obtain 104.8 g of target PAG1 (yield: 88%). The 1HNMR of the obtained PAG1 is shown in Fig. 1, and the 19FNMR is shown in Fig. 2.

IR (D-ATR): ν = 3087, 3002, 2906, 2852, 1785, 1727, 1477, 1448, 1344, 1240, 1180, 1103, 1076, 1035, 1010, 997, 943, 750, 684, 65142, 55142 , 522, 501 cm ^-1

[Example 1-2]

After mixing 417 g of ammonium salt 2, 268 g of cationic intermediate 2, 1400 g of pure water, and 2000 g of methylene chloride, the mixture was stirred and aged for 1 hour. After the organic layer was separated and taken, the organic layer was washed 6 times with 600 g of pure water and 6 times with 600 g of 20 wt% methanol aqueous solution. 25 g of activated carbon was added to the obtained organic layer, and the mixture was stirred overnight at room temperature. After removing activated carbon by filtration, the organic layer was washed once with 600 g of 1% hydrochloric acid, twice with 600 g of pure water, once with 600 g of 1% hydrochloric acid, and three times with 600 g of pure water. Further, it was washed once with 600 g of 0.04 eq. aqueous ammonia, three times with 600 g of pure water, once with 600 g of 0.5% hydrochloric acid, and three times with 600 g of pure water. The organic layer was concentrated, and PGMEA was added and concentrated again to obtain a 50 wt% PGMEA solution. The concentrate was added dropwise into 3.5 L of diisopropyl ether to precipitate crystals. After stirring for 1 hour, this was separated by filtration, rinsed with diisopropyl ether, and finally heated and dried at 50°C under reduced pressure to obtain 535 g of target PAG2 (yield: 86%). The 1HNMR of the obtained PAG2 is shown in Fig. 3, and the 19FNMR is shown in Fig. 4.

IR (D-ATR): ν = 3089, 2907, 2853, 1785, 1729, 1476, 1449, 1344, 1237, 1180, 1104, 1076, 1035, 1010, 947, 761, 707, 681, 642, 585, 55 , 525 cm ^-1

[Examples 1-3 to 1-9] Synthesis of other PAGs (PAG-3 to PAG-9)

PAG-3 to PAG-9 were synthesized by a known organic synthesis method using corresponding raw materials.

[2] Synthesis of polymers

The polymer used in the resist composition of the present invention was synthesized by the method shown below. In addition, Mw of the obtained polymer was measured as a polystyrene conversion value by GPC using THF or DMF as a solvent.

[Synthesis Example 1] Synthesis of Resist Polymer 1

Under a nitrogen atmosphere, p-hydroxystyrene (27.8 g), 1-methylcyclopentyl methacrylate (72.2 g) and dimethyl 2,2'-azobisisobutyrate (6.08 g) were dissolved in PGMEA (155 g). solution was prepared. The solution was added dropwise over 6 hours to PGMEA (78 g) stirred at 80°C under a nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was added dropwise to n-hexane (3000 g) after stirring at 80°C for 2 hours and cooling to room temperature. The precipitated solid material was separated by filtration and vacuum dried at 50°C for 20 hours to obtain resist polymer 1 as a solid white powder. The yield was 85 g and the yield was 85%.

[Synthesis Examples 2 to 7] Synthesis of resist polymers 2 to 7

Resist polymers 2 to 7 shown below were prepared in the same manner as in Synthesis Example 1 except that the type of monomer and the compounding ratio were changed.

[3] Preparation of resist composition

[Examples 2-1 to 2-40, Comparative Examples 1-1 to 1-38]

Onium salts of the present invention (PAG-1 to PAG-9), comparative photoacid generators PAG-A to PAG-H, resist polymers 1 to 7, other photoacid generators PAG-X to PAG-Z, quencher Q-1 -Q-4 and alkali-soluble surfactant SF-1, with the composition shown in Tables 1 and 2 below, were dissolved in a solvent containing 0.01% by mass of surfactant A (manufactured by Omnova Co., Ltd.) to prepare a solution, A resist composition was prepared by filtering the solution with a 0.2 μm Teflon (registered trademark) filter.

