JP2005091807A - Resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist composition which has high sensitivity to high-energy rays such as far ultraviolet rays, an electron beams, and X rays and can form a pattern with a superior contrast through development using an alkali solution. <P>SOLUTION: The resist composition contains (A) a polymer which reacts with acid to become alkali-soluble, (B) a polymer having a repeating unit represented by formula (I) (where R1 and R2 are each independently a hydrogen atom, a halogen atom, a C1 to C20 hydrocarbon group, etc., R3 is a C1 to C20 hydrocarbon group or a heterocyclic group, R4 is a C1 to C20 hydrocarbon oxy group, a C1 to C20 hydrocarbon group, a C1 to C20 hydrocarbon thio group or a C1 to C20 mono- or dihydrocarbon amino group, M is a silicon atom, a germanium atom, a tin atom, or a lead atom, and (n) is 0, 1, or 2), and (C) an acid producing agent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a resist composition suitable for microfabrication technology, which has high sensitivity to high energy rays such as deep ultraviolet rays, electron beams, and X-rays, and can be patterned by developing with an alkaline aqueous solution.

It is known that it is effective to add a solubility inhibitor to control the dissolution characteristics of the resist and improve the patterning characteristics. The dissolution inhibitor is required to have (1) high transparency to exposure light, (2) etching resistance, and (3) the property that the solubility in an alkaline developer is remarkably changed by the action of an acid. Examples of the polymer compound include a copolymer of p-butoxystyrene and tert-butyl acrylate, a copolymer of p-butoxystyrene and maleic anhydride, and the like. (See Patent Document 1)
JP 7-49569 A

  However, there is a problem that there is a limit to improving the contrast performance even when a conventionally known polymer dissolution inhibitor is used.

  An object of the present invention is to provide a resist composition that has high sensitivity to high energy rays such as deep ultraviolet rays, electron beams, and X-rays, and can form a pattern with excellent contrast by developing with an alkaline aqueous solution. And

  As a result of intensive studies to solve the above problems, the present inventors can solve the above problems by using a polymer having a special structure in which the main chain is easily cleaved by an acid as a dissolution inhibitor. The invention has been completed.

That is, the present invention
(1) (A) a polymer that becomes alkali-soluble by reaction with an acid, (B) formula (I)

(Wherein R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a C1-C20 hydrocarbon group, a heterocyclic group, a cyano group, a nitro group, a C (═O) R ₄ group, S (O ) _N R ₄ group, P (═O) (R ₄ ) ₂ group, M (R ₄ ) ₃ group, R ₃ represents a C1-C20 hydrocarbon group or heterocyclic group, and R ₄ represents C1 -C20 hydrocarbon oxy group, C1-C20 hydrocarbon group, C1-C20 hydrocarbon thio group, mono- or di-C1-C20 hydrocarbon amino group, M is silicon atom, germanium atom, tin atom A polymer containing a repeating unit represented by the formula: and a lead atom, wherein n represents 0, 1, or 2; and (C) an acid generator. Regarding
(2) In the compound represented by formula (I), R ₁ and R ₂ each independently represent a C1-C20 hydrocarbon group, and R ₃ represents a C1-C20 hydrocarbon group or heterocyclic group. The resist composition as described in (1),
(3) In the compound represented by the formula (I), R ₃ represents the formula (II)

(In the formula, R ₅ represents a hydrogen atom or a group that decomposes or leaves with an acid, R ₆ represents a fluorine atom or a C1-C6 hydrocarbon group that may be substituted with a fluorine atom, and m represents 1 represents an integer of 1 to 3, p represents an integer of 0 or 1 to 3, represents m + p ≦ 5, and when m is 2 or more, R ₅ may be the same or different. , P is 2 or more, R ₆ may be the same or different.) The resist composition according to (1) or (2),
(4) The number average molecular weight of the polymer having a repeating unit represented by formula (I) is 2,000 to 50,000, according to any one of (1) to (3) Resist composition,
(5) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer having a repeating unit represented by the formula (I) is in the range of 1.01 to 3.00. The resist composition according to any one of (1) to (4),
(6) (A) A polymer that becomes alkali-soluble by reaction with an acid is represented by the formula (III)

(Wherein R ₇ represents a hydrogen atom or a C1-C6 alkyl group optionally substituted with a fluorine atom, R ₈ represents an organic group which is decomposed or eliminated by an acid, and R ₉ represents A fluorine atom, or a C1-C6 hydrocarbon group optionally substituted with a fluorine atom, r represents an integer of 1 to 3, s represents an integer of 0 or 1 to 3, r + s ≦ 5, and when r is 2 or more, R ₈ may be the same or different, and when s is 2 or more, R ₉ may be the same or different. It is a polymer which has a repeating unit, It is related with the resist composition in any one of Claims 1-5 characterized by the above-mentioned.

  By using the composition of the present invention, it has high sensitivity to high energy rays such as deep ultraviolet rays, electron beams, and X-rays, and it can form a pattern with excellent contrast by developing with an alkaline aqueous solution. Can be said to have high utility value.

The composition of the present invention contains (A) a polymer that becomes alkali-soluble upon reaction with an acid, (B) a polymer having a repeating unit represented by formula (I), and (C) an acid generator. It is characterized by that.
(I) Polymer that becomes alkali-soluble by reaction with acid As a polymer that has the property of becoming alkali-soluble by reaction with acid, novolac resin, phenol resin, acrylic resin, and copolymers thereof are used. In order to control the solubility, the phenolic hydroxyl group or the carboxylic acid or the like is preferably used by protecting all or a part thereof with an organic group that is decomposed or eliminated by an acid. As a particularly preferred polymer, a polymer having a repeating unit represented by the formula (III) can be exemplified.

In formula (III), R ₇ represents a hydrogen atom or a C1-C6 alkyl group optionally substituted with a fluorine atom, R ₈ represents an organic group that decomposes or leaves with an acid, and R ₉ Represents a fluorine atom or a C1-C6 hydrocarbon group which may be substituted with a fluorine atom, r represents an integer of 1 to 3, and s represents an integer of 0 or 1 to 3. R + s ≦ 5 and when r is 2 or more, R ₈ may be the same or different, and when s is 2 or more, R ₉ may be the same or different.

Specific examples of the C1-C6 hydrocarbon group which may be substituted with a fluorine atom represented by R ₇ and R ₉ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an s-butyl group. Group, isobutyl group, t-butyl group, n-pentyl group, trifluoromethyl group, difluoromethyl group, 2-fluoroethyl group and the like can be exemplified.

Specific examples of R ₈ include methoxymethyl group, 2-methoxyethoxymethyl group, tetrahydropyranyl group, 4-methoxytetrahydropyranyl group, tetrahydrofuranyl group, triphenylmethyl group, trimethylsilyl group, 2- (trimethylsilyl) Examples thereof include an ethoxymethyl group, a t-butyldimethylsilyl group, a trimethylsilylmethyl group, and a substituent as shown in the following formula.

(Wherein k represents 0 or 1). Furthermore, the following formula

Wherein R ₁₄ represents a C1-C20 unsubstituted or alkoxy-substituted alkyl group, a C5-C10 cycloalkyl group, or a C6-C20 unsubstituted or alkoxy-substituted aryl group, and R ₁₅ represents hydrogen or A C1-C3 alkyl group, and R ₁₆ represents a hydrogen, a C1-C6 alkyl group, or a C1-C6 alkoxy group). Specific examples include 1-methoxyethyl group, 1-ethoxyethyl group, 1-methoxypropyl group, 1-methyl-1-methoxyethyl group, 1- (isopropoxy) ethyl group and the like. The substitution position of the hydroxyl group or alkoxy group (OR ₈ group) is not particularly limited, but the meta position or para position is preferred.

  Specific examples of the polymer that becomes alkali-soluble by an acid include homopolymers and copolymers using the following monomers.

