KR20080046579A - Positive resist compositions and patterning process - Google Patents

Abstract

A positive type resist composition is provided to form a pattern having improved resolution, mask fidelity, and reduced line edge roughness in a photolithography using a high energy ray as a light source. A positive type resist composition includes a resin component(A) which is soluble in an alkali developer by an action of an acid, and (B) a compound which reacts to actinic rays or radioactive rays to generate an acid. The resin component(A) is a polymer compound having a repeating unit represented by the following formula 1. The compound(B) generating an acid is a sulfonium salt compound represented by the following formula 2.

Description

Positive Resist Compositions and Patterning Process

The present invention is (1) a positive resist material suitable for microfabrication techniques, excellent in resolution and mask fidelity, and particularly capable of providing a pattern having a small line edge roughness, and (2) a pattern using the resist material. It relates to a forming method.

In recent years, finer pattern rule has been required in accordance with the higher integration and higher speed of LSI, and the development of microfabrication technology using far ultraviolet lithography and vacuum ultraviolet lithography has been actively progressed. Photolithography, which already uses KrF excimer laser light with a wavelength of 248 nm as a light source, plays a central role in actual production of semiconductor devices, but studies using ArF excimer laser light with a wavelength of 193 nm to realize further miniaturization. It is also underway and has been used for some trial production. However, ArF excimer laser lithography is immature as a technique, and various problems remain to be used for actual production in earnest.

Properties required for resist materials corresponding to ArF excimer laser lithography are transparency at wavelength 193 nm and dry etching resistance, both of which are 2-ethyl-2-adamantyl group, 2-methyl- Resist materials having a poly (meth) acrylic acid derivative having a bulky acid-decomposable protecting group represented by 2-adamantyl group as a base resin have been proposed (Patent Document 1: Japanese Patent Laid-Open No. 9-73173, Patent) Document 2: Japanese Patent Laid-Open No. 9-90637). Although several materials have been proposed since then, they are common in most cases in that they use a resin having a high backbone and a carboxylic acid moiety protected with a large volume of tertiary alkyl groups.

In recent years, finer pattern layout has progressed, and fluctuations in pattern line width (line edge roughness, LER) have become a problem. For example, in the processing of the gate electrode portion of the LSI circuit fabrication process, if the LER is bad, problems such as leakage current are caused to deteriorate the electrical characteristics of the transistor. Several factors can be considered as a cause of LER. The main cause is one in which the affinity between the base resin and the developer is poor, that is, the solubility in the developer of the base resin is poor. The carboxylic acid protecting group used conventionally is a bulky tertiary alkyl group, and since it has high hydrophobicity, it is generally bad in solubility. Especially in the case where high resolution such as the formation of fine grooves is required, the LER is large, so that the dimensions become uneven. Conventionally known LER reduction measures include increasing the amount of the photoacid generator added (Non-Patent Document 1: Journal of Photopolymer Science and Technology, Vol. 19, N0.3, 2006, 327-334). However, the characteristics of exposure dose dependence, mask fidelity, and pattern rectangularity may deteriorate extremely at that time, and the effect was not sufficient.

On the other hand, a method of improving LER by using a resin containing fluoroalcohol as a partial structure has also been proposed (Non-Patent Document 3: Journal of Photopolymer Science and Technology, Vol. 18, N0.3, 2005, 381-387). ). In this case, the solubility of the base resin in the alkali developer is improved by introducing fluoroalcohol, but there is also a negative effect of promoting acid diffusion in the heat treatment after exposure (post-exposure bake, PEB). Deterioration occurred and it became a state in which sufficient process window (focus depth, exposure amount margin, etc.) cannot be obtained.

[Patent Document 1] Japanese Patent Application Laid-Open No. 9-73173

[Patent Document 2] Japanese Patent Application Laid-Open No. 9-90637

[Non-Patent Document 1] Journal of Photopolymer Science and Technology, Vol. 19, N0.3, 2006, 313-318

[Non-Patent Document 2] Journal of Photopolymer Science and Technology, Vol. 19, N0.3, 2006, 327-334

[Non-Patent Document 3] Journal of Photopolymer Science and Technology, Vol. 18, N0.3, 2005, 381-387

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and in the photolithography using a high energy ray such as an ArF excimer laser light as a light source, a positive resist capable of providing a pattern with improved resolution and reduced mask fidelity, particularly LER, can be provided. It is an object to provide a material and a pattern forming method using the resist material.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, as a result, the positive resist material which makes the sulfonium salt compound which has a specific structure into an acid generator is made into the base resin using the high molecular compound comprised by the specific repeating unit. Mask fidelity can be secured while having high resolution performance, and in particular, LER has also been found to be a very useful resist material for small precise microfabrication.

That is, the present invention provides the following positive resist material and pattern forming method.

Claim 1:

A resin component (A) which is soluble in an alkaline developer by the action of an acid, and a compound (B) which generates an acid in response to actinic radiation or radiation, wherein the resin component (A) is represented by the following formula (1) A positive resist material, wherein the compound (B) generating a acid is a sulfonium salt compound represented by the following formula (2).

(Wherein R ¹ each independently represents a hydrogen atom or a methyl group. R ² represents a fluorine-containing substituent having 1 to 15 carbon atoms. N is 1 or 2. a, b, c, and d are each a repeating unit. A, b, c, and d are 0.01 or more and less than 1, respectively, and a + b + c + d = 1.)

(In formula, R <^3> , R <^4> , R <^5> represents a C1-C20 linear, branched or cyclic monovalent hydrocarbon group which may respectively contain a hydrogen atom or a hetero atom independently. R <^6> is hetero C7-C30 linear, branched or cyclic monovalent hydrocarbon group which may contain an atom.)

Claim 2:

The process of apply | coating the resist material of Claim 1 on a board | substrate, the process of exposing with high energy rays or an electron beam through a photomask after heat processing, and the process of developing using a developing solution after heat processing, It characterized by the above-mentioned. Pattern formation method.

Claim 3:

The pattern forming process which includes the process of apply | coating the resist material of Claim 1 on a board | substrate, the process of exposing with a high energy ray or an electron beam through a photomask after heat processing, and the process of developing using a developing solution after heat processing. In which a liquid having a refractive index of at least 1 is interposed between the resist coating film and the projection lens to perform liquid immersion exposure.

Claim 4:

The pattern forming process which includes the process of apply | coating the resist material of Claim 1 on a board | substrate, the process of exposing with a high energy ray or an electron beam through a photomask after heat processing, and the process of developing using a developing solution after heat processing. In which a protective film is further applied on the resist coating film, and a liquid immersion exposure is performed by interposing a liquid having a refractive index of 1 or more between the protective film and the projection lens.

The resist material of the present invention has very high resolution in microfabrication techniques, especially ArF lithography, and can provide good mask fidelity, in particular, a pattern with a small LER, which is very useful for precise microfabrication.

Hereinafter, the resist material of this invention is explained in full detail. Incidentally, in the following description, the asymmetric carbon may be present in the structure represented by the chemical formula, and enantiomers or diastereomers may be present, but in this case, these isomers are represented by one formula. Representatively. These isomers may be used alone or as a mixture.

The resist material of the present invention contains a resin component (A) which is soluble in an alkaline developer by the action of an acid, and a compound (B) which generates an acid in response to actinic radiation or radiation, wherein the resin component (A) It is a high molecular compound which has a repeating unit represented by General formula (1), and the compound (B) which generate | occur | produces an acid is a positive resist material characterized by the sulfonium salt compound represented by following General formula (2).

<Formula 1>

Here, in formula (1), each R ¹ independently represents a hydrogen atom or a methyl group. R ² represents a fluorine-containing substituent having 1 to 15 carbon atoms. n is 1 or 2.

Although the following can be illustrated specifically as a repeating unit represented by General formula (4a), It is not limited to this.

(R ¹ is as described above.)

a, b, c and d each represent the abundance of the repeating unit, and a, b, c and d are each 0.01 or more and less than 1, and a + b + c + d = 1. The preferable range of each abundance is as follows.

0.20≤a≤0.50, more preferably 0.25≤a≤0.40

0.10 ≦ b ≦ 0.30, more preferably 0.15 ≦ b ≦ 0.25

0.01 <c≤0.60, more preferably 0.05≤c≤0.45

0.01 <d ≦ 0.40, more preferably 0.05 ≦ d ≦ 0.30

In addition, a + b + c + d = 1 means that the total amount of the repeating units a, b, c, d in the polymer compound containing the repeating units a, b, c, d is 100 mol based on the total amount of all the repeating units. It is%.

<Formula 2>

In Formula 2, R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may include a hetero atom, and a hetero atom Specific examples of the hydrocarbon group which may include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl and n-hexyl groups , Cyclopentyl group, cyclohexyl group, ethylcyclopentyl group, butylcyclopentyl group, ethylcyclohexyl group, butylcyclohexyl group, adamantyl group, ethyl adamantyl group, butyl adamantyl group, and any carbon of these groups -O-, -S-, -SO-, -SO _2- , -NH-, -C (= O)-, -C (= O) O-, -C (= O) NH - group or a hetero-atom group, such as the insert, there can be mentioned groups substituted with any of functional groups such as hydrogen atoms are _{-OH, -NH 2, -CHO, -CO} 2 H. R ⁶ represents a linear, branched or cyclic monovalent hydrocarbon group having 7 to 30 carbon atoms which may contain a hetero atom, and specific examples thereof may be exemplified, but the present invention is not limited thereto.