In addition, in Tables 1 and 2, solvents, comparative photoacid generators PAG-A to PAG-H, other photoacid generators PAG-X to PAG-Z, quenchers Q-1 to Q-4, and alkali-soluble surfactants (Fluorinated Polymer) SF-1 is as follows.

·PAG-A to PAG-H:

・PAG-X to PAG-Z:

SF-1:

· Q-1 to Q-4:

·solvent:

S-1: PGMEA (propylene glycol monomethyl ether acetate)

S-2: GBL (γ-butyrolactone)

· Surfactant A:

3-methyl-3-(2,2,2-trifluoroethoxymethyl)oxetane/tetrahydrofuran/2,2-dimethyl-1,3-propanediol copolymer (manufactured by Omnova Co., Ltd.)

[4] Evaluation of resist composition: EUV exposure patterning evaluation (hole pattern evaluation)

[Examples 3-1 to 3-40, Comparative Examples 2-1 to 2-38]

The resist compositions (R-1 to R-40) of the present invention and the resist compositions for comparison (R-41 to R-78) were mixed with a 20 nm film manufactured by BRUWER SCIENCE using Clean Track Lithius ProZ manufactured by Tokyo Electron. A thick organic antireflection film AL-412 was coated on the substrate, and baked on a hot plate at 105 DEG C for 60 seconds to form a 50 nm resist film. Using an EUV exposure machine NXE3300 manufactured by ASML, a lattice pattern having dimensions of 27.5 nm at a pitch of 46 nm on a mask is exposed, and after exposure, an appropriate PEB temperature is applied for each resist composition, and then a 2.38% tetramethylammonium aqueous solution is applied to the wafer. It was discharged while rotating and developed for a total of 30 seconds, the alkali solution was washed away with water, and the water was removed by rotating the wafer at a high speed.

[Sensitivity evaluation]

The created resist pattern was observed with a CD-SEM CG-5000 manufactured by Hitachi High-Technologies, and the exposure amount at which the hole diameter was 23 nm at a pitch of 46 nm was determined as the optimal exposure amount Eop (mJ/cm 2 ).

[MEF evaluation]

When the dimension on the mask is a pitch of 46 nm and the grating pattern is 27.5 nm, when a hole diameter of around 23 nm is observed when observed by CD-SEM, the dimension on the mask is a pitch of 46 nm and the grating pattern is 26.0 nm, 26.5 nm, The CD of the hole pattern at 27.0 nm, 27.5 nm, 28.0 nm, 28.5 nm, and 29.0 nm is measured. The dimensions on the mask and the inclination of the observed CD were taken as MEF (Mask Error Enhancement Factor). An MEF of about 3.0 or less is regarded as good.

[Dimension uniformity (CDU) evaluation]

The obtained hole pattern was observed with a CD-SEM CG-5000 manufactured by Hitachi High Technologies, 32 hole diameters were measured at one hole per sample, and 49 holes were measured from one SEM image. A triplicate (3σ) of the calculated standard deviation (σ) was obtained, 30 SEM images were acquired, and the average value of the standard deviations was taken as CDU. CDU means that the smaller the value, the better the dimensional uniformity. A CDU of approximately 3.2 or less is regarded as good.

From the results shown in Table 3, it was found that the resist compositions (Examples) of the present invention had good sensitivity and were excellent in MEF and CDU. On the other hand, as shown in Table 4, conventional photoacid generators PAG-A to PAG-E (see Patent Documents 1 to 4), PAG-F in which W1 does not contain a hetero atom, PAG-H, and W2 are hetero atoms. The resist composition (comparative example) using PAG-G and PAG-H containing atoms had insufficient MEF and CDU. From the above, it has been revealed that the resist composition of the present invention is particularly suitable as a material for EUV lithography.

In addition, this invention is not limited to the said embodiment. The above embodiment is an example, and anything having substantially the same configuration and exhibiting the same effect as the technical concept described in the claims of the present invention is included in the technical scope of the present invention.