  4-hydroxystyrene, 3-hydroxystyrene, 4-hydroxy-α-methylstyrene, 4-t-butoxystyrene, 3-t-butoxystyrene, 4-t-butoxy-α-methylstyrene, 4- (1′- Ethoxy-ethoxy) styrene, 3- (1′-ethoxy-ethoxy) styrene, 4- (1′-ethoxy-ethoxy) -α-methylstyrene, 4- (1′-ethoxy-propoxy) styrene, 3- (1 '-Ethoxy-propoxy) styrene, 4- (1'-ethoxy-propoxy) -α-methylstyrene, 4- (1'-cyclohexyl-ethoxy) styrene, 3- (1'-cyclohexyl-ethoxy) styrene, 4- (1′-cyclohexyl-ethoxy) -α-methylstyrene, 4- (1′-butoxy-ethoxy) styrene, 3- (1′-buto X-ethoxy) styrene, 4- (1′-butoxy-ethoxy) -α-methylstyrene, 4-t-butoxycarbonyloxystyrene, 3-t-butoxycarbonyloxystyrene, 4-t-butoxycarbonyloxy-α- Methyl styrene, 4-tetrahydropyranyl styrene, 3-tetrahydropyranyl styrene, 4-tetrahydropyranyl-α-methyl styrene, 4-tetrahydrofuranyl styrene, 3-tetrahydrofuranyl styrene, 4-tetrahydrofuranyl-α-methyl styrene, Acrylic acid, methacrylic acid, itaconic acid, acrylic acid-t-butyl, methacrylic acid-t-butyl, itaconic acid di-t-butyl, acrylic acid-t-amyl, methacrylic acid-t-amyl, itaconic acid di-t -Amyl, acrylic acid-1-alkylcyclope Til, methacrylic acid-1-alkylcyclopentyl, di-1-alkylcyclopentyl itaconate, acrylic acid-1-alkylcyclohexyl, methacrylic acid-1-alkylcyclohexyl, itaconic acid di-1-alkylcyclohexyl, acrylic acid-1-alkyl Cyclopentenyl, methacrylate-1-alkylcyclopentenyl, di-1-alkylcyclopentenyl itaconate, -1-alkylcyclohexenyl acrylate, -1-alkylcyclohexenyl methacrylate, di-1-alkylcyclohexenyl itaconate, Alkyl adamantyl acrylate, alkyl adamantyl methacrylate, norbornenecarboxylic acid-t-butyl, norbornenecarboxylic acid-t-amyl, norbornenecarboxylic acid-1-alkylcyclopentyl, Rubornenecarboxylic acid-1-alkylcyclohexyl, norbornenecarboxylic acid-t-amyl, norbornenecarboxylic acid-1-alkylcyclopentyl, norbornenecarboxylic acid-1-alkylcyclohexyl, norbornenecarboxylic acid-1-alkylcyclopentenyl, norbornenecarboxylic acid -1-alkylcyclohexenyl and the like.

  In polymers produced from the above monomers, phenols protected by acid-decomposable or detachable protecting groups or carboxylic acids protected by acid-decomposable or detachable protecting groups and unprotected phenols Or it is preferable that carboxylic acids are included. In a copolymer produced from a monomer protected with an acid-decomposable or detachable protecting group and an unprotected monomer, the degree of substitution of the protecting group is preferably 5 to 50 mol% of the OH group, preferably Is preferably 10 to 30 mol%. When the amount is 5 mol% or more, the resist film is less rubbed, and when the amount is 50 mol% or less, the resolving power hardly decreases. Moreover, it is preferable that the weight average molecular weight shall be 5,000-100,000.

Further, if necessary, a monomer that does not participate in a change in dissolution rate due to an acid or a monomer that does not participate in a reaction with an acid in order to provide other properties, that is, adhesion to the substrate, etching resistance, etc. Can be used together. Specific examples of such monomers include alkoxystyrenes such as styrene, methoxystyrene, ethoxystyrene, propoxystyrene, and isopropoxystyrene, methylcarboxystyrene, ethylcarboxystyrene, propoxycarboxystyrene, and isopropoxycarboxystyrene. Examples thereof include hydroxycarboxystyrenes such as 2-hydroxyethoxystyrene and 2-hydroxypropoxystyrene, and norbornene derivatives such as maleic anhydride, norbornene, hydroxynorbornene and dihydroxynorbornene. The monomers can be used alone or in admixture of two or more.
(II) A polymer having a repeating unit represented by the formula (I).

In the repeating unit represented by the formula (I) used in the present invention, R ₁ and R ₂ are each independently a hydrogen atom, a fluorine atom, a C1-C20 hydrocarbon group, a heterocyclic group, a cyano group, or a nitro group. , C (═O) R ₄ group, S (O) _n R ₄ group, P (═O) (R ₄ ) ₂ group, M (R ₄ ) ₃ group, and R ₄ is a C1-C20 hydrocarbon. Represents an oxy group, a C1-C20 hydrocarbon group, a C1-C20 hydrocarbon thio group, a mono- or di-C1-C20 hydrocarbon-substituted amino group, and M represents a silicon atom, a germanium atom, a tin atom, or a lead atom. N represents 0, 1, or 2. Specific examples of R ₁ and R ₂ include hydrogen atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, s-butyl group, isobutyl group, n -Pentyl group, s-pentyl group, isopentyl group, neopentyl group, n-hexyl group, s-hexyl group, 1,1-dimethyl-n-hexyl group, n-heptyl group, n-decyl group, n-dodecyl group C1-C20 alkyl group, vinyl group, allyl group, 2-butenyl group, 1-methyl-2-propenyl group, 4-octenyl group, etc. C2-C20 alkynyl group, ethynyl group, propargyl group, 1-methyl -C2-C20 alkynyl group such as propynyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, 1-methylcyclopentyl group, 1-methylcyclohexyl group, -C3-C20 alicyclic hydrocarbon group such as adamantyl group, 1-methyladamantyl group, 2-adamantyl group, 2-methyl-2-adamantyl group, norbornyl group, phenyl group, 1-naphthyl group, 9-anthracenyl C6-C20 aromatic hydrocarbon group such as a group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-furanyl group, 2-thienyl group, 3-thienyl group, 1-pyrrolo group, 2- Oxazolyl group, 3-isoxazolyl group, 2-thiazolyl group, 3-isothiazolyl group, 1-pyrazolyl group, 4-pyrazolyl group, 2-imidazolyl group, 1,3,4-oxadiazol-2-yl, 1,2 , 4-oxadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-triazol-2-yl Yl, 1,2,3-thiadiazol-5-yl, 1,2,3-triazol-4-yl, 1,2,3,4-tetrazol-5-yl, pyrimidin-2-yl, pyrimidine-4- Yl, pyrazin-2-yl, pyridazin-3-yl, 1,2,4-triazin-6-yl, 1,3,5-triazin-2-yl, 1-pyrrolidinyl group, 1-piperidyl group, 4- Heterocyclic groups such as morpholinyl group, 2-tetrahydrofuranyl group, 4-tetrahydropyranyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl C1-C20 alkoxycarbonyl group such as a group, C1-C20 alkylthiocarbonyl group such as methylthiocarbonyl group, N, N- Substituted or unsubstituted carbamoyl groups such as methylcarbamoyl group, methylsulfenyl group, phenylsulfenyl group, methylsulfinyl group, phenylsulfenyl group, methylsulfonyl group, phenylsulfonyl group, methylsulfuryl group, N, N-dimethylsulfa Substituted or unsubstituted sulfamoyl group such as moyl group, phosphonyl group such as dimethylphosphonyl group, bismethylthiophosphonyl group, tetramethylaminophosphonyl group, trimethylsilyl group, t-butyldimethylsilyl group, phenyldimethylsilyl group, trimethylstane Examples thereof include a nyl group and a triphenylplanvanyl group.

R ₃ represents a C1 to C20 hydrocarbon group or heterocyclic group, and specific examples thereof include the same substituents as exemplified for R ₁ and R ₂ .

Each of the substituents R _{1 to} R ₃ shown above can further have a substituent at an appropriate carbon position. As the substituent, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, Perfluoroethyl group, cyclopropyl group, cyclohexyl group, vinyl group, allyl group, phenyl group, 4-chlorophenyl group, 4-methoxyphenyl group, substituted phenyl group such as 3,4-dimethylphenyl group, propargyl group, 2-hydroxy Carbonization of -1,1,1,3,3,3-hexafluoro-2-propyl group, 2- (ethoxymethoxy) -1,1,1,3,3,3-hexafluoro-2-propyl group, etc. Hydrogen group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, isobutoxy group, t-butyl group Xyl group, fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, phenoxy group, 4-chlorophenoxy group, benzyloxy group, phenethyloxy group, t-butoxycarbonyloxy group, tetrahydropyranyloxy group, phenoxyethoxy group, ethoxy Alkoxy groups such as ethoxy group, trimethylsilyloxy group, t-butoxycarbonylmethoxy group, amino group, methylamino group, dimethylamino group, amino group such as t-butoxycarbonylamino group, methylthio group, phenylthio group, 2-pyridylthio group Alkyl, aryl, or heterocyclic thio group such as methylsulfinyl group and methylsulfonyl group or its oxidant, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group Group, C1-C20 alkoxycarbonyl group such as n-butoxycarbonyl group, t-butoxycarbonyl group, C2-C20 acyl group such as acetyl group, propanoyl group, benzoyl group, 2-pyridylcarbonyl group, cyano group, nitro group Examples include groups.