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

In said Formula (1), the unit introduced by the abundance ratio a is a unit protected by the special tertiary alkyl-type protecting group which has an oxanorbornane ring in carboxylic acid. Since this protecting group has very high hydrophilicity compared with the conventional carboxylic acid protecting group, it has high affinity for the rinse liquid. Therefore, it is thought that the dissolution of the resin deprotected by the acid to the rinse liquid can be increased, and as a result, the LER of the pattern can be reduced. In addition, it is thought that the lactone unit introduced in the abundance ratio c and the fluorine-containing functional group unit introduced in the abundance ratio d can increase the developer affinity and further reduce the LER. However, since these lactone units and fluorine-containing functional group units have low acid diffusion suppressing ability and diffuse acid during post-exposure heat treatment (post-exposure bake, PEB), resolution performance such as exposure dose dependence, density dependence, and mask fidelity is achieved. Has a defect that worsens As a result of earnestly researching to solve such a problem, the present inventors have found that a 1,1,3,3,3-pentafluoropropanesulfonic acid derivative having a bulky partial structure or a functional group is an acid having a very low diffusivity. The sulfonium salt compound represented by the above formula (2) as the acid generating agent is very useful as an acid generator, and the combination of the sulfonium salt compound and the polymer compound having a repeating unit represented by the above formula (1) provides resolution and line edge roughness. The inventors found that an excellent resist material can be obtained, and the present invention has been completed.

Although the following are specifically mentioned as a preferable structure of a resin component (A), It is not limited to this.

When the weight average molecular weight (Mw) of the resin component (A) in this invention is measured using the gel permeation chromatography (GPC) by polystyrene conversion, it is 2,000-30,000, Preferably it is 3,000-20,000. If it is out of this range and the molecular weight is too small, a good pattern shape cannot be obtained. If the molecular weight is too high, the dissolution rate difference before and after exposure may not be secured, and resolution may decrease.

In addition, the said resin component (A) can be obtained by copolymerizing the (meth) acrylic acid ester derivative monomer corresponding to each repeating unit according to well-known methods, such as a radical polymerization method, and all the high molecular compounds of the Example mentioned later are required (meth ) Acrylic acid ester derivative monomer is copolymerized according to the conventional method of radical polymerization.

Although the following can be illustrated specifically as a preferable composition of the compound (B) which generate | occur | produces an acid in response to actinic light or a radiation, It is not limited to this.

Another resin component may be added to the resist material of this invention in addition to the resin component (A) which consists of a high molecular compound represented by the said General formula (1).

As a resin component different from a resin component (A) here, although the weight average molecular weight 1,000-100,000, Preferably 3,000-30,000 high molecular compound represented by following General formula (R1) and / or following General formula (R2) is mentioned, It is not limited to. In addition, the said weight average molecular weight shows the polystyrene conversion value by gel permeation chromatography (GPC).

Here, R ⁰⁰¹ represents a hydrogen atom, a methyl group or CH ₂ CO ₂ R ⁰⁰³ .

R ⁰⁰² represents a hydrogen atom, a methyl group or CO ₂ R ⁰⁰³ .

R ⁰⁰³ represents a linear, 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, tert- Amyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, ethylcyclopentyl, butylcyclopentyl, ethylcyclohexyl, butylcyclohexyl, adamantyl, ethyladamantyl, A butyl adamantyl group etc. can be illustrated.

R ⁰⁰⁴ represents a monovalent hydrocarbon group containing at least one group selected from a hydrogen atom or a fluorine-containing substituent having 1 to 15 carbon atoms, a carboxyl group and a hydroxyl group, and specifically, a hydrogen atom, carboxyethyl, carboxybutyl, carboxycyclopentyl, Carboxycyclohexyl, Carboxynorbornyl, Carboxyadamantyl, Hydroxyethyl, Hydroxybutyl, Hydroxycyclopentyl, Hydroxycyclohexyl, Hydroxynorbornyl, Hydroxyadamantyl, [2,2,2 -Trifluoro-1-hydroxy-1- (trifluoromethyl) ethyl] cyclohexyl, bis [2,2,2-trifluoro-1-hydroxy-1- (trifluoromethyl) ethyl] Cyclohexyl etc. can be illustrated.

At least one of R ⁰⁰⁵ to R ⁰⁰⁸ represents a carboxyl group or a monovalent hydrocarbon group containing at least one group selected from a fluorine-containing substituent having 1 to 15 carbon atoms, a carboxyl group and a hydroxyl group, and the remaining ones each independently represent a hydrogen atom or carbon number 1 to 15 linear, branched or cyclic alkyl groups are represented. As a monovalent hydrocarbon group containing 1 or more types chosen from a C1-C15 fluorine-containing substituent, a carboxyl group, and a hydroxyl group, Specifically, carboxymethyl, carboxyethyl, carboxybutyl, hydroxymethyl, hydroxyethyl, hydroxybutyl 2-carboxyethoxycarbonyl, 4-carboxybutoxycarbonyl, 2-hydroxyethoxycarbonyl, 4-hydroxybutoxycarbonyl, carboxycyclopentyloxycarbonyl, carboxycyclohexyloxycarbonyl, Carboxynorbornyloxycarbonyl, carboxyadamantyloxycarbonyl, hydroxycyclopentyloxycarbonyl, hydroxycyclohexyloxycarbonyl, hydroxynorbornyloxycarbonyl, hydroxyadamantyl oxycarbonyl , [2,2,2-trifluoro-1-hydroxy-1- (trifluoromethyl) ethyl] cyclohexyloxycarbonyl, bis [2,2,2-trifluoro-1-hydroxy -1- (Triflu Romero naphthyl) ethyl] and the like can be given cyclohexyloxy Brassica Viterbo carbonyl.

As a C1-C15 linear, branched or cyclic alkyl group, the thing similar to what was illustrated by R <^003> can be illustrated specifically ,.

R ⁰⁰⁵ to R ⁰⁰⁸ (two of these, for example R ⁰⁰⁵ and R ⁰⁰⁶ , R ⁰⁰⁶ and R ⁰⁰⁷ , R ⁰⁰⁷ and R ^008, etc.) may combine with each other to form a ring with the carbon atoms to which they are bonded In this case, at least one of R ⁰⁰⁵ to R ⁰⁰⁸ represents a divalent hydrocarbon group containing at least one group selected from a fluorine-containing substituent having 1 to 15 carbon atoms, a carboxyl group and a hydroxyl group, and the rest are each independently a single bond or hydrogen. A straight or branched or cyclic alkyl group having 1 to 15 carbon atoms is represented. As a bivalent hydrocarbon group containing 1 or more types chosen from a C1-C15 fluorine-containing substituent, a carboxyl group, and a hydroxyl group, Specifically, the monovalent hydrocarbon group containing 1 or more types chosen from the said fluorine-containing substituent, a carboxyl group, and a hydroxyl group is mentioned. The thing etc. which removed one hydrogen atom from what was illustrated can be illustrated. Specific examples of the linear, branched or cyclic alkyl group having 1 to 15 carbon atoms include those exemplified for R ⁰⁰³ .

R ⁰⁰⁹ represents a monovalent hydrocarbon group containing a C3-C15 -CO ₂ -partial structure, specifically 2-oxooxolan-3-yl, 4,4-dimethyl-2-oxooxolane-3- Il, 4-methyl-2-oxooxan-4-yl, 2-oxo-1,3-dioxolan-4-ylmethyl, 5-methyl-2-oxooxolan-5-yl, etc. can be illustrated. have.

At least one of R ⁰¹⁰ to R ⁰¹³ represents a monovalent hydrocarbon group containing a -CO ₂ -substructure having 2 to 15 carbon atoms, and the others are each independently a hydrogen atom or a straight, branched or cyclic ring having 1 to 15 carbon atoms An alkyl group is shown. 2 to 15 carbon atoms of -CO ₂ - Examples of the monovalent hydrocarbon group containing a partial structure, specifically, 2-oxo-3-yloxy oxide solran Brassica Viterbo carbonyl, 4,4-dimethyl-2-oxo-3-oxide solran Iloxycarbonyl, 4-methyl-2-oxooxan-4-yloxycarbonyl, 2-oxo-1,3-dioxolan-4-ylmethyloxycarbonyl, 5-methyl-2-oxooxolane- 5-yloxycarbonyl etc. can be illustrated. As a C1-C15 linear, branched or cyclic alkyl group, the thing similar to what was illustrated by R <^003> can be illustrated specifically ,.

R ⁰¹⁰ to R ⁰¹³ (two of these, for example R ⁰¹⁰ and R ⁰¹¹ , R ⁰¹¹ and R ⁰¹² , R ⁰¹² and R ^013, etc.) may combine with each other to form a ring with the carbon atoms to which they are bonded In that case, at least one of R ⁰¹⁰ to R ⁰¹³ represents a divalent hydrocarbon group containing a C 1 -C 15 -CO ₂ -substructure, and the rest are each independently a single bond, a hydrogen atom or a C 1 -C 15 group. Linear, branched or cyclic alkyl groups. 1 to 15 carbon atoms of -CO ₂ - Examples of the divalent hydrocarbon group containing a partial structure, specifically, 1-oxide-2-oxa-1,3-small-diyl, 1,3-dioxo-2-oxa-propane -1,3-diyl, 1-oxo-2-oxabutane-1,4-diyl, 1,3-dioxo-2-oxabutane-1,4-diyl and the like, the -CO ₂ -partial structure The thing etc. which removed one hydrogen atom from what was illustrated by the containing monovalent hydrocarbon group can be illustrated. Specific examples of the linear, branched or cyclic alkyl group having 1 to 15 carbon atoms include those exemplified for R ⁰⁰³ .