Claims (18)

(A) a resin containing a repeating unit having an acid labile group and at least one repeating unit having an aromatic substituent, (B) a photoacid generator represented by the general formula (B-1), (C) a solvent, and (D) a resin different from the resin of component (A) and containing fluorine having at least one type selected from repeating units represented by the following formulas (D-1), (D-2) and (D-3). A resist composition comprising a resin.

(In the formula, W ₁ represents a cyclic divalent hydrocarbon group containing a hetero atom of 4 to 12 carbon atoms. W ₂ represents a cyclic monovalent hydrocarbon group having 4 to 14 carbon atoms and not containing a hetero atom. Rf is It is a divalent organic group represented by the general formula, A ₁ and A ₂ each independently represent a hydrogen atom or a trifluoromethyl group, B ₁ and B ₂ each independently represent a hydrogen atom or a fluorine atom, and * represents a carbon atom. represents the number of bonds with the carbonyloxy group, m represents 0 to 4, and n represents 1. M ⁺ represents at least one onium selected from cations represented by the following formulas (b1) and (b2) It is a cation, and in the following formulas (b1) and (b2), R ⁴¹ to R ⁴⁵ are each independently a straight-chain, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. , R ⁴¹ , R ⁴² and R ⁴³ may be bonded to each other to form a ring together with the sulfur atom in the formula.

However, the cation represented by the above formula (b1) excludes the sulfonium cation represented by the following formula.

R ¹ to ^{R 3} in the above formula are each independently a straight-chain, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, or R ¹ and R ² , R ¹ and R ³ , or R ² and R ³ may be bonded to each other to form a ring together with the benzene ring to which they are bonded and the nitrogen atom therebetween. When p, q and/or r is 2 or more, a plurality of R ¹ to ^{R 3} may be the same as or different from each other, and a plurality of R ¹ to ^{R 3} are mutually bonded to each other to form a carbon atom on the benzene ring to which they are bonded. You may form a ring together. R ⁴ and R ⁵ are each independently a straight-chain, branched or cyclic monovalent hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom. R ⁴ and R ⁵ may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. p and q are each independently an integer of 0 to 5; r is an integer from 0 to 4.)

(In the formula, R ^A is each independently a hydrogen atom or a methyl group. R ₅₁ and R ₅₂ are each independently a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. R ₅₃ is a single bond or straight chain or branched divalent hydrocarbon group having 1 to 5 carbon atoms R ₅₄ , R ₅₅ and R ₅₆ are each independently a hydrogen atom or a straight chain, branched or cyclic carbon number 1 to 15 of, a monovalent hydrocarbon group, a fluorinated monovalent hydrocarbon group or an acyl group, or an acid labile group, when R ₅₄ , R ₅₅ and R ₅₆ are a monovalent hydrocarbon group or a fluorinated monovalent hydrocarbon group, some of these carbon atoms are ether groups Alternatively, it may be substituted with a carbonyl group. R ₅₇ is a straight-chain, branched or cyclic hydrocarbon group having a (v+1) valence of 1 to 20 carbon atoms or a fluorinated hydrocarbon group. v is an integer of 1 to 3.) The resist composition according to claim 1, wherein W ₁ in the general formula (B-1) is a cyclic divalent hydrocarbon group containing a lactone ring structure having 6 to 12 carbon atoms. The resist composition according to claim 1, wherein W ₂ in the general formula (B-1) is a polycyclic monovalent hydrocarbon group having 7 to 14 carbon atoms and not containing a hetero atom. The resist composition according to claim 2, wherein W ₂ in the general formula (B-1) is a polycyclic monovalent hydrocarbon group having 7 to 14 carbon atoms and not containing a hetero atom. The resist composition according to claim 1, wherein the Rf group in the general formula (B-1) is selected from groups represented by the following formulas (Rf-1) and (Rf-3) to (Rf-6).

(* represents the number of bonds with the carbonyloxy group.) The resist composition according to claim 2, wherein the Rf group in the general formula (B-1) is selected from groups represented by the following formulas (Rf-1) and (Rf-3) to (Rf-6).