Specific examples of R _{1 to} R ₃ having these substituents include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, 3, 3, 3 -Haloalkyl groups such as trifluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group, haloalkenyl groups such as tetrafluoroethenyl group, 2,2-difluoroethenyl group, methoxymethyl group, methoxy Alkylalkyl group such as ethyl group, phenoxymethyl, alkylthioalkyl group such as methylthiomethyl group, phenylthiomethyl group or arylthioalkyl group, benzyl group, diphenylmethyl group, trityl group, phenethyl group, aralkyl group, benzoylmethyl group , Acylalkyl groups such as acetylmethyl group, cyanomethyl groups, etc. It can be exemplified.

Further, as R ₃ , a substituent represented by the formula (II) can be preferably exemplified. In the substituent represented by the formula (II), R ₅ represents a hydrogen atom, a group that decomposes or leaves with an acid, m represents an integer of 1 to 3, and when m is 2 or more, R ₅ may be the same or different. Here, specific examples of the group that can be decomposed or eliminated by an acid include the same substituents as those exemplified for R ₈ .

R ₆ represents a fluorine atom or a C1-C20 hydrocarbon group. Specifically, among the substituents exemplified for R ₁ and R ₂ , the same substituents as the corresponding examples may be exemplified. The substitution position is not particularly limited. p represents an integer of 0 or 1 to 3, and has a relationship of m + p ≦ 5. When p is 2 or more, R ₆ may be the same or different.

  Specific examples of the substituent represented by the formula (II) include 4-hydroxyphenyl group, 4-hydroxy-3-methylphenyl group, 4-t-butoxyphenyl group, 4-tetrahydropyranyloxyphenyl group, 4 -Phenoxyethoxyphenyl group, 4-trimethylsilyloxyphenyl group, 4-t-butoxycarbonyloxyphenyl group, 4-t-butoxycarbonylmethoxyphenyl group, 2,3-difluoro-4-hydroxyphenyl group, 2,3-difluoro -4-t-butoxyphenyl group, 2,6-difluoro-4-hydroxyphenyl group, 2,6-difluoro-4-t-butoxyphenyl group, 3,5-difluoro-4-hydroxyphenyl group, 3,5 -Difluoro-4-t-butoxyphenyl group, 2,3,5,6-tetrafluoro-4-hydroxy Phenyl group, 2,3,5,6-tetrafluoro-4-t-butoxyphenyl group, 2-trifluoromethyl-4-hydroxyphenyl group, 2-trifluoromethyl-4-t-butoxyphenyl group, 2- Trifluoromethyl-6-fluoro-4-hydroxyphenyl group, 2-trifluoromethyl-6-fluoro-4-t-butoxyphenyl group, 3-trifluoromethyl-5-fluoro-4-hydroxyphenyl group, 3- Trifluoromethyl-5-fluoro-4-t-butoxyphenyl group, 4- (1-ethoxyethoxy) phenyl group, 4- (2-hydroxy-1,1,1,3,3,3-hexafluoro-2 -Propyl) phenyl group, 4- (2-ethoxymethoxy-1,1,1,3,3,3-hexafluoro-2-propyl) phenyl group and the like. Can.

Further, the substituent represented by the formula (II) exemplified as a preferred embodiment of R ₃ can be preferably exemplified as the substituent of R ₁ and R ₂ .

In addition, the substituents represented by R _{1 to} R ₃ do not have to be the same in all the repeating units represented by the formula (I), and two or more kinds can be appropriately mixed and used. For example, as a substituent for R ₃ , a p-methoxyphenyl group and a p- (1-ethoxyethoxy) phenyl group can be mixed at a molar ratio of 1/99 to 99/1.

  The polymer having a repeating unit represented by the formula (I) in the present invention includes a polymer consisting only of the repeating unit represented by the formula (I), and the repeating unit represented by the formula (I) and the formula (I The polymer which consists of repeating units other than the repeating unit represented by I) is meant.

  Specific examples of the repeating unit other than the repeating unit represented by the formula (I) include a repeating unit represented by the formula (IV).

In the formula (IV), R ₃₁ , R ₃₂ and R ₃₃ each independently represents a hydrogen atom, a fluorine atom, a C1-20 linear, branched or cyclic alkyl group or a fluorinated alkyl group. , R ₃₄ represents a hydroxyl group or a C 6-20 aromatic hydrocarbon group which may be substituted with an alkoxy group, or a CO ₂ R ₃₅ group, and R ₃₅ represents a C 1 to C 20 hydrocarbon group, preferably Represents an acid labile group.

  In this case, as the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, A cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, an n-octyl group and the like can be exemplified, and those having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms are preferable. The fluorinated alkyl group is one in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and includes a trifluoromethyl group, a 2,2,2-trifluoroethyl group, 3, Examples include 3,3-trifluoropropyl group and 1,1,2,3,3,3-hexafluoropropyl group.

As the aromatic hydrocarbon group C6~20 hydroxyl group or a hydrogen atom may be substituted with a hydroxyl group which is substituted in R _34, specifically, to illustrate the substituent represented by the following formula (V) Can do.

In the formula, R ₄₀ represents a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms or a fluorinated alkyl group, and specific examples thereof are the same substitutions as the specific examples illustrated for R ₃₁ above. Examples of the group include X, a fluorine atom, and R ₄₁ a C1-C20 hydrocarbon group, preferably an acid labile group. a, b, c, and d each represent an integer of 0 or 1 to 5, and a + b + c + d is any of 0 to 5.

In R ₄₁ , the C1-C20 hydrocarbon group can be exemplified by the same substituents as those exemplified for R ₁ , and various acid labile groups can be selected. Examples include groups represented by the following formula (VI), (VII), or (VIII), trialkylsilyl groups having 1 to 6 carbon atoms, oxoalkyl groups having 4 to 20 carbon atoms, and the like of each alkyl group. be able to.

In the formulas (VI) and (VII), R ₅₁ and R ₅₄ are monovalent hydrocarbon groups such as linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, oxygen atoms, sulfur atoms, nitrogen atoms And may contain a hetero atom such as a fluorine atom.

R ₅₂ and R ₅₃ are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom or a fluorine atom. R ₅₂ and R ₅₃ , R ₅₂ and R ₅₄ , and R ₅₃ and R ₅₄ may be bonded to each other to form a ring. h represents 0 or an integer of 1 to 10.

More preferably, R _{51 to} R ₅₄ are the following groups. R ₅₁ is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the above formula (VIII And a tertiary alkyl group specifically includes a tert-butyl group, a tert-amyl group, a 1,1-diethylpropyl group, a 1-ethylcyclopentyl group, a 1-butylcyclopentyl group, 1- Specific examples of the trialkylsilyl group include an ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, and 2-methyl-2-adamantyl group. Include trimethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group, etc. The body, the 3-oxo-cyclohexyl group, 4-methyl-2-oxooxan-4-yl group, and 5-methyl-5-oxo-dioxolane-4-yl group.

R ₅₂ and R _{53 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, specifically a methyl group, an ethyl group, a propyl group or an isopropyl group. N-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group and the like. R ₅₄ represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, a linear, branched, or cyclic alkyl group, Examples include those in which a part of hydrogen atoms are substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like. Specifically, a 4-hydroxybutyl group, a 2-butoxyethyl group, 4 Examples thereof include substituted alkyl groups such as -hydroxymethyl-1-cyclohexylmethyl group, 2-hydroxyethoxy-2-ethyl group, 6-hydroxyhexyl group and 1,3-dioxolan-2-one-4-methyl group.

R ₅₂ and R ₅₃ , R ₅₂ and R ₅₄ , R ₅₃ and R ₅₄ may form a ring, and in the case of forming a ring, R ₅₂ , R ₅₃ and R ₅₄ each have 1 to 18 carbon atoms, Preferably it represents 1-10 linear or branched alkylene groups.

  Specific examples of the formula (VI) include a t-butoxycarbonyl group, a t-butoxycarbonylmethyl group, a t-amyloxycarbonyl group, a t-amyloxycarbonylmethyl group, a 1,1-diethylpropyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2-cyclopentenyloxycarbonyl Examples thereof include a methyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

  Among the acid labile groups represented by the above formula (VII), as linear or branched ones, specifically, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an n-butoxymethyl group, Isopropoxymethyl group, t-butoxymethyl group, 1-methoxy-ethyl group, 1-ethoxy-ethyl group, 1-methoxy-propyl group, 1-methoxy-butyl group, 1-ethoxy-propyl group, 1-ethoxy- Propyl group, 1-n-propoxyethyl group, 1-n-propoxyethyl group, 1-n-propoxy-propyl group, 1-n-butoxy-butyl group, 1-n-propoxy-butyl group, 1-cyclopentyloxy -Ethyl group, 1-cyclohexyloxy-ethyl group, 2-methoxy-2-propyl group, 2-ethoxy-2-propyl group and the like can be exemplified.