R ⁰¹⁴ represents a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group, and specifically, norbornyl, bicyclo [3.3.1] nonyl, tricyclo [5.2.1.0 ^2,6 ] decyl , Adamantyl, norbornylmethyl, adamantylmethyl and alkyl or cycloalkyl substituents thereof and the like can be exemplified.

R ⁰¹⁵ represents an acid labile group, and specific examples thereof will be described later.

R ⁰¹⁶ represents a hydrogen atom or a methyl group.

R ⁰¹⁷ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, specifically, 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. can be illustrated.

X represents CH ₂ or an oxygen atom.

k is 0 or 1;

Various acid labile groups of R ⁰¹⁵ may be used, but any of the known acid labile groups conventionally used in resist materials, particularly chemically amplified resist materials, are groups that are deprotected by an acid generated from a photoacid generator described below. Although specifically, the group represented by the following formulas (L1) to (L4), a C4-C20, preferably a C3-C15 tertiary alkyl group, each alkyl group each has a C1-C6 trialkylsilyl group, And an oxoalkyl group having 4 to 20 carbon atoms.

Here, the broken line indicates the number of bonds.

In the formula (L1), R ^L01 and R ^L02 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 hydrogen atom, a methyl group, an ethyl group, A propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, adamantyl group, etc. can be illustrated. . R ^L03 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, and a linear, branched or cyclic alkyl group, and a part of these hydrogen atoms is hydroxyl, alkoxy The thing substituted by group, an oxo group, an amino group, an alkylamino group, etc. can be mentioned, Specifically, the same thing as said ^RL01 , ^RL02 can be illustrated as a linear, branched, or cyclic alkyl group, As a substituted alkyl group, Etc. can be illustrated.

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

In formula (L2), R ^L04 is a C4-C20, preferably a C4- ^C15 tertiary alkyl group, each alkyl group has a C1-C6 trialkylsilyl group, a C4-C20 oxoalkyl group or the above formula The group represented by (L1) is specifically represented as tert-butyl group, tert-amyl group, 1,1-diethylpropyl group, 2-cyclopentylpropan-2-yl group, 2-cyclohexyl propane -2-yl group, 2- (bicyclo [2.2.1] heptan-2-yl) propan-2-yl group, 2- (adamantan-1-yl) propan-2-yl group, 2- (tricyclo [ 5.2.1.0 ^2,6 ] decane-8-yl) propan-2-yl group, 2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane-3-yl) propan-2-yl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2 -Methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 8-methyl-8-tricyclo [5.2.1.0 ^2,6 ] decyl, 8- Ethyl-8-tricyclo [5.2.1.0 ^2,6 ] decyl, 3-methyl-3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecyl, 3-ethyl-3-tetracyclo [4.4 .0.1 ^2,5 .1 ^7,10 ] dodecyl and the like, and specific examples of the trialkylsilyl group include trimethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group and the like. Specific examples of the oxoalkyl group include 3-oxocyclohexyl group, 4-methyl-2-oxooxan-4-yl group, 5-methyl-2-oxooxolane-5-yl group and the like. y is an integer of 0-6.

In formula (L3), R ^L05 represents a linear, branched or cyclic alkyl group which may be substituted with 1 to 10 carbon atoms, or an aryl group which may be substituted with 6 to 20 carbon atoms, and specifically, an alkyl group which may be substituted 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, b Linear, branched or cyclic alkyl groups such as cyclo [2.2.1] heptyl group, and some of these hydrogen atoms are hydroxyl, alkoxy, carboxyl, alkoxycarbonyl, oxo, amino, alkylamino, cyano, mercapto, alkyl A thio group, a sulfo group, or the like, or a part of these methylene groups are substituted with an oxygen atom or a sulfur atom, and the like. Examples of the aryl group which may be substituted include a phenyl group, a methylphenyl group and a naphthyl group. , Antril , It may be mentioned, such as phenanthryl group, a pyrenyl group. m is 0 or 1, n is any of 0, 1, 2, 3, and is a number which satisfy | fills 2m + n = 2 or 3.

In formula (L4), R ^L06 represents a linear, branched or cyclic alkyl group which may be substituted with 1 to 10 carbon atoms, or an aryl group which may be substituted with 6 to 20 carbon atoms, and specifically the same as R ^L05 . Can be illustrated. R ^L07 To R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 15 carbon atoms, and specifically, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, sec-butyl group, tert- Butyl, tert-amyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl and cyclo Linear, branched or cyclic alkyl groups such as pentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group and cyclohexylbutyl group, and some of these hydrogen atoms are hydroxyl group, alkoxy group, carboxyl group, alkoxycarbonyl group, oxo group, amino group, alkylamino group And cyano group, mercapto group, alkylthio group, sulfo group and the like and the like. R ^L07 to R ^L16 may combine with each other to form a ring together with the carbon atom to which they are bonded (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 , and the like, in which case a divalent hydrocarbon group having 1 to 15 carbon atoms is shown, and specifically, one hydrogen atom is removed from the exemplified above monovalent hydrocarbon group. Thing etc. can be illustrated. In addition, R ^L07 to R ^L16 may be bonded to adjacent carbons without any intervening ones to form a double bond (for example, R ^L07 and R ^L09 , R ^L09 and R ^L15 and R ^L13 and R ^L15 Etc).

Specific examples of the linear or branched group among the acid labile groups represented by the general formula (L1) include the following groups.

As an cyclic thing among the acid labile groups represented by the said general formula (L1), specifically, the tetrahydrofuran-2-yl group, 2-methyl tetrahydrofuran-2-yl group, the tetrahydropyran-2-yl group, and 2-methyl tetra Hydropyran-2-yl group etc. can be illustrated.

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

Specific examples of the acid labile group of formula (L3) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl and 1- sec-butylcyclopentyl, 1-cyclohexylcyclopentyl, 1- (4-methoxybutyl) cyclopentyl, 1- (bicyclo [2.2.1] heptan-2-yl) cyclopentyl, 1- (7- Oxabicyclo [2.2.1] heptan-2-yl) cyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-methyl-2-cyclopentenyl, 1-ethyl-2-cyclopentenyl, 1 -Methyl-2-cyclohexenyl, 1-ethyl-2-cyclohexenyl, etc. can be illustrated.

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

In the formulas (L4-1) to (L4-4), the broken line indicates the bonding position and the bonding direction. R ^L41 each independently represents a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and specifically, 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. can be illustrated.

Enantiomers or diastereomers may be present in the above formulas (L4-1) to (L4-4), but the above formulas (L4-1) to (L4-4) are all stereoisomers. Representatively. These stereoisomers may be used alone or as a mixture.

For example, the said general formula (L4-3) shall represent and represent 1 type or 2 types of mixtures chosen from the group represented by the following general formula (L4-3-1) and (L4-3-2).

In addition, the said general formula (L4-4) shall represent the 1 type, or 2 or more types of mixtures chosen from the group represented by the following general formula (L4-4-1)-(L4-4-4).

Formulas (L4-1) to (L4-4), (L4-3-1), (L4-3-2) and (L4-4-1) to (L4-4-4) are enan Thio isomers and enantio isomer mixtures are also represented representatively.

Also, the bonding directions of the formulas (L4-1) to (L4-4), (L4-3-1), (L4-3-2) and (L4-4-1) to (L4-4-4) Since each of these is an exo side with respect to a bicyclo [2.2.1] heptane ring, high reactivity in an acid catalyst removal reaction is implement | achieved (refer Unexamined-Japanese-Patent No. 2000-336121). In the preparation of monomers having tertiary exo-alkyl groups having these bicyclo [2.2.1] heptane skeletons as substituents, endo-alkyl groups represented by the following formulas (L4-1-endo) to (L4-4-endo) Although it may contain the monomer substituted by, in order to implement | achieve favorable reactivity, it is preferable that an exo ratio is 50 mol% or more, and it is more preferable that an exo ratio is 80 mol% or more.

As an acid labile group of the said general formula (L4), the following group can be illustrated specifically ,.

Moreover, as a C4-C20 tertiary alkyl group, each alkyl group, a C1-C6 trialkylsilyl group, a C4-C20 oxoalkyl group, specifically, the same thing as what was illustrated by ^RL04 , etc. can be illustrated, for example. have.

R ⁰¹⁶ represents a hydrogen atom or a methyl group. R ⁰¹⁷ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms.

a1 ', a2', a3 ', b1', b2 ', b3', c1 ', c2', c3 ', d1', d2 ', d3', e 'is a number greater than or equal to 1 and less than a1' + It satisfies a2 '+ a3' + b1 '+ b2' + b3 '+ c1' + c2 '+ c3' + d1 '+ d2' + d3 '+ e' = 1. f ', g', h ', i', j ', o', p 'are numbers of 0 or more and less than 1, and f' + g '+ h' + i '+ j' + o '+ p' = Satisfies 1 x ', y' and z 'are integers of 0 to 3 and satisfy 1≤x' + y '+ z'≤5 and 1≤y' + z'≤3.

Each repeating unit of the formulas (R1) and (R2) may introduce two or more kinds at the same time. By using a some unit as each repeating unit, the performance at the time of making it into a resist material can be adjusted.

In addition, that the sum of each said unit here 1 shows that the total amount of these repeating units in a high molecular compound containing each repeating unit is 100 mol% with respect to the total amount of all the repeating units.