(* represents the number of bonds with the carbonyloxy group.) The resist composition according to claim 3, wherein the Rf group in the general formula (B-1) is selected from groups represented by the following formulas (Rf-1) and (Rf-3) to (Rf-6).

(* represents the number of bonds with the carbonyloxy group.) The resist composition according to claim 4, wherein the Rf group in the general formula (B-1) is selected from groups represented by the following formulas (Rf-1) and (Rf-3) to (Rf-6).

(* represents the number of bonds with the carbonyloxy group.) The resist composition according to claim 1, wherein one of the repeating units having an aromatic substituent in the resin of component (A) is a repeating unit represented by the following formula (A-1).

(Wherein, R ^A represents a hydrogen atom or a methyl group. R ₆₁ represents a hydrogen atom or a straight-chain, branched or cyclic hydrocarbon group which may be interposed with a hetero atom having 1 to 10 carbon atoms. R ₆₂ represents a hetero atom intervening. Represents an optional straight-chain, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms, t is an integer from 1 to 3, u is an integer satisfying u≤5+2s-t, s is 0 or 1 .L ₁ represents either a single bond or -C(=O)O-, -C(=O)NH-.) The resist composition according to claim 1, wherein one of the repeating units having an aromatic substituent in the resin of component (A) is a repeating unit represented by the following general formulas (A-2) to (A-4): .

(In the formula, R ^A is each independently a hydrogen atom or a methyl group, R ²⁰¹ is a single bond, a phenylene group, -OR ²¹⁰ - or -C(=O)-Z ² -R ²¹⁰ -. Z ² is an oxygen atom or NH, R ²¹⁰ is a straight-chain, branched or cyclic alkylene group having 1 to 6 carbon atoms, an alkenylene group or a phenylene group, and a carbonyl group (-CO-), an ester group (-COO-), an ether group (- L ₂ represents a single bond or -Z ³ -C(=O)-O-, and Z ³ is a straight-chain or branched chain which may be substituted with a heteroatom having 1 to 20 carbon atoms. represents a monovalent or cyclic divalent hydrocarbon group, Z ¹ is a single bond, methylene group, ethylene group, phenylene group, fluorinated phenylene group, -OR ²¹¹ - or -C(=O)-Z ⁴ -R ²¹¹ -. Z ⁴ is an oxygen atom or NH, R ²¹¹ is a straight-chain, branched or cyclic alkylene group, alkenylene group or phenylene group having 1 to 6 carbon atoms, which may contain a carbonyl group, ester group, ether group or hydroxyl group. ^{and M - represents a non - nucleophilic} counter ion ^. Represents a preferably straight-chain or branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ²⁰² and R ²⁰³ may combine with each other to form a ring with the sulfur atom in the formula; Alternatively, any two or more of R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ or any two or more of R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ may be bonded to each other to form a ring together with the sulfur atom in the formula. The repeating units represented by -2) to (A-4) have one or more aromatic substituents.) delete A step of applying the resist composition according to any one of claims 1 to 10 on a substrate and subjecting it to heat treatment to form a resist film, a step of exposing the resist film to high energy rays, and exposure using a developer A pattern formation method comprising the step of developing a resist film. The pattern forming method according to claim 12, wherein the high energy ray is an ArF excimer laser with a wavelength of 193 nm or a KrF excimer laser with a wavelength of 248 nm. 13. The pattern formation method according to claim 12, wherein the exposure is immersion exposure in which a liquid having a refractive index of 1.0 or more is interposed between a resist film and a projection lens. 14. The pattern formation method according to claim 13, wherein the exposure is immersion exposure in which a liquid having a refractive index of 1.0 or more is interposed between a resist film and a projection lens. 15. The pattern formation method according to claim 14, wherein a protective film is further formed on the resist film, and immersion lithography is performed with the liquid interposed between the protective film and a projection lens. 16. The pattern forming method according to claim 15, wherein a protective film is further formed on the resist film, and immersion lithography is performed with the liquid interposed between the protective film and a projection lens. The pattern formation method according to claim 12, wherein the high energy ray is an electron beam or an extreme ultraviolet ray having a wavelength of 3 to 15 nm.

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