  Specific examples of the acid labile group represented by the above formula (VIII) include cyclic tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, 2 -A methyltetrahydropyran-2-yl group etc. can be illustrated. As the formula (4), a 1-ethoxy-ethyl group, a 1-n-butoxy-ethyl group, and a 1-ethoxy-n-propyl group are preferable.

In the formula (VIII), R ₅₅ , R ₅₆ , and R ₅₇ are monovalent hydrocarbon groups such as a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom. Hetero atoms, fluorine atoms and the like, and R ₅₅ and R ₅₆ , R ₅₅ and R ₅₇ , and R ₅₆ and R ₅₇ may be bonded to each other to form a ring.

  The tertiary alkyl group represented by the formula (VIII) includes t-butyl group, 1,1-diethyl-n-propyl group, 1-ethylnorbornyl group, 1-methylcyclohexyl group, 1-ethylcyclopentyl group, 2 -(2-Methyl) adamantyl group, 2- (2-ethyl) adamantyl group, tert-amyl group and the like can be mentioned.

  Moreover, as a tertiary alkyl group represented by Formula (VII), the functional group shown below can be illustrated concretely.

Here, R ₆₁ and R ₆₄ represent a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, Examples include sec-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclopropylmethyl group and the like. R ₆₂ is a monovalent hydrocarbon radical such as a hydrogen atom, it contains a heteroatom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, or an alkyl group which may through a hetero atom having 1 to 6 carbon atoms. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom, and —OH, —OR (R is an alkyl group having 1 to 20 carbon atoms, particularly 1 to 16 carbon atoms, the same applies hereinafter), —O—, — S -, - S (= O ) -, - NH 2, -NHR, -NR 2, -NH -, - can contain or intervening as NR-.

_Examples of R ₆₃ include a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, particularly 1 to 16 carbon atoms, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, or an alkoxyalkyl group. It can be either branched or annular. Specifically, methyl group, hydroxymethyl group, ethyl group, hydroxyethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, methoxy group, methoxymethoxy Group, ethoxy group, tert-butoxy group and the like.

Examples of the trialkylsilyl group in which each alkyl group used as the acid labile group of R ₄₁ has 1 to 6 carbon atoms include a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group.

Examples of the oxoalkyl group having 4 to 20 carbon atoms used as the acid labile group for R ₄₁ include a 3-oxocyclohexyl group and a group represented by the following formula.

Furthermore, the acid labile group of R ₄₁ may be an acetal bridging group represented by the following formula (IX) or (X).

In formula, _R71 , _R72 shows a hydrogen atom or a C1-C8 linear, branched or cyclic alkyl group. Alternatively, R ₇₁ and R ₇₂ may be bonded to form a ring, and when forming a ring, R ₇₁ and R ₇₂ represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ₇₃ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, e is an integer of 1 to 7, and f and g are 0 or an integer of 1 to 10. A represents an (e + 1) -valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and these groups may intervene a hetero atom, Alternatively, a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group, or a fluorine atom. B represents —CO—O—, —NHCO—O— or —NHCONH—.

  Specific examples of the crosslinked acetal represented by the formulas (IX) and (X) include the following formulas.

  Specific examples of the repeating unit (IV) having a functional group represented by the formula (V) include repeating units obtained by polymerizing the following monomers.

  Styrene, α-methylstyrene, fluorostyrene, 1,1-diphenylethylene, stilbene, 4-hydroxystyrene, 4-hydroxy-α-methylstyrene, 4-hydroxy-3-methyl-styrene, 4-t-butoxy-styrene 4-tetrahydropyranyloxy-styrene, 4-phenoxyethoxy-styrene, 4-trimethylsilyloxy-styrene, 4-t-butoxycarbonyloxy-styrene, 4-t-butoxycarbonylmethoxy-styrene, 2,3-difluoro- 4-hydroxystyrene, 2,3-difluoro-4-t-butoxy-styrene, 2,6-difluoro-4-hydroxy-styrene, 2,6-difluoro-4-t-butoxy-styrene, 3,5-difluoro -4-hydroxy-styrene, 3,5-difluoro -4-tert-butoxy-styrene, 2,3,5,6-tetrafluoro-4-hydroxy-styrene, 2,3,5,6-tetrafluoro-4-tert-butoxy-styrene, 2-trifluoromethyl -4-hydroxy-styrene, 2-trifluoromethyl-4-t-butoxy-styrene, 2-trifluoromethyl-6-fluoro-4-hydroxy-styrene, 2-trifluoromethyl-6-fluoro-4-t -Butoxy-styrene, 3-trifluoromethyl-5-fluoro-4-hydroxy-styrene, 3-trifluoromethyl-5-fluoro-4-tert-butoxy-styrene, 4- (1-ethoxyethoxy) -styrene, 4- (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) -styrene, 4- (2-ethoxymethoxy-1,1, , 3,3,3-hexafluoro-2-propyl) -styrene, 2,3-difluoro-4-hydroxystyrene, 2,3-difluoro-4-tert-butoxy-α-fluoro-styrene, 2,6- Difluoro-4-hydroxy-α-fluoro-styrene, 2,6-difluoro-4-t-butoxy-α-fluoro-styrene, 3,5-difluoro-4-hydroxy-α-fluoro-styrene, 3,5- Difluoro-4-t-butoxy-α-fluoro-styrene, 2,3,5,6-tetrafluoro-4-hydroxy-α-fluoro-styrene, 2,3,5,6-tetrafluoro-4-t- Butoxy-α-fluoro-styrene, 2-trifluoromethyl-4-hydroxy-α-fluoro-styrene, 2-trifluoromethyl-4-t-butoxy-α-fluoro Styrene, 2-trifluoromethyl-6-fluoro-4-hydroxy-α-fluoro-styrene, 2-trifluoromethyl-6-fluoro-4-tert-butoxy-α-fluoro-styrene, 3-trifluoromethyl- 5-fluoro-4-hydroxy-α-fluoro-styrene, 3-trifluoromethyl-5-fluoro-4-t-butoxy-α-fluoro-styrene, 4- (1-ethoxyethoxy) -α-methyl-styrene 4- (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) -α-fluoro-styrene, 4- (2-ethoxymethoxy-1,1,1,3, 3,3-hexafluoro-2-propyl) -α-fluoro-styrene and the like.

Furthermore, when R ₃₄ is a CO ₂ R ₃₅ group, R ₃₅ can be exemplified by the same substituents as those exemplified for R ₄ . In this case, as a combination of R _{31 to} R _33, a combination as shown in the following formula can be preferably used. (Repeated unit obtained when polymerizing the following compounds.)

Specific examples of the repeating unit having a CO ₂ R ₃₅ group include methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethyl hexyl acrylate, octyl acrylate, and tert-octyl acrylate. , Chloroethyl acrylate, 2-ethoxyethyl acrylate, 2,2-dimethyl-3-ethoxypropyl acrylate, 5-ethoxypentyl acrylate, 1-methoxyethyl acrylate, 1-ethoxyethyl acrylate, 1-methoxypropyl acrylate, 1-methyl -1-methoxyethyl acrylate, 1- (isopropoxy) ethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc. Acrylic acid esters,
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-ethoxyethyl methacrylate, 4-methoxybutyl methacrylate, 5-methoxypentyl methacrylate, 2 , 2-dimethyl-3-ethoxypropyl methacrylate, 1-methoxyethyl methacrylate, 1-ethoxyethyl methacrylate, 1-methoxypropyl methacrylate, 1-methyl-1-methoxyethyl methacrylate, 1- (isopropoxy) ethyl methacrylate, furfuryl Methacrylate, tetrahydrofurfuryl methacrylate, etc. Methacrylic acid esters, methyl crotonate, ethyl crotonate, propyl crotonate, amyl crotonate, cyclohexyl crotonate, ethyl hexyl crotonate, octyl crotonate, crotonic acid-t-octyl, chloroethyl crotonate, 2-ethoxyethyl crotonate 2,2-dimethyl-3-ethoxypropyl crotonate, 5-ethoxypentyl crotonate, 1-methoxyethyl crotonate, 1-ethoxyethyl crotonate, 1-methoxypropyl crotonate, 1-methyl-1-methoxy Crotonic acid esters such as ethyl crotonate, 1- (isopropoxy) ethyl crotonate, benzyl crotonate, methoxybenzyl crotonate, furfuryl crotonate, tetrahydrofurfuryl crotonate, etc. Dimethyl citrate, diethyl itaconate, dipropyl itaconate, diamyl itaconate, dicyclohexyl itaconate, bis (ethylhexyl) itaconate, dioctyl itaconate, di-t-octyl itaconate, bis (chloroethyl) itaconate, bis (2- Ethoxyethyl) itaconate, bis (2,2-dimethyl-3-ethoxypropyl) itaconate, bis (5-ethoxypentyl) itaconate, bis (1-methoxyethyl) itaconate, bis (1-ethoxyethyl) itaconate, bis (1 -Methoxypropyl) itaconate, bis (1-methyl-1-methoxyethyl) itaconate, bis (1- (isopropoxy) ethyl) itaconate, dibenzylitaconate, bis (methoxybenzyl) itaconate, diflufuryl Examples thereof include repeating units derived from itaconic acid esters such as taconate and ditetrahydrofurfururitaconate. Furthermore, the repeating unit represented by a following formula can be illustrated.