Although the following can be illustrated specifically as a repeating unit introduce | transduced in composition ratio a1 'and the composition ratio f' in general formula (R2) in the said General formula (R1), It is not limited to this.

Although the following can be illustrated specifically as a repeating unit introduce | transduced in composition ratio b1 'in the said General formula (R1), It is not limited to this.

Although the following can be illustrated specifically as a repeating unit introduce | transduced into composition ratio g 'in composition ratio d1' and (R2) in the said General formula (R1), It is not limited to this.

Although the following can be illustrated specifically as a high molecular compound comprised by the repeating unit of composition ratio a1 ', b1', c1 ', and d1' in the said General formula (R1), It is not limited to this.

Although the following can be illustrated specifically as a high molecular compound comprised by the repeating unit of composition ratio a2 ', b2', c2 ', d2', and e 'in the said General formula (R1), It is not limited to this.

Although the following can be illustrated concretely as a high molecular compound comprised from the repeating unit of composition ratio a3 ', b3', c3 ', and d3' in the said General formula (R1), It is not limited to this.

Although the following are specifically mentioned as a high molecular compound of the said General formula (R2), It is not limited to this.

When the compounding quantity of the said other high molecular compound makes the total amount with the said resin component (A) of this invention 100 mass parts, Preferably it is 0-80 mass parts, More preferably, it is 0-60 mass parts, More preferably, it is 0-50. Although it is a mass part, when mix | blending, it is preferable to set it as 20 mass parts or more, especially 30 mass parts or more. When the compounding quantity of the said other high molecular compound is too big | large, the characteristic of the resin component (A) of this invention may not be exhibited, and a fall of resolution and deterioration of a pattern shape may be caused. In addition, the said other high molecular compound is not limited to 1 type, It can add 2 or more types. By using a plurality of high molecular compounds, the performance of the resist material can be adjusted.

The resist material of this invention is a compound (B) which generate | occur | produces an acid in response to actinic light or a radiation, and may contain (B ') other than the sulfonium compound represented by the said General formula (2). As the component (B '), any compound may be used as long as it generates an acid by high energy ray irradiation, and any known photoacid generator conventionally used as a resist material, particularly a chemically amplified resist material, may be used. Preferred photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethanes, N-sulfonyloxyimide, oxime-O-sulfonate acid generators, and the like. Although detailed below, these can be used individually or in mixture of 2 or more types.

Sulfonium salts are salts of sulfonium cations with sulfonates or bis (substituted alkyl sulfonyl) imides, tris (substituted alkyl sulfonyl) methides, and as the sulfonium cations, triphenylsulfonium, (4-tert-butoxyphenyl ) Diphenylsulfonium, bis (4-tert-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium, (3-tert-butoxyphenyl) diphenylsulfonium, bis (3 -tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) sulfonium, (3,4-di tert-butoxyphenyl) diphenylsulfonium, bis (3,4-di tert- Butoxyphenyl) phenylsulfonium, tris (3,4-ditert-butoxyphenyl) sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl ) Diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl Sulfonium, 2-naphthyldiphenylsulfonium, dimethyl 2-naphthylsulfonium, 4 Hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium, diphenylmethylsulfonium, dimethyl Phenylsulfonium, 2-oxo-2-phenylethylthiacyclopentanium, 4-n-butoxynaphthyl-1-thiacyclopentanium, 2-n-butoxynaphthyl-1-thiacyclopentanium, etc. Examples of the sulfonate include trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfonate, dodecafluorohexanesulfonate, pentafluoroethylperfluorocyclohexanesulfonate and heptadeca. Fluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, mesitylenesulfonate, 2 , 4,6-triisopropylbenzenesulfonate, toluene Sulfonate, benzenesulfonate, 4- (4'-toluenesulfonyloxy) benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, 2- Benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy) propanesulfonate, 1,1 , 3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1, 3,3,3-pentafluoro-2-proyloxypropanesulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 2- (4-tert-butyl Benzoyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 2-adamantanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 2-acetyl Oxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2-hydroxy Propanesulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate, 1,1-difluoro-2-naphthyl-ethanesulfonate, 1,1,2,2 -Tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] Dodeca-3-en-8-yl) ethanesulfonate, and the like. Examples of the bis (substituted alkyl sulfonyl) imide include bistrifluoromethylsulfonylimide, bispentafluoroethylsulfonylimide, Bisheptafluoropropylsulfonylimide, 1,3-propylenebissulfonylimide, and the like. Examples of the tris (substituted alkyl sulfonyl) methide include tristrifluoromethylsulfonylmethide, and these And sulfonium salts in combination.

Iodonium salts are salts of iodonium cations with sulfonates or bis (substituted alkyl sulfonyl) imides, tris (substituted alkyl sulfonyl) methides, and diphenyliodonium, bis (4-tert-butylphenyl) Aryl iodonium cations such as iodonium, 4-tert-butoxyphenylphenyl iodonium, 4-methoxyphenylphenyl iodonium and sulfonates, trifluoromethanesulfonate, pentafluoroethanesulfonate, Nonafluorobutanesulfonate, dodecafluorohexanesulfonate, pentafluoroethylperfluorocyclohexanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluoro Robenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, mesitylenesulfonate, 2,4,6-triisopropylbenzenesulfonate, toluenesulfonate, benzenesulfonate, 4 -(4-toluenesulfonyloxy) benzenesulfo Acetate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy) propanesulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfo Acetate, 2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2-proyloxypropanesulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 2- (4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropanesulfo Acetate, 2-adamantanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropane Fonate, 1,1-difluoro-2-naphthyl-ethanesulfonate, 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1 , 2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-en-8-yl) ethanesulfonate, and the like, and bis (substituted) Examples of the alkyl sulfonyl) imide include bistrifluoromethylsulfonylimide, bispentafluoroethylsulfonylimide, bisheptafluoropropylsulfonylimide, 1,3-propylenebissulfonylimide, and the like. Examples of the tris (substituted alkyl sulfonyl) methide include tristrifluoromethylsulfonylmethide, and iodonium salts of a combination thereof can be given.

Examples of sulfonyl diazomethane include bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (2-methylpropylsulfonyl) diazomethane and bis (1,1-dimethylethyl Sulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (perfluoroisopropylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) Diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (2-naphthylsulfonyl) diazomethane, bis (4-acetyloxyphenylsulfonyl) diazomethane, bis (4- Methanesulfonyloxyphenylsulfonyl) diazomethane, bis (4- (4-toluenesulfonyloxy) phenylsulfonyl) diazomethane, bis (4-n-hexyloxy) phenylsulfonyl) diazomethane, Bis (2-methyl-4- (n-hexyloxy) phenylsulfonyl) diazomethane, bis (2,5-dimethyl-4- (n-hexyloxy) phenylsulfonyl) diazomethane, bis ( 3,5-dimethyl-4- (n-hexyloxy) phenylsulfonyl) diazomethane, bis (2- Methyl-5-isopropyl-4- (n-hexyloxy) phenylsulfonyl) diazomethane, 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, 2 Bissulfonyl such as naphthylsulfonylbenzoyldiazomethane, 4-methylphenylsulfonyl 2-naphthoyldiazomethane, methylsulfonylbenzoyldiazomethane and tert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane Diazomethane and sulfonyl-carbonyl diazomethane are mentioned.

Examples of the N-sulfonyloxyimide type photoacid generator include succinimide, naphthalenedicarboxylic acid imide, phthalic acid imide, cyclohexyl dicarboxylic acid imide, 5-norbornene-2,3-dicarboxylic acid imide, Imide skeleton, such as 7-oxabicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid imide, trifluoromethanesulfonate, pentafluoroethanesulfonate, and nonafluorobutanesulfonate , Dodecafluorohexanesulfonate, pentafluoroethylperfluorocyclohexanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4 Trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, mesitylenesulfonate, 2,4,6-triisopropylbenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate , Octanesulfonate, dodecyl Gensulfonate, butanesulfonate, methanesulfonate, 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy) propanesulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3 , 3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2-proyloxypropanesulfonate, 2-naphthoyloxy-1,1,3,3,3-penta Fluoropropanesulfonate, 2- (4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 2-adamantanecarbonyloxy-1,1,3, 3,3-pentafluoropropanesulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2-hydride Oxypropanesulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate, 1,1-difluoro-2-naphthyl-ethanesulfonate, 1,1,2, 2-tetrafluor Rho-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca- And compounds of a combination such as 3-en-8-yl) ethanesulfonate.

Examples of the benzoin sulfonate type photoacid generator include benzointosylate, benzoin mesylate, benzoin butanesulfonate, and the like.

As the pyrogallol trisulfonate type photoacid generator, all of the hydroxyl groups of pyrogallol, fluoroglycinol, catechol, resorcinol, and hydroquinone may be substituted with trifluoromethanesulfonate, pentafluoroethanesulfonate, and nonafluoro Robutanesulfonate, dodecafluorohexanesulfonate, pentafluoroethylperfluorocyclohexanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzene Sulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfo , Methanesulfonate, 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy Propanesulfonate, 1,1,3 , 3,3-pentafluoro-2-pivaloyloxypropanesulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3, 3,3-pentafluoro-2-proyloxypropanesulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 2- (4-tert-butylbenzoyloxy ) -1,1,3,3,3-pentafluoropropanesulfonate, 2-adamantanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 2-acetyloxy- 1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate, 1,1,3,3,3-penta Fluoro-2-tosyloxypropanesulfonate, 1,1-difluoro-2-naphthyl-ethanesulfonate, 1,1,2,2-tetrafluoro-2- (norbornan-2-yl ) Ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-en-8-yl) ethanesulfonate, etc. The compound substituted by the above is mentioned.

Examples of the nitrobenzylsulfonate type photoacid generator include 2,4-dinitrobenzylsulfonate, 2-nitrobenzylsulfonate, and 2,6-dinitrobenzylsulfonate. Specific examples of the sulfonate include trifluoromethane sulfo , Pentafluoroethanesulfonate, nonafluorobutanesulfonate, dodecafluorohexanesulfonate, pentafluoroethylperfluorocyclohexanesulfonate, heptadecafluorooctanesulfonate, 2,2,2- Trifluoroethane tansulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octane Sulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-penta Fluoro-2- (4- Nylbenzoyloxy) propanesulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3- Pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2-proyloxypropanesulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropane Sulfonate, 2- (4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 2-adamantanecarbonyloxy-1,1,3,3,3 Pentafluoropropanesulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropanesulfo Nate, 1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate, 1,1-difluoro-2-naphthyl-ethanesulfonate, 1,1,2,2-tetra Fluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca -3-en-8-yl) ethanesulfonate, etc. Can be mentioned. Moreover, the compound which substituted the nitro group of the benzyl side by the trifluoromethyl group can also be used similarly.

Examples of sulfone type photoacid generators include bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane, 2,2-bis (phenylsulfonyl) propane, 2,2 -Bis (4-methylphenylsulfonyl) propane, 2,2-bis (2-naphthylsulfonyl) propane, 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2-cyclohexylcarbonyl-2 -(p-toluenesulfonyl) propane, 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one, and the like.

The glyoxime derivative type photoacid generator can mention the compound of Unexamined-Japanese-Patent No. 2906999 and Unexamined-Japanese-Patent No. 9-301948, Specifically, bis-O- (p-toluenesulfonyl) -alpha. -Dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-O- (p -Toluenesulfonyl) -2,3-pentanedioneglyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylgly Oxime, bis-O- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-O- (2,2,2-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (10-camphorsulfonyl) -α-dimethylglyoxime, Bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O- (p- Lifluoromethylbenzenesulfonyl) -α-dimethylglyoxime, bis-O- (xylenesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -nioxime, bis-O -(2,2,2-trifluoroethanesulfonyl) -nioxime, bis-O- (10-camphorsulfonyl) -nioxime, bis-O- (benzenesulfonyl) -nioxime, bis-O -(p-fluorobenzenesulfonyl) -nioxime, bis-O- (p-trifluoromethylbenzenesulfonyl) -nioxime, bis-O- (xylenesulfonyl) -nioxime, etc. are mentioned. .

In addition, the oxime sulfonates described in US Pat. No. 6004724, in particular (5- (4-toluenesulfonyl) oxyimino-5H-thiophen-2-ylidene) phenylacetonitrile, (5- (10-campo) Sulfonyl) oxyimino-5H-thiophen-2-ylidene) phenylacetonitrile, (5-n-octanesulfonyloxyimino-5H-thiophen-2-ylidene) phenylacetonitrile, (5- (4 -Toluenesulfonyl) oxyimino-5H-thiophen-2-ylidene) (2-methylphenyl) acetonitrile, (5- (10-camposulfonyl) oxyimino-5H-thiophen-2-ylidene) ( 2-methylphenyl) acetonitrile, (5-n-octanesulfonyloxyimino-5H-thiophen-2-ylidene) (2-methylphenyl) acetonitrile, and the like, and also described in US Pat. (5- (4- (4-toluenesulfonyloxy) benzenesulfonyl) oxyimino-5H-thiophen-2-ylidene) phenylacetonitrile, (5- (2,5-bis (4-toluenesulfonyl Oxy) benzenesulfonyl) oxyimino-5H-thiophene 2-ylidene) phenyl acetonitrile, etc. are mentioned. .

The oxime sulfonates described in US Pat. No. 6,627,38, Japanese Patent Application Laid-Open No. 2000-314956, in particular 2,2,2-trifluoro-1-phenyl-ethanone oxime-O-methylsulfonate, 2, 2,2-trifluoro-1-phenyl-ethanone oxime-O- (10-camphorylsulfonate), 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (4- Methoxyphenylsulfonate), 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (1-naphthylsulfonate), 2,2,2-trifluoro-1-phenyl- Ethanone oxime-O- (2-naphthylsulfonate), 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (2,4,6-trimethylphenylsulfonate), 2, 2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime-O- (10-camphorylsulfonate), 2,2,2-trifluoro-1- (4-methylphenyl) -eta Nonoxime-O- (methylsulfonate), 2,2,2-trifluoro-1- (2-methylphenyl) -ethanone oxime-O- (10-camphorylsulfonate), 2,2,2- Trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (10-camphorylsulfonei ), 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (1-naphthylsulfonate), 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (2-naphthylsulfonate), 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime -O- (10-camphorylsulfonate), 2,2,2-trifluuro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (1-naphthylsulfonate), 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (2-naphthylsulfonate), 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O-methylsulfonate, 2,2,2-trifluoro-1- (4-methylthiophenyl) -ethanone oxime-O-methylsulfonate, 2, 2,2-trifluoro-1- (3,4-dimethoxyphenyl) -ethanone oxime-O-methylsulfonate, 2,2,3,3,4,4,4-heptafluoro-1- Phenyl-butanone oxime-O- (10-camphorylsulfonate), 2,2,2-trifluoro-1- (phenyl) -ethanone oxime-O-methylsulfonate, 2,2,2-tri Fluoro-1- (phenyl) -ethanone oxime-O- 10-camphorylsulfonate, 2,2,2-trifluoro-1- (phenyl) -ethanone oxime-O- (4-methoxyphenyl) sulfonate, 2,2,2-trifluoro-1 -(Phenyl) -ethanone oxime-O- (1-naphthyl) sulfonate, 2,2,2-trifluoro-1- (phenyl) -ethanone oxime-O- (2-naphthyl) sulfonate , 2,2,2-trifluoro-1- (phenyl) -ethanone oxime-O- (2,4,6-trimethylphenyl) sulfonate, 2,2,2-trifluoro-1- (4 -Methylphenyl) -ethanone oxime-O- (10-camphoryl) sulfonate, 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime-O-methylsulfonate, 2,2 , 2-trifluoro-1- (2-methylphenyl) -ethanone oxime-O- (10-camphoryl) sulfonate, 2,2,2-trifluoro-1- (2,4-dimethylphenyl) Ethanone oxime-O- (1-naphthyl) sulfonate, 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (2-naphthyl) sulfo Nate, 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (10-camphoryl) sulfonate, 2,2,2-trifluoro- 1- (2,4,6-trimethyl Yl) -ethanone oxime-O- (1-naphthyl) sulfonate, 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (2- Naphthyl) sulfonate, 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O-methylsulfonate, 2,2,2-trifluoro-1- (4 -Thiomethylphenyl) -ethanone oxime-O-methylsulfonate, 2,2,2-trifluoro-1- (3,4-dimethoxyphenyl) -ethanone oxime-O-methylsulfonate, 2,2 , 2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- (4-methylphenyl) sulfonate, 2,2,2-trifluoro-1- (4-methoxyphenyl) -Ethanone oxime-O- (4-methoxyphenyl) sulfonate, 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- (4-dodecylphenyl) Sulfonate, 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O-octylsulfonate, 2,2,2-trifluoro-1- (4-thiomethylphenyl ) -Ethanone oxime-O- (4-methoxyphenyl) sulfonate, 2,2,2-trifluoro-1- (4-thiomethylphenyl) -ethanone oxime-O- (4-dode Phenyl) sulfonate, 2,2,2-trifluoro-1- (4-thiomethylphenyl) -ethanone oxime-O-octylsulfonate, 2,2,2-trifluoro-1- (4-thio Methylphenyl) -ethanone oxime-O- (2-naphthyl) sulfonate, 2,2,2-trifluoro-1- (2-methylphenyl) -ethanone oxime-O-methylsulfonate, 2,2, 2-trifluoro-1- (4-methylphenyl) -ethanone oxime-O-phenylsulfonate, 2,2,2-trifluoro-1- (4-chlorophenyl) -ethanone oxime-O-phenyl Sulfonate, 2,2,3,3,4,4,4-heptafluoro-1- (phenyl) -butanone oxime-O- (10-camphoryl) sulfonate, 2,2,2-trifluoro Rho-1-naphthyl-ethanone oxime-O-methylsulfonate, 2,2,2-trifluoro-2-naphthyl-ethanone oxime-O-methylsulfonate, 2,2,2-trifluoro Rho-1- [4-benzylphenyl] -ethanone oxime-O-methylsulfonate, 2,2,2-trifluoro-1- [4- (phenyl-1,4-dioxa-but-1- Yl) phenyl] -ethanone oxime-O-methylsulfonate, 2,2,2-trifluoro-1-naphthyl-ethanone oxime-O-propylsulfonate, 2,2,2-trifluoro-2-naphthyl-ethanone oxime-O-propylsulfonate, 2,2,2-trifluoro-1- [4-benzylphenyl] -ethanone oxime-O- Propylsulfonate, 2,2,2-trifluoro-1- [4-methylsulfonylphenyl] -ethanone oxime-O-propylsulfonate, 1,3-bis [1- (4-phenoxyphenyl) -2,2,2-trifluoroethanone oxime-O-sulfonyl] phenyl, 2,2,2-trifluoro-1- [4-methylsulfonyloxyphenyl] -ethanone oxime-O-propyl Sulfonate, 2,2,2-trifluoro-1- [4-methylcarbonyloxyphenyl] -ethanone oxime-O-propylsulfonate, 2,2,2-trifluoro-1- [6H, 7H-5,8-dioxonaphtho-2-yl] -ethanone oxime-O-propylsulfonate, 2,2,2-trifluoro-1- [4-methoxycarbonylmethoxyphenyl]- Ethanone oxime-O-propylsulfonate, 2,2,2-trifluoro-1- [4- (methoxycarbonyl)-(4-amino-1-oxa-penta-1-yl) -phenyl] Ethanone oxime-O-propylsulfonate, 2,2,2-trifluoro-1- [3,5-dimethyl-4-ethoxyphenyl] -eta Oxime-O-propylsulfonate, 2,2,2-trifluoro-1- [4-benzyloxyphenyl] -ethanone oxime-O-propylsulfonate, 2,2,2-trifluoro-1- [2-thiophenyl] -ethanone oxime-O-propylsulfonate and 2,2,2-trifluoro-1- [1-dioxa-thiophen-2-yl] -ethanone oxime-O-propyl Sulfonate, 2,2,2-trifluoro-1- (4- (3- (4- (2,2,2-trifluoro-1- (trifluoromethanesulfonyloxyimino) -ethyl) -Phenoxy) -propoxy) -phenyl) ethanone oxime (trifluoromethanesulfonate), 2,2,2-trifluoro-1- (4- (3- (4- (2,2,2,2) -Trifluoro-1- (1-propanesulfonyloxyimino) -ethyl) -phenoxy) -propoxy) -phenyl) ethanone oxime (1-propanesulfonate), 2,2,2-trifluoro -1- (4- (3- (4- (2,2,2-trifluoro-1- (1-butanesulfonyloxyimino) -ethyl) -phenoxy) -propoxy) -phenyl) ethanone Oxime (1-butanesulfonate) and the like, and also 2,2,2-triples described in the specification of US Pat. Oro-1- (4- (3- (4- (2,2,2-trifluoro-1- (4- (4-methylphenylsulfonyloxy) phenylsulfonyloxyimino) -ethyl) -phenoxy) -Propoxy) -phenyl) ethanone oxime (4- (4-methylphenylsulfonyloxy) phenylsulfonate), 2,2,2-trifluoro-1- (4- (3- (4- (2, 2,2-trifluoro-1- (2,5-bis (4-methylphenylsulfonyloxy) benzenesulfonyloxy) phenylsulfonyloxyimino) -ethyl) -phenoxy) -propoxy) -phenyl) eta Nonoxime (2,5-bis (4-methylphenylsulfonyloxy) benzenesulfonyloxy) phenylsulfonate) and the like.