  Furthermore, as a repeating unit other than the repeating unit represented by the formula (I), a compound represented by the formula (XI) can be exemplified.

In the formula (XI), R ₈₁ and R ₈₂ each independently represent a hydrogen atom, a fluorine atom, a C1-C20 hydrocarbon group, a heterocyclic group, a cyano group, a nitro group, a C (═O) R ₄ group, Represents an S (O) nR ₄ group, a P (═O) (R ₄ ) ₂ group, and an M (R ₄ ) ₃ group. Specifically, the same substituents as those exemplified for R ₁ are exemplified. be able to.

  The polymer having the repeating unit represented by the formula (I) in the present invention is represented by the polymer consisting only of the repeating unit represented by the formula (I) and the formula (I) as described above. Means a polymer comprising a repeating unit other than the repeating unit represented by formula (I), and the polymerization mode of the repeating unit represented by formula (I) and the other repeating unit is particularly limited. Any of random polymerization, block polymerization, partial block polymerization, and alternating polymerization can be used.

  Moreover, the mixing ratio of the repeating unit represented by the formula (I) and the other repeating units is not particularly limited, and can be arbitrarily set in a molar ratio of 99/1 to 1/99.

  The number average molecular weight of the polymer having a repeating unit represented by the formula (I) is not particularly limited. However, when used for a resist or the like, in consideration of etching resistance, alkali solubility, etc., 2,000 to 50,000 The range of is preferable. The molecular weight distribution, which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is not particularly limited, but is in the range of 1.01 to 3.00, 1 A range of .01 to 1.50 is preferred.

  As a method for producing a polymer having a repeating unit represented by the formula (I), specifically, a ketene represented by the following formula (XII) and an aldehyde represented by the formula (XIII) are converted into an anionic polymerization initiator. A method for anionic polymerization in the presence can be exemplified.

In the formula, R ₉₁ corresponds to R ₁ , R ₉₂ corresponds to R ₂ , and R ₉₃ corresponds to R ₃ , respectively, and a substituent that hinders anionic polymerization, such as a substituent having an active hydrogen atom, The substituent which excluded the substituent etc. which are reactive with an anionic polymerization initiator is represented.

  The solvent used for anionic polymerization is not particularly limited as long as it is a polar solvent that does not participate in the polymerization reaction and is compatible with the polymer. Specifically, aliphatic solvents such as n-hexane and n-heptane are used. Hydrocarbons, alicyclic hydrocarbons such as cyclohexane and cyclopentane, aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether, tetrahydrofuran (THF) and dioxane, as well as anisole and hexamethyl phosphor The organic solvent normally used in anionic polymerization, such as amide, can be mentioned. Moreover, these solvent can be used individually by 1 type or as a 2 or more types of mixed solvent.

  Examples of the anionic polymerization initiator include alkali metals or organic alkali metals. Examples of the alkali metals include lithium, sodium, potassium, cesium, sodium-potassium alloys, and the like. Alkylated products, allylated products, arylated products and the like of the above alkali metals can be used. Specifically, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, ethylsodium, lithium biphenyl, lithium Naphthalene, lithium triphenyl, sodium naphthalene, potassium naphthalene, α-methylstyrene sodium dianion, 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, 1,1-diphenylmethyl potassium 1,4-dilithio-2-butene, 1,6-dilithiohexane, polystyryllithium, cumylpotassium, cumylcesium and the like. These compounds may be used alone or in combination of two or more. Can be used.

  In the reaction, compounds represented by the formulas (XII) and (XIII) are usually added to an anionic polymerization initiator, and anionic living polymerization is performed. These series of reactions are carried out in the range of −100 to 0 ° C., preferably −70 to −20 ° C. under an inert gas such as argon or nitrogen, or under high vacuum. The molar ratio of the ketene represented by the formula (XII) to be used and the aldehyde represented by the formula (XIII) is not particularly limited, but is preferably in the range of 99/1 to 50/50. Further, as described above, the ketene represented by the formula (XII) and the aldehyde represented by the formula (XIII) can be used singly or in combination of two or more.

In the polymer in which R ₃ is a substituent represented by the formula (II), a compound in which R ₅ is a hydrogen atom is polymerized with a compound having a functional group other than a hydrogen atom, and the functional group is removed. In this case, only part of the functional group can be eliminated by controlling the reaction. For example, the reaction for partially or completely removing the protecting group of the phenolic hydroxyl group that is unstable to acids includes the solvents exemplified in the polymerization reaction, alcohols such as methanol and ethanol, and ketones such as acetone and methyl ethyl ketone. , Polyhydric alcohol derivatives such as methyl cellosolve, ethyl cellosolve, one or more kinds of mixed solvents such as water, hydrochloric acid, sulfuric acid, hydrogen chloride gas, hydrobromic acid, p-toluenesulfonic acid, Trichloroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, general formula XHSO ₄ (wherein X represents an alkali metal such as Li, Na, K, etc.) and an acid reagent such as bisulfate are usually used as catalysts. It is carried out at a temperature between room temperature and 150 ° C. Further, when a silyl group is used as a protecting group, a fluorine anion compound such as quaternary ammonium fluoride can also be used.

The amount of the acidic reagent to be used is sufficient as the catalyst amount, but usually the average molecular weight of the whole polymer is obtained from the molar fraction of each unit and the molecular weight of each unit, and each of the total weight, average molecular weight, and molar fraction of each polymer is determined. The number of moles of the unit is determined, and is in the range of 0.1 to 3 equivalents, preferably 0.1 to 1 equivalents relative to the number of moles of the alkoxy group (OR ₅ group).

Moreover, another functional group can also be introduce | transduced into the hydroxyl part obtained as mentioned above. The above-described operation has been described by taking the substituent of R ₃ as an example, but it can also be performed on the same substituent as OR ₅ on R ₁ and R ₂ .

  The polymer having a repeating unit represented by the formula (I) has a property that the main chain is easily cleaved by an acid as described in Examples. In the composition in this invention, it can be used as a dissolution inhibitor for making contrast clear by mixing with alkali-soluble resin.

The blending amount of the polymer having a repeating unit represented by formula (I) is 0 to 50 parts, preferably 5 to 50 parts, more preferably 100 parts by weight of alkali-soluble polymer (parts by weight, hereinafter the same). It is 10-30 parts, and can be used individually or in mixture of 2 or more types. If the blending amount is less than 5 parts, the resolution may not be improved, and if it exceeds 50 parts, the film thickness of the pattern may be reduced and the resolution may be lowered.
(III) Acid generator The acid generator used in the present invention is not limited as long as it is a compound capable of generating an acid upon irradiation with radiation and does not adversely affect the formation of a resist pattern, but particularly around 248.4 nm. The light transmittance of the resist composition is high and the transparency of the resist composition can be maintained, or the light transparency is increased by exposure and the transparency of the resist composition can be maintained, or the acid generation efficiency is high, so a small amount can be added. An acid generator that exhibits an effect is preferred. Specific examples of particularly preferable acid generators include compounds represented by the following formula (XIV), formula (XV), formula (XVI), formula (XVII), and formula (XVIII). .

(Wherein R ₁₀₀ and R ₁₀₁ each independently represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or an aralkyl group, and W represents a sulfonyl group or a carbonyl group.)

(In the formula, R ₁₀₃ and R ₁₀₄ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁₀₅ represents a linear, branched or cyclic group having 1 to 6 carbon atoms. Represents an alkyl group, an aralkyl group, or an optionally substituted phenyl group, and V represents a sulfonyl group or a carbonyl group.)

(Wherein, R _106, R ₁₀₇ and R ₁₀₈ are independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a t- butoxycarbonyl group, R ₁₀₉ Represents a fluorine-containing alkyl group having 1 to 8 carbon atoms, an optionally substituted phenyl group, or a 10-camphor group, Y represents a sulfur atom or an iodine atom, and when Y is an iodine atom, z represents 0. And z represents 1 in the case of a sulfur atom.)

(In the formula, R ₁₁₀ represents an alkyl group having 1 to 6 carbon atoms, a fluorine-containing alkyl group having 1 to 8 carbon atoms, an optionally substituted phenyl group, or a 10-camphor group.)