Oximesulfonate α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, which is described in Japanese Patent Laid-Open No. 9-95479, Japanese Patent Laid-Open No. 9-230588, or as a prior art in the text; α- (p-chlorobenzenesulfonyloxyimino) -phenylacetonitrile, α- (4-nitrobenzenesulfonyloxyimino) -phenylacetonitrile, α- (4-nitro-2-trifluoromethylbenzenesulfonyl Oxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -4-chlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyl Oxyimino) -2,6-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylaceto Nitrile, α- (benzenesulfonyloxyimino) -2-thienylacetonitrile, α- (4-dodecylbenzenesulfonyloxyimino) -phenylacetonitrile , α-[(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α- (tosyloxy Mino) -3-thienylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (iso Propylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclohexenyl Acetonitrile, (alpha)-(isopropylsulfonyloxyimino) -1-cyclohexenyl acetonitrile, (alpha)-(n-butylsulfonyloxyimino) -1-cyclohexenyl acetonitrile, etc. are mentioned.

An oxime sulfonate represented by the following formula (for example, specific examples are described in WO2004 / 074242).

( ^Wherein R ^S1 represents a substituted or unsubstituted haloalkylsulfonyl or halobenzenesulfonyl group. R ^S2 represents a C1-C11 haloalkyl group. Ar ^S1 represents a substituted or unsubstituted. Aromatic groups or heteroaromatic groups.)

Specifically 2- [2,2,3,3,4,4,5,5-octafluoro-1- (nonafluorobutylsulfonyloxyimino) -pentyl] -fluorene, 2- [2, 2,3,3,4,4-pentafluoro-1- (nonafluorobutylsulfonyloxyimino) -butyl] -fluorene, 2- [2,2,3,3,4,4,5, 5,6,6-Decafluoro-1- (nonafluorobutylsulfonyloxyimino) -hexyl] -fluorene, 2- [2,2,3,3,4,4,5,5-octafluoro Rho-1- (nonafluorobutylsulfonyloxyimino) -pentyl] -4-biphenyl, 2- [2,2,3,3,4,4-pentafluoro-1- (nonafluorobutylsulphur) Ponyloxyimino) -butyl] -4-biphenyl, 2- [2,2,3,3,4,4,5,5,6,6-decafluoro-1- (nonnafluorobutylsulfonyloxyi Mino) -hexyl] -4-biphenyl etc. are mentioned.

Moreover, as bisoxime sulfonate, the compound of Unexamined-Japanese-Patent No. 9-208554, especially bis ((alpha)-(4-toluenesulfonyloxy) imino) -p-phenylenediacetonitrile, bis ( α- (benzenesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (methanesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (butanesulfonyl Oxy) imino) -p-phenylenediacetonitrile, bis (α- (10-camphorsulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (4-toluenesulfonyloxy) Imino) -p-phenylenediacetonitrile, bis (α- (trifluoromethanesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (4-methoxybenzenesulfonyloxy) Imino) -p-phenylenediacetonitrile, bis (α- (4-toluenesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (benzenesulfonyloxy) imino)- m-phenylenediacetonitrile, bis (α- (methanesulfonyloxy) imino) -m-phenyl Diacetonitrile, bis (α- (butanesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (10-camphorsulfonyloxy) imino) -m-phenylenediacetonitrile, Bis (α- (4-toluenesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (trifluoromethanesulfonyloxy) imino) -m-phenylenediacetonitrile, bis ((alpha)-(4-methoxybenzenesulfonyloxy) imino) -m-phenylenediacetonitrile etc. are mentioned.

Among them, preferred photoacid generators include sulfonium salts, bissulfonyldiazomethanes, N-sulfonyloxyimide, oxime-O-sulfonates, and glyoxime derivatives. More preferable photoacid generators are sulfonium salt, bissulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate. Specifically, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium pentafluorobenzenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium 4- ( 4'-toluenesulfonyloxy) benzenesulfonate, triphenylsulfonium-2,4,6-triisopropylbenzenesulfonate, 4-tert-butoxyphenyldiphenylsulfonium p-toluenesulfonate, 4-tert -Butoxyphenyldiphenylsulfonium camphorsulfonate, 4-tert-butoxyphenyldiphenylsulfonium 4- (4'-toluenesulfonyloxy) benzenesulfonate, tris (4-methylphenyl) sulfonium camphorsulfonate, Tris (4-tert butylphenyl) sulfonium camphorsulfonate, 4-tert-butylphenyldiphenylsulfonium camphorsulfonate, 4-tert-butylphenyldiphenylsulfonium nonafluoro-1-butanesulfonate, 4- tert-Butylphenyldiphenylsulfonium pentafluoroethylperfluorocyclohexanesulfonate, 4-tert-part Tylphenyldiphenylsulfonium perfluoro-1-octanesulfonate, triphenylsulfonium 1,1-difluoro-2-naphthyl-ethanesulfonate, triphenylsulfonium 1,1,2,2-tetra Fluoro-2- (norbornan-2-yl) ethanesulfonate, bis (tert-butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsul Ponyyl) diazomethane, bis (4-n-hexyloxy) phenylsulfonyl) diazomethane, bis (2-methyl-4- (n-hexyloxy) phenylsulfonyl) diazomethane, bis (2 , 5-dimethyl-4- (n-hexyloxy) phenylsulfonyl) diazomethane, bis (3,5-dimethyl-4- (n-hexyloxy) phenylsulfonyl) diazomethane, bis (2 -Methyl-5-isopropyl-4- (n-hexyloxy) phenylsulfonyl) diazomethane, bis (4-tert-butylphenylsulfonyl) diazomethane, N-camphorsulfonyloxy-5-nor Bornen-2,3-dicarboxylic acidimide, Np-toluenesulfonyloxy-5-norbornene-2,3-dicarboxylic acidimide, 2- [2,2,3,3,4,4 , 5,5-octafluoro-1- (no Fluorobutylsulfonyloxyimino) -pentyl] -fluorene, 2- [2,2,3,3,4,4-pentafluoro-1- (nonafluorobutylsulfonyloxyimino) -butyl]- Fluorene, 2- [2,2,3,3,4,4,5,5,6,6-decafluoro-1- (nonafluorobutylsulfonyloxyimino) -hexyl] -fluorene Can be mentioned.

Although the addition amount of the photo-acid generator (B) and (B ') in the resist material of this invention may be sufficient, 100 mass of base polymers (resin component (A) of this invention, and other resin components as needed) in a resist material. 0.1-40 mass parts with respect to a part, Preferably it is 0.1-20 mass parts. If the ratio of the photo-acid generator is too high, there is a possibility of deterioration of resolution and problems of foreign matters during development / resist stripping. About the compounding ratio of (B) and (B '), when each addition amount is set to [B] and [B'], Preferably 0.1 <= [B] / ([B] + [B ']) <= 1, more preferably 0.3 ≦ [B] / ([B] + [B ']) ≦ 1, and still more preferably 0.5 ≦ [B] / ([B] + [B']) ≦ 1. . If the blending ratio of the photoacid generator (B) is too low, the exposure dose dependence, the density dependence, and the mask fidelity may be deteriorated. In addition, the said photo-acid generator (B) and (B ') can also be used individually or in mixture of 2 or more types. Moreover, the transmittance | permeability in a resist film can also be controlled with the addition amount using the photo-acid generator with low transmittance | permeability in an exposure wavelength.