(In the formula, R ₁₁₁ and R ₁₁₂ each independently represent a hydrogen atom, a methyl group, or an ethyl group, and R ₁₁₁ and R ₁₁₂ have an aromatic ring group or a bridged alicyclic hydrocarbon group having an unsaturated bond. R ₁₁₃ represents an alkyl group having 1 to 6 carbon atoms, a fluorine-containing alkyl group having 1 to 8 carbon atoms, an optionally substituted phenyl group, or a 10-camphor group.)
Specifically, preferred acid generators include those represented by formula (XIV) such as 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl). ) Diazomethane, bis (1-methylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-cyclohexylsulfonyl-3,3-dimethylbutan-2-one 1-diazo-1- (1,1-dimethylethylsulfonyl) -3,3-dimethylbutan-2-one and the like.

  Specific examples of the acid generator represented by the formula (XV) include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylbenzenesulfonyl) diazomethane, bis (p-tert-butylphenylsulfonyl) diazomethane, bis (P-chlorobenzenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl-p-toluenesulfonyldiazomethane, 1-p-toluenesulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1- (p-toluene) Examples include sulfonyl) -3,3-dimethylbutan-2-one and the like.

  Specific examples of the acid generator represented by the formula (XVI) include triphenylsulfonium / trifluoromethanesulfonate, triphenylsulfonium / perfluorobutanesulfonate, triphenylsulfonium / perfluorooctanesulfonate, triphenylsulfonium / p-toluenesulfonate. , Triphenylsulfonium ・ 10-camphorsulfonate, diphenyl-p-tolylsulfonium ・ trifluoromethanesulfonate, diphenyl-p-tolylsulfonium ・ perfluorobutanesulfonate, diphenyl-p-tolylsulfonium ・ perfluorooctanesulfonate, diphenyl-p-tolyl Sulfonium ・ p-toluenesulfonate, diphenyl-p-tolylsulfonium ・ 10-camphorsulfonate, diphenyl-p-tert- Butylphenylsulfonium / trifluoromethanesulfonate, diphenyl-p-tert-butylphenylsulfonium / perfluorobutanesulfonate, diphenyl-p-tert-butylphenylsulfonium / perfluorooctanesulfonate, diphenyl-p-tert-butylphenylsulfonium / p- Toluenesulfonate, diphenyl-p-tert-butylphenylsulfonium · 10-camphorsulfonate, diphenyl-p-tert-butylphenylsulfonium · p-fluorobenzenesulfonate, diphenyl-p-cyclohexylphenylsulfonium · trifluoromethanesulfonate, diphenyl-p- Cyclohexylphenylsulfonium perfluorobutanesulfonate, diphenyl-p-cyclohexylphenylsulfonium Fluorooctanesulfonate, diphenyl-p-cyclohexylphenylsulfonium / p-toluenesulfonate, diphenyl-p-tert-butoxyphenylsulfonium / trifluoromethanesulfonate, diphenyl-p-tert-butoxyphenylsulfonium / perfluorobutanesulfonate, diphenyl-p- tert-butoxyphenylsulfonium / perfluorooctanesulfonate, diphenyl-p-tert-butoxyphenylsulfonium / p-toluenesulfonate, diphenyl-p-tert-butoxycarbonyloxyphenylsulfonium / perfluorooctanesulfonate, diphenyl-p-tert-butoxy Carbonyloxyphenylsulfonium ・ 10-camphorsulfonate, diphenyl-p-tert-butoxycarbonyloxyphene Rusuruhoniumu-p-toluenesulfonate can be exemplified 4,4'--tert- butyl diphenyl iodonium-10-camphorsulfonate, and the like.

  Specific examples of the acid generator represented by the formula (XVII) include 1,2,3-tris-methanesulfonyloxybenzene, 1,2,3-tris-trifluoromethanesulfonyloxybenzene, 1,2,3-tris. -Perfluorooctanesulfonyloxybenzene, 1,2,3-tris-perfluorobutanesulfonyloxybenzene, 1,2,3-tris-p-toluenesulfonyloxybenzene, 1,2,3-tris-10-camphorsulfonyl Oxybenzene, 1,2,3-tris-trifluoroacetyloxybenzene, 1,2,4-tris-methanesulfonyloxybenzene, 1,2,4-tris-trifluoromethanesulfonyloxybenzene, 1,2,4- Tris-3-tris-perfluorooctanesulfonyloxybenzene, 1,2,4-tris-p-toluenesulfonyloxybenzene, 1,2,4-tris-perful It can be exemplified Rob Tan sulfonyloxy benzene.

  Examples of the acid generator represented by the formula (XVIII) include succinimide / trifluoromethanesulfonate, succinimide / perfluorobutanesulfonate, succinimide / perfluorooctanesulfonate, succinimide / p-toluenesulfonate, succinate. Acid imide, 10-camphor sulfonate, succinimide, methane sulfonate, succinimide, 1-methylethane sulfonate, succinimide, benzene sulfonate, dimethyl succinimide, trifluoromethane sulfonate, dimethyl succinimide, perfluorooctane sulfonate , Dimethyl succinimide / p-toluene sulfonate, phthalic imide / trifluoromethane sulfonate, phthalic imide / perfluorobutane sulfonate, phthalic acid Imido perfluorooctane sulfonate, phthalic imide p-toluene sulfonate, phthalic imide 10-camphor sulfonate, phthalic imide methane sulfonate, phthalic imide benzene sulfonate, 5-norbornene-2,3-dicarboximide Trifluoromethanesulfonate, 5-norbornene-2,3-dicarboximidePerfluorobutanesulfonate, 5-norbornene-2,3-dicarboximidePerfluorooctanesulfonate, 5-norbornene-2,3-dicarboximide Examples include p-toluenesulfonate, 5-norbornene-2,3-dicarboximide, 10-camphorsulfonate, 5-norbornene-2,3-dicarboximide, methanesulfonate, and the like.

  When used as a resist composition, one or more polymers having a repeating unit represented by formula (I) and an alkali-soluble polymer are mixed to generate an acid represented by formulas (XIV) to (XVIII). It is preferable to use 1 type selected from an agent or 2 or more types in combination. As a preferable example in the case of using two or more kinds of acid generators in combination, the light transmittance is good, the high transparency of the resist composition can be maintained, the heat treatment (PEB) temperature dependency after exposure is small, and An acid generator represented by the formula (XIV) that generates a weak acid by exposure, and a formula (XV), a formula (XVI), or a formula (XVII) that has a high acid generation efficiency or generates a strong acid for a certain exposure amount. Or it is preferable to use in combination with the acid generator represented by the formula (XVIII) from the viewpoint of improving the shape of the skirt of the pattern and removing the scum, and among them, the acid generator represented by the formula (XIV) and the formula It is particularly preferable to use in combination with an acid generator represented by (XV) or / and formula (XVI).

  Moreover, as a constituent ratio of the acid generator when two or more acid generators are used in combination, the formula (XV), the formula (XVI), or the formula with respect to 100 parts by weight of the acid generator represented by the formula (XIV) The acid generator represented by (XVII) is 1 to 70 parts by weight, preferably 10 to 50 parts by weight.

In addition, various triphenylsulfonium salts and diphenyliodonium salts conventionally used (anions of these onium salts include PF ₆ ⁻ , AsF ₆ ⁻ , BF ₄ ^{− and the} like) and tris (trichloro). Methyl) -s-triazine / triethanolamine, tris (trichloromethyl) -s-triazine / acetamide and the like, or a compound represented by the above formulas (XIV) to (XVIII) It can be used by mixing.

  The blending amount of the acid generator is preferably 0.2 to 15 parts, more preferably 0.5 to 8 parts, and less than 0.2 parts with respect to 100 parts of the total base resin (parts by weight, the same applies hereinafter). The amount of acid generated during exposure is small, and the sensitivity and resolution may be inferior. If the amount exceeds 15 parts, the transmittance of the resist may be lowered and the resolution may be inferior.

The composition of this invention can contain the following components as needed other than (A)-(C) component.
(D) Organic solvent The organic solvent is not particularly limited as long as it is an organic solvent in which the components (A) to (C) can be dissolved. Specifically, cyclohexanone, methyl-2-n-amyl ketone, etc. Ketones, alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol mono Ethers such as ethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, lactic acid ester Examples include esters such as chill, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate These can be used alone or in admixture of two or more, but are not limited thereto. In the present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, and ethyl lactate, which are most excellent in solubility of the acid generator in the resist component, as well as propylene glycol monomethyl ether acetate, which is a safety solvent, are used. And mixed solvents thereof are preferably used.
(E) Basic compound As the basic compound, a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By mixing such a basic compound, , The acid diffusion rate in the resist film is suppressed, resolution is improved, sensitivity change after exposure is suppressed, substrate and environment dependency is reduced, exposure margin, pattern profile, etc. can be improved (JP-A-5-232706, JP-A-5-249683, JP-A-5-158239, JP-A-5-24962, JP-A-5-257282, JP-A-5-289322, JP-A-5-289340, etc.).