Moreover, the compound (acid propagation compound) which decomposes | dissolves with an acid and produces | generates an acid can also be added to the resist material of this invention. For these compounds, see J. Photopolym. Sci. and Tech., 8. 43-44, 45-46 (1995)], [J. Photopolym. Sci. and Tech., 9. 29-30 (1996).

Examples of the acid propagation compound include tert-butyl-2-methyl-2-tosyloxymethylacetoacetate, 2-phenyl-2- (2-tosyloxyethyl) -1,3-dioxolane, and the like. It doesn't happen. Among known photoacid generators, compounds having poor stability, particularly thermal stability, often exhibit acid propagation compounding properties.

As addition amount of the acid propagation compound in the resist material of this invention, it is 0-2 mass parts with respect to 100 mass parts of base polymers in a resist material, Preferably it is 0-1 mass part. When the addition amount is too large, it is difficult to control diffusion, resulting in deterioration of resolution and deterioration of pattern shape.

The resist material of this invention contains (C) organic solvent in addition to the said (A) and (B) component, and if necessary, (D) nitrogen-containing organic compound, (E) surfactant, (F) It may contain an external component.

As an organic solvent which is (C) component used by this invention, any may be sufficient as it is an organic solvent in which base resin, an acid generator, another additive, etc. can melt | dissolve. As such an organic solvent, for example, ketones such as cyclohexanone and methyl amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2 Alcohols such as propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether and the like, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether Esters, such as acetate, and lactones, such as (gamma) -butyrolactone, These can be mentioned individually or 2 types It can be used by mixing phase, but is not limited to this. In the present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate and the mixed solvent having the highest solubility of the acid generator in the resist component are preferably used.

As for the usage-amount of the organic solvent, 200-3,000 mass parts, especially 400-2,500 mass parts are preferable with respect to 100 mass parts of base polymers.

Moreover, 1 type (s) or 2 or more types can be mix | blended with the resist material of this invention as (D) component.

As the nitrogen-containing organic compound, a compound capable of suppressing the diffusion rate when the acid generated from the acid generator is diffused in the resist film is suitable. By blending the nitrogen-containing organic compound, the diffusion rate of the acid in the resist film is suppressed and the resolution is improved, the sensitivity change after exposure can be suppressed, or the substrate and the environmental dependence can be reduced, and the exposure margin and pattern profile can be improved. .

As such a nitrogen-containing organic compound, any known nitrogen-containing organic compound conventionally used in resist materials, particularly chemically amplified resist materials, may be used. Examples thereof include primary, secondary and tertiary aliphatic amines, hybrid amines, aromatic amines, Heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amides, imides, carbamate, and the like. Can be mentioned.

Specifically, as the primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amyl Amine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like are exemplified, and secondary aliphatic As amines, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, di Hexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyl tetraethylene pentamine etc. are illustrated, and tertiary aliphatic amines are mentioned. West trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexyl Amines, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethylmethylenediamine, N, N , N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyltetraethylenepentamine and the like are exemplified.

In addition, examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, and the like. 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-di Nitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g. pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole and the like), oxazole derivatives (e.g. oxazole, isoxazole, etc.), thiazole derivatives ( For example, thiazole, isothiazole, etc., imidazole derivatives (for example, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole) ), Pyrazole derivatives, furazane derivatives, pyrroline derivatives (e.g. pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g. pyrrolidine, N-methylpyrrolidine, Pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g. pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1- Butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimeth Oxypyridine, 4-pyrrolidinopyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivative, pyrimidine derivative, pyrazine derivative, pyrazoline derivative, pyrazolidine derivative, py Ferridine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, Smallindole derivatives, 1H-indazole derivatives, indolin derivatives, quinoline derivatives (e.g., quinoline, 3-quinolinecarbonitrile, etc.), 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 derivatives, guanine derivatives, guanosine derivatives, uracil Derivatives, uridine derivatives and the like.

As the nitrogen-containing compound having a carboxyl group, for example, aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (e.g., nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylosin, 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-pyridine sulfonic acid, p-toluene sulfonic acid pyridinium, and the like. As the nitrogen-containing compound having a hydroxyl group, the nitrogen-containing compound having a hydroxyphenyl group, the alcoholic nitrogen-containing compound, 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolmethanol hydrate, monoethanolamine, Diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodietan , 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-hydroxy Ethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-quinuclidinol, 3 -Tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. are illustrated. . As the amides, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, 1-cyclohexylpyrrolidone Etc. are illustrated. Phthalimide, succinimide, maleimide, etc. are illustrated as imides. Examples of carbamates include N-t-butoxycarbonyl-N, N-dicyclohexylamine, N-t-butoxycarbonylbenzimidazole, oxazolidinone and the like.

Moreover, the nitrogen containing organic compound represented by following General formula (B) -1 is illustrated.

(In the formula, n = 1, 2 or 3. The side chain X may be the same or different and may be represented by the following formulas (X1) to (X3).

The side chain Y represents the same or different hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may include an ether group or a hydroxyl group. In addition, Xs may be bonded to each other to form a ring.)

Here, R ³⁰⁰ , R ³⁰² and R ³⁰⁵ are linear or branched alkylene groups having 1 to 4 carbon atoms, R ³⁰¹ and R ³⁰⁴ are hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, and a hydroxy group One or more of an ether group, an ester group, and a lactone ring may be included.

R ³⁰³ is a single bond or a straight or branched alkylene group having 1 to 4 carbon atoms, R ³⁰⁶ is a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms, and a hydroxy group, ether group, ester group, or lactone ring One or more may be included.

Specific examples of the compound represented by the formula (B) -1 include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, and tris {2- (2- Methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1- Ethoxypropoxy) ethyl} amine, tris [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10- Diazabicyclo [8.8.8] hexacoic acid, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eichoic acid, 1,4,10,13-tetraoxa-7, 16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris (2-acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2- valeryloxy Ethyl) amine, tris (2- Valoyloxyoxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-tert- Butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycar Carbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine, N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N- Bis (2-hydroxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2- Hydroxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-methoxyethoxy Carbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2- Acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl ) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis ( 2-acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N- Bis (2-acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxy Carbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxy on Tyl) 2- (4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (4-formyloxybutoxycarbonyl) ethylamine, N, N- Bis (2-formyloxyethyl) 2- (2-formyloxyethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxy Hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1- Propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl ) Bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl ] Amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2- Cetoxyethyl) amine, N-methylbis (2-pivaloyloxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-part Methoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxy Carbonylmethyl) amine, β- (diethylamino) -δ-valerolactone are exemplified.

Moreover, the nitrogen containing organic compound which has a cyclic structure represented by following General formula (B) -2 is illustrated.

(Wherein, X is as described above, R ³⁰⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms, and may include one or a plurality of carbonyl, ether, ester or sulfide groups.)

Specific examples of the formula (B) -2 include 1- [2- (methoxymethoxy) ethyl] pyrrolidine, 1- [2- (methoxymethoxy) ethyl] piperidine, 4- [2- ( Methoxymethoxy) ethyl] morpholine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxyethoxy) methoxy] Ethyl] piperidine, 4- [2-[(2-methoxyethoxy) methoxy] ethyl] morpholine, 2- (1-pyrrolidinyl) ethyl acetate, 2-piperidinoethyl acetate, acetic acid 2 Morpholinoethyl, 2- (1-pyrrolidinyl) ethyl formic acid, 2-piperidinoethyl propionic acid, 2-morpholinoethyl, methoxyacetic acid 2- (1-pyrrolidinyl) ethyl, 4- [2- (methoxycarbonyloxy) ethyl] morpholine, 1- [2- (t-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycar Bonyloxy) ethyl] morpholine, 3- (1-pyrrolidinyl) methyl propionate, 3-piperidinopropionate methyl, 3-morpholinopropionate methyl, 3- (thiomorpholino) propionate , 2-methyl-3- (1-pyrrolidinyl) methyl propionate, ethyl 3-morpholinopropionate, 3-piperidinopropionic acid methoxycarbonylmethyl, 3- (1-pyrrolidinyl) propionic acid 2-hydride Oxyethyl, 3-morpholinopropionic acid 2-acetoxyethyl, 3- (1-pyrrolidinyl) propionic acid 2-oxotetrahydrofuran-3-yl, 3-morpholino propionic acid tetrahydrofurfuryl, 3-py Ferridinopropionic acid glycidyl, 3-morpholinopropionic acid 2-methoxyethyl, 3- (1-pyrrolidinyl) propionic acid 2- (2-methoxyethoxy) ethyl, 3-morpholinopropionate butyl, 3 -Piperidinopropionic acid cyclohexyl, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, 1 Methyl pyrrolidinyl acetate, methyl piperidinoacetic acid, methyl morpholino acetate, methyl thiomorpholinoacetic acid, ethyl 1-pyrrolidinyl acetate, morpholi 2-methoxyethyl acetate, 2-methoxyacetic acid 2-morpholinoethyl, 2- (2-methoxyethoxy) acetic acid 2-morpholinoethyl, 2- [2- (2-methoxyethoxy) Ethoxy] acetic acid 2-morpholinoethyl, hexanoic acid 2-morpholinoethyl, octanoic acid 2-morpholinoethyl, decanoic acid 2-morpholinoethyl, lauric acid 2-morpholinoethyl, myristic Acid 2-morpholinoethyl, palmitic acid 2-morpholinoethyl, stearic acid 2-morpholinoethyl are illustrated.