  Examples of such basic compounds include primary, secondary, and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, and sulfonyl groups. A nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like. Particularly, an aliphatic amine is preferably used.

  Specifically, primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert- Amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc. are exemplified as secondary aliphatic amines. Dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, disi Lopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepenta Examples of tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, and tripentylamine. , Tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, Examples include cetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like. Is done.

  Examples of hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (eg, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3- Methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5- Dinitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dim Lupyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg oxazole, isoxazole etc.), thiazole derivatives (eg thiazole, isothiazole etc.), imidazole derivatives (eg imidazole, 4-methylimidazole, 4 -Methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.) ), Imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethyl) Lysine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine Derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (eg quinoline, 3-quinoline carbo Nitriles), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine Examples include derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

  Furthermore, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine. , Phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like, and examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and the like. Nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemeta Hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) Ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propane Diol, 8-hydroxy Loridine, 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. Illustrated. Examples of amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Examples of the imide derivative include phthalimide, succinimide, maleimide, tris {2- (methoxymethoxy) ethyl} amine, tris {2- (methoxyethoxy) ethyl} amine, tris [2-{(2-methoxyethoxy) methoxy} ethyl]. Amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1 -Ethoxypropoxy) ethyl} amine, tris [2-{(2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] ] Hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5. ] Eicosane, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown- 6 etc. can be illustrated.

  Especially tertiary amines, aniline derivatives, pyrrolidine derivatives, pyridine derivatives, quinoline derivatives, amino acid derivatives, nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, Tris {2- (methoxymethoxy) ethyl} amine, tris {(2- (2-methoxyethoxy) ethyl} amine, tris [2-{(2-methoxyethoxy) methyl} ethyl] amine, 1-aza-15- Crown-5 and the like are preferable.

In addition, the said basic compound can be used individually by 1 type or in combination of 2 or more types, The compounding quantity is 2 parts or less with respect to 100 parts of all base resins, Preferably it is 0.01-2 parts, Especially. 0.01-1 part is preferred. If the blending amount is less than 0.01 part, there is no blending effect, and if it exceeds 2 parts, the sensitivity may be too low.
(F) Aromatic carboxylic acid An aromatic compound having a group represented by ≡C—COOH in the molecule can be added to the resist composition of the present invention. By blending the component (F), the PED stability of the resist can be improved, and the edge roughness on the nitride film substrate can be improved. Specific examples of such a compound include compounds represented by the following formulae.

  The aromatic compound having a group represented by ≡C—COOH in the molecule can be used alone or in combination of two or more.

The amount of the aromatic compound having a group represented by ≡C—COOH in the molecule is 5 parts or less, preferably 0.1 to 5 parts, more preferably 1 to 3 parts relative to 100 parts of the base resin. is there. If the amount is less than 0.1 part, the tailing on the nitride film substrate and the effect of improving PED may not be sufficiently obtained. If the amount is more than 5 parts, the resolution of the resist material may be lowered.
(G) Dissolution Control Agent A dissolution control agent can be added to the resist material of the present invention for adjusting the dissolution rate, thereby improving the contrast. As a dissolution controller, an average molecular weight of 100 to 1,000, preferably 150 to 800, and a compound having two or more phenolic hydroxyl groups in the molecule, the entire hydrogen atom of the phenolic hydroxyl group is converted to an acid labile group. As an average, 0 to 100 mol% of the substituted compound is blended.

  The substitution rate of the hydrogen atom of the phenolic hydroxyl group by an acid labile group is on average 0 mol% or more, preferably 30 mol% or more of the entire phenolic hydroxyl group, and the upper limit is more preferably 100 mol%. Is 80 mol%.

  In this case, examples of the compound having two or more phenolic hydroxyl groups include the compounds shown below.

  Here, as the acid labile group of the dissolution controller, a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms, and an oxoalkyl group having 4 to 20 carbon atoms, respectively. Etc.

  The compounding amount of the compound in which the phenolic hydroxyl group is partially substituted with an acid labile group (dissolution control agent) is 0 to 50 parts, preferably 5 to 50 parts, more preferably 10 to 30 parts relative to 100 parts of the base resin. It can be used alone or in admixture of two or more. If the blending amount is less than 5 parts, the resolution may not be improved, and if it exceeds 50 parts, the film thickness of the pattern may be reduced and the resolution may be lowered.

The dissolution control agent as described above can be synthesized by chemically reacting an acid labile group with a compound having a phenolic hydroxyl group in the same manner as the base resin.
(H) Ultraviolet Absorber Further, the resist material of the present invention may contain a compound having a molar absorbance at a wavelength of 248 nm of 10,000 or less as an ultraviolet absorber. This makes it possible to design and control a resist having an appropriate transmittance for substrates having different reflectivities.

  Specifically, pentalene, indene, naphthalene, azulene, peptalene, biphenylene, indacene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, acanthrylene, triphenylene, pyrene, chrysene, naphthalene, preaden, picene Perylene, pentaphene, pentacene, benzophenanthrene, anthraquinone, anthrone benzanthrone, 2,7-dimethoxynaphthalene, 2-ethyl-9,10-dimethoxyanthcerane, 9,10-dimethylanthracene, 9-ethoxyanthracene, 1,2 -Condensed polycyclic hydrocarbon derivatives such as naphthoquinone and 9-fluorene, condensed heterocyclic derivatives such as thioxanthen-9-one, thianthrene and dibenzothiophene, 2,3,4-to Vitroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone, 4,4′-bis (dimethylamino) benzophenone And benzophenone derivatives such as squaric acid derivatives such as squaric acid and dimethyl squarate.

  Examples of the ultraviolet absorber include bis (4-hydroxyphenyl) sulfoxide, bis (4-tert-butoxyphenyl) sulfoxide, bis (4-tert-butoxycarbonyloxyphenyl) sulfoxide, and bis [4- (1-ethoxyethoxy). ) Phenyl] sulfoxide derivatives such as diaryl sulfoxide derivatives, bis (4-hydroxyphenyl) sulfone, bis (4-tert-butoxyphenyl) sulfone, bis (4-tert-butoxycarbonyloxyphenyl) sulfone, bis [4- (1- Diarylsulfone derivatives such as ethoxyethoxy) phenyl] sulfone, bis [4- (1-ethoxypropoxy) phenyl] sulfone, benzoquinonediazide, naphthoquinonediazide, anthraquinonediazide, diazofluorene, diazote Diazo compounds such as laron and diazophenantrone, naphthoquinone-1,2-diazide-5-sulfonic acid chloride and 2,3,4-trihydroxybenzophenone complete or partial ester compound, naphthoquinone-1,2-diazide- A quinonediazide group-containing compound such as a complete or partial ester compound of 4-sulfonic acid chloride and 2,4,4′-trihydroxybenzophenone can also be used.

  As the UV absorber, tert-butyl 9-anthracenecarboxylate, tert-amyl 9-anthracenecarboxylate, tert-methoxymethyl 9-anthracenecarboxylate, tert-ethoxyethyl 9-anthracenecarboxylate, 9-anthracenecarboxylic acid tert-tetrahydropyranyl, 9-anthracenecarboxylic acid tert-tetrahydrofuranyl, naphthoquinone-1,2-diazide-5-sulfonic acid chloride and partial ester compound of 2,3,4-trihydroxybenzophenone .

  The blending amount of the ultraviolet absorber is preferably 0 to 10 parts, more preferably 0.5 to 10 parts, and still more preferably 1 to 5 parts with respect to 100 parts of the base resin.

  Other additives Furthermore, an acetylene alcohol derivative can be mix | blended with the resist composition of this invention, and, thereby, storage stability can be improved. Specifically, Surfinol 61, Surfinol 82, Surfinol 104, Surfinol 104E, Surfinol 104H, Surfinol 104A, Surfinol TG, Surfinol PC, Surfinol 440, Surfinol 465, Surfinol 485 (Air) Products and Chemicals Inc.), Surfynol E1004 (Nisshin Chemical Industry Co., Ltd.) and the like can be exemplified.

  The amount of the acetylene alcohol derivative added is 2% by weight or less, preferably 0.01 to 2% by weight, more preferably 0.02 to 1% by weight in 100% by weight of the resist composition. When the amount is less than 0.01% by weight, the effect of improving the coating property and storage stability may not be sufficiently obtained. When the amount is more than 2% by weight, the resolution of the resist material may be lowered.

  Surfactant To the resist material of the present invention, a surfactant conventionally used for improving coatability can be added as an optional component in addition to the above components. In addition, the addition amount of an arbitrary component can be made into a normal amount in the range which does not inhibit the effect of this invention.

  Here, the surfactant is preferably nonionic, and examples thereof include perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, and fluorinated organosiloxane compound. For example, Florard “FC-430”, “FC-431” (all manufactured by Sumitomo 3M Limited), Surflon “S-381”, “S-383” (all manufactured by Asahi Glass Co., Ltd.), Unidyne “DS- 401 ”,“ DS-403 ”,“ DS-451 ”(all manufactured by Daikin Industries, Ltd.), MegaFuck“ F-171 ”“ F-172 ”“ F-173 ”“ F-177 ”(Dainippon) Ink Industry Co., Ltd.), “X-70-092”, “X-70-093” (all manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. Preferably, Florard “FC-430” (manufactured by Sumitomo 3M Co., Ltd.), “X-70-093” (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

  In order to form a pattern using the resist composition of the present invention, a known lithography technique can be employed. For example, a film thickness of 0.5 can be formed on a substrate such as a silicon wafer by spin coating or the like. It is applied to a thickness of ˜2.0 μm and prebaked on a hot plate at 60 to 150 ° C. for 1 to 10 minutes, preferably 80 to 120 ° C. for 1 to 5 minutes. Next, a mask for forming a target pattern is placed over the resist film, and a high-energy ray such as far ultraviolet ray having a wavelength of 300 nm or less, an excimer laser, an X-ray, or an electron beam is applied in an exposure amount of about 1 to 200 mJ / cm2, preferably Is irradiated at a temperature of about 10 to 100 mJ / cm 2 and then post-exposure baking (PEB) on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 120 ° C. for 1 to 3 minutes. Further, 0.1-5%, preferably 2-3% tetramethylammonium hydroxide (TMAH) or other alkaline aqueous developer is used for 0.1-3 minutes, preferably 0.5-2 minutes. A target pattern is formed on the substrate by developing by a conventional method such as a (dip) method, a paddle method, or a spray method. The material of the present invention is particularly suitable for fine patterning using deep ultraviolet rays of 254 to 193 nm or excimer laser, X-rays and electron beams among high energy rays. In addition, when the above range deviates from the upper limit and the lower limit, the target pattern may not be obtained.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to an Example.
Reference example 1
(1) Synthesis of ethylphenylketene (EPK) In a nitrogen atmosphere, a THF solution of 55 g (0.3 mol) of 2-phenylbutyryl chloride was added dropwise to a THF mixed solution of 91 g (0.9 mol) of triethylamine. One hour later, the precipitated triethylamine hydrochloride was filtered, and the filtrate was distilled under reduced pressure to obtain EPK (60 to 70 ° C./4 mmHg). Yield 30 g (70% yield).
(2) 4- (t-Butoxycarbonyloxy) benzaldehyde (BOCBA)
In a nitrogen atmosphere, 24.4 g (0.2 mol) of 4-hydroxybenzaldehyde was dissolved in 200 ml of THF, 52.4 g (0.24 mol) of di-t-butyl dicarbonate, and 15 mg of N, N-dimethylaminopyridine. (0.2 mmol) was added and stirred at room temperature overnight. After neutralization by adding an aqueous Na ₂ CO ₃ solution, the solution was separated, and the upper layer was washed with water until pH = 7. MgSO ₄ was added, dehydrated and filtered, concentrated and recrystallized from methanol to obtain BOCBA. Yield 35 g (80% yield).
(3) Alternating copolymerization of EPK and BOCBA Lithium chloride (1.9 g, 45 mmol) was heated and vacuum dried, and then added with 100 ml of THF in a nitrogen atmosphere and cooled to -40 ° C. Further, 4.4 g (32 mmol) of BOCBA and 4.4 g (30 mmol) of EPK were added, and then 0.93 ml (1.5 mmol) of n-BuLi in hexane was added, and the reaction was continued at −40 ° C. for 30 minutes. After stopping the reaction by adding methanol, the mixture was added to a large amount of methanol for reprecipitation, and the resulting precipitate was filtered and dried under reduced pressure to obtain 8.5 g of white powdery polymer (a). When the polymer (a) was analyzed by gel permeation chromatography (hereinafter abbreviated as “GPC”), it was a monodisperse polymer with Mn = 8000 and Mw / Mn = 1.18.
Reference example 2
After dissolving 50 g of poly (p-hydroxystyrene) [Nippon Soda Co., Ltd. VP-15000, Mn = 18000, Mw / Mn = 1.10] in 200 ml of ethyl acetate under nitrogen atmosphere, 15 g of ethyl vinyl ether and 0. 3 ml was added and stirred at room temperature for one day. Next, water was added to the reaction solution for separation, and washing was repeated until neutrality. After concentration, the polymer was precipitated by pouring it into a large amount of methanol, filtered, washed and then vacuum dried to obtain polymer (b). When GPC analysis of the polymer (b) was carried out, it was Mn = 21000, Mw / Mn = 1.10, and the acetal group protection rate measured by NMR was 42%.

30 parts by weight of polymer (a) is mixed with 70 parts by weight of polymer (b) and dissolved in propylene glycol monomethyl ether acetate (PGMEA) so as to have a resin solid content concentration of 12%. Further, triphenylsulfonium trifluoromethanesulfonate Was added so that it might become 1.0 weight% with respect to resin solid content, and the resist solution was adjusted. A film was formed on a silicon wafer using the resist solution by a spin coater and heated on a hot plate at 90 ° C. for 60 seconds to obtain a thin film having a thickness of 400 nm. After exposure with light from an ultra high pressure mercury lamp (illuminance of 10 mW at 365 nm), the plate was heated at 110 ° C. for 90 seconds, and then the dissolution rate was measured using a 2.38% tetramethylammonium hydroxide aqueous solution. The relationship between exposure dose and dissolution rate is summarized in FIG.
Comparative Example 1
Except that the polymer (b) was used alone, the dissolution rate was measured in the same manner as in the Examples, and the relationship between the exposure amount and the dissolution rate is summarized in FIG.

  From FIG. 1, it was found that the composition of the present invention can control dissolution at a low exposure amount as compared with Comparative Example 1 that does not include a polymer having a repeating unit represented by formula (I). Since the dissolution rate rapidly increased at a high exposure amount, it was found that a pattern having excellent contrast can be formed by using the composition of the present invention.

FIG. 1 is a graph showing the relationship between the exposure amount and the dissolution rate in Example 1.

Claims (6)

(A) a polymer that becomes alkali-soluble upon reaction with an acid, (B) formula (I)

(Wherein R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a C1-C20 hydrocarbon group, a heterocyclic group, a cyano group, a nitro group, a C (═O) R ₄ group, S (O ) _N R ₄ group, P (═O) (R ₄ ) ₂ group, M (R ₄ ) ₃ group, R ₃ represents a C1-C20 hydrocarbon group or heterocyclic group, and R ₄ represents C1 -C20 hydrocarbon oxy group, C1-C20 hydrocarbon group, C1-C20 hydrocarbon thio group, mono- or di-C1-C20 hydrocarbon amino group, M is silicon atom, germanium atom, tin atom A polymer containing a repeating unit represented by: a lead atom, n representing any one of 0, 1, or 2; and (C) an acid generator. Stuff. In the compound represented by the formula (I), R ₁ and R ₂ each independently represent a C1 to C20 hydrocarbon group, and R ₃ represents a C1 to C20 hydrocarbon group or a heterocyclic group, The resist composition according to claim 1. In the compound represented by the formula (I), R ₃ represents the formula (II)

(In the formula, R ₅ represents a hydrogen atom or a group that decomposes or leaves with an acid, R ₆ represents a fluorine atom or a C1-C6 hydrocarbon group that may be substituted with a fluorine atom, and m represents 1 represents an integer of 1 to 3, p represents an integer of 0 or 1 to 3, represents m + p ≦ 5, and when m is 2 or more, R ₅ may be the same or different. And p is 2 or more, R ₆ may be the same or different.) The resist composition according to claim 1 or 2, wherein The resist composition according to any one of claims 1 to 3, wherein the polymer having a repeating unit represented by the formula (I) has a number average molecular weight of 2,000 to 50,000. The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer having a repeating unit represented by the formula (I) is in the range of 1.01 to 3.00. The resist composition according to any one of claims 1 to 4, wherein (A) A polymer that becomes alkali-soluble upon reaction with an acid is represented by the formula (III)

(Wherein R ₇ represents a hydrogen atom or a C1-C6 alkyl group optionally substituted with a fluorine atom, R ₈ represents an organic group which is decomposed or eliminated by an acid, and R ₉ represents A fluorine atom, or a C1-C6 hydrocarbon group optionally substituted with a fluorine atom, r represents an integer of 1 to 3, s represents an integer of 0 or 1 to 3, r + s ≦ 5, and when r is 2 or more, R ₈ may be the same or different, and when s is 2 or more, R ₉ may be the same or different. The resist composition according to claim 1, wherein the resist composition is a polymer having a repeating unit.

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