Moreover, the nitrogen containing organic compound containing the cyano group represented by the following general formula (B) -3-(B) -6 is illustrated.

( ^Wherein X, R ³⁰⁷ and n are as described above, and R ³⁰⁸ and R ³⁰⁹ are the same or different linear or branched alkylene groups having 1 to 4 carbon atoms.)

As the nitrogen-containing organic compound containing the cyano group represented by the formulas (B) -3 to (B) -6, specifically 3- (diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl ) -3-aminopropiononitrile, N, N-bis (2-acetoxyethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl) -3-aminopropiononitrile, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-sia Noethyl) -N- (2-methoxyethyl) -3-aminopropionate, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionate, N- (2 -Acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropionate, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyano Ethyl) -N- (2-hydroxyethyl) -3-aminopropiononitrile, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropy Nonnitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) -N -(3-hydroxy-1-propyl) -3-aminopropiononitrile, N- (3-acetoxy-1-propyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N -(2-cyanoethyl) -N- (3-formyloxy-1-propyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N-tetrahydrofurfuryl-3-amino Propiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N- Bis (2-acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [ 2- (methoxymethoxy) ethyl] aminoacetonitrile, N-cyanomethyl-N- (2-methoxyethyl) -3-aminopropionate, N-cyanomethyl-N- (2-hydroxyethyl ) -3-Aminopropionate, N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate, N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N -(2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile, N-cyanomethyl-N- (2 -Methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1- Propyl) aminoacetonitrile, N- (3-acetoxy-1-propyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) amino Acetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidine Lopiononitrile, 4-morpholin propiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, 3-diethylaminopropionate cyanomethyl, N, N- Bis (2-hydroxyethyl) -3-aminopropionate cyanomethyl, N, N-bis (2-acetoxyethyl) -3-aminopropionate cyanomethyl, N, N-bis (2-formyloxyethyl ) -3-aminopropionate cyanomethyl, N, N-bis (2-methoxyethyl) -3-aminopropionate cyanomethyl, N, N-bis [2- (methoxymethoxy) ethyl] -3- Cyanomethyl aminopropionate, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-formyloxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N- Bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2- ( Methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl), 1-pyrrolidine propanoic acid cyanomethyl, 1-piperidine propionate cyanomethyl, 4-morpholine propionate cyanomethyl, 1- Pyrrolidine propionic acid (2-cyanoethyl), 1-piperidine propionic acid (2-cyanoethyl), 4-morpholine propionic acid (2-cyanoethyl), etc. are illustrated.

Moreover, the nitrogen containing organic compound which has an imidazole skeleton and a polar functional group represented by following General formula (B) -7 is illustrated.

(In the formula, R ³¹⁰ is an alkyl group having a linear, branched or cyclic polar functional group having 2 to 20 carbon atoms. As the polar functional group, a hydroxyl group, a carbonyl group, an ester group, an ether group, a sulfide group, a carbonate group, Any one or a plurality of cyano groups and acetal groups, wherein R ³¹¹ , R ³¹² , and R ³¹³ are hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups or aralkyl groups.)

Moreover, the nitrogen containing organic compound which has the benzimidazole skeleton represented by the following general formula (B) -8 and a polar functional group is illustrated.

(Wherein, R ³¹⁴ is a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group or an aralkyl group having 1 to 10 carbon atoms. R ³¹⁵ is a linear, branched or cyclic polar functional group having 1 to 20 carbon atoms. An alkyl group having at least one of ester, acetal and cyano, and at least one of hydroxyl, carbonyl, ether, sulfide and carbonate groups. May be.)

Moreover, the nitrogen-containing heterocyclic compound which has a polar functional group represented by following formula (B) -9 and (B) -10 is illustrated.

(Wherein A is a nitrogen atom or —CR ^322. B is a nitrogen atom or —CR ^323. R ³¹⁶ is an alkyl group having a linear, branched or cyclic polar functional group having 2 to 20 carbon atoms, and as a polar functional group) At least one hydroxyl group, carbonyl group, ester group, ether group, sulfide group, carbonate group, cyano group or acetal group R ³¹⁷ , R ³¹⁸ , R ³¹⁹ , R ³²⁰ are hydrogen atoms, R ³¹⁷ and R ³¹⁸ , R ³¹⁹ and R ³²⁰ may be bonded to each other to form a benzene ring, naphthalene ring or pyridine ring, R ³²¹ may be a hydrogen atom, straight, branched having 1 to 10 carbon atoms is a branched or cyclic alkyl group, or an aryl group. R ^322, R ³²³ is a straight-chain hydrogen atoms, having 1 to 10 carbon atoms, branched or cyclic alkyl group, or an aryl group. R ³²¹ and R ³²³ is a benzene ring or a naphthalene ring by combining Can be formed.)

Moreover, the nitrogen containing organic compound which has an aromatic carboxylic acid ester structure represented by following General formula (B) -11-(B) -14 is illustrated.

(Wherein, R ³²⁴ is an aryl group having 6 to 20 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms, and some or all of the hydrogen atoms are halogen atoms, straight, branched or cyclic alkyl groups having 1 to 20 carbon atoms, carbon atoms is 6 to 20 aryl group, an alkoxy group having a carbon number of 7 to 20, an aralkyl group, having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or may be substituted with an alkylthio group having 1 to 10 carbon atoms. R ³²⁵ is CO ₂ R ³²⁶ , OR ³²⁷ or a cyano group R ³²⁶ is an alkyl group having 1 to 10 carbon atoms in which some methylene groups may be substituted with oxygen atoms, and R ³²⁷ is an alkyl group having 1 to 10 carbon atoms in which some methylene groups may be substituted with oxygen atoms; Is an alkyl group or an acyl group R ³²⁸ is a single bond, methylene group, ethylene group, sulfur atom or —O (CH ₂ CH ₂ O) _n — group n is 0, 1, 2, 3 or 4. R ³²⁹ Is a hydrogen atom, a methyl group, an ethyl group or a phenyl group. Is a nitrogen atom or CR ^330. Y is a nitrogen atom or CR ^331. Z is a nitrogen atom or CR ^332. R ³³⁰ , R ³³¹ , R ³³² are each independently a hydrogen atom, a methyl group or a phenyl group, or R ³³⁰ and R ³³¹ or R ³³¹ and R ³³² may combine to form an aromatic ring having 6 to 20 carbon atoms or a heteroaromatic ring having 2 to 20 carbon atoms.)

Moreover, the nitrogen containing organic compound which has a 7-oxanorbornan 2-carboxylic acid ester structure represented by following General formula (B) -15 is illustrated.

(Wherein, R ³³³ is hydrogen or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. R ³³⁴ and R ³³⁵ are each independently ether, carbonyl, ester, alcohol, sulfide, nitrile, amine , An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, which may contain one or a plurality of polar functional groups such as imine, amide, and the like. R ³³⁴ and R ³³⁵ may combine with each other to form a hetero ring or heteroaromatic ring having 2 to 20 carbon atoms.)

Moreover, it is preferable that the compounding quantity of a nitrogen containing organic compound is 0.001-4 mass parts, especially 0.01-2 mass parts with respect to 100 mass parts of all base resins. If the blending amount is less than 0.001 part by mass, there is no blending effect. If the blending amount exceeds 4 parts by mass, the sensitivity may be too low.

In addition to the above components, a commonly used surfactant can be added to the resist material of the present invention in order to improve applicability. In addition, the addition amount of an arbitrary component can be used as a normal amount in the range which does not prevent the effect of this invention.

As the surfactant, nonionic ones are preferable, and perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkyl EO adduct, fluorine-containing organosiloxane compound and the like Can be mentioned. For example, Florade "FC-430", "FC-431" (all are manufactured by Sumitomo 3M Corporation), Saffron "S-141", "S-145", "KH-10", "KH-" 20 "," KH-30 "," KH-40 "(all Asahi Glass Co., Ltd. make), United" DS-401 "," DS-403 "," DS-451 "(all Daikin high school (note) ) Manufacture), mega pack "F-8151" (made by Dainippon Ink Industries Co., Ltd.), "X-70-092", "X-70-093" (all Shin-Etsu Chemical Co., Ltd. make) Can be mentioned. Preferably, Flora "FC-430" (made by Sumitomo 3M Co., Ltd.), "KH-20", "KH-30" (all are manufactured by Asahi Glass Co., Ltd.), "X-70-093" (New) Saga Chemical Co., Ltd. product) is mentioned.

In the resist material of the present invention, any component other than the above components is ubiquitous on the top of the coating film, and the hydrophilic and hydrophobic balance of the surface is adjusted or the water repellency is increased, or when the coating film is in contact with water or other liquid, It is also possible to add a polymer compound having a function of preventing inflow. In addition, the addition amount of the said high molecular compound can be used as a normal amount in the range which does not prevent the effect of this invention.

Here, as a high molecular compound ubiquitous on a coating film, the polymer containing a 1 type, or 2 or more types of fluorine-containing unit, the copolymer, and the copolymer containing a fluorine-containing unit and other units are preferable. Although the following can be illustrated specifically as a fluorine-containing unit and other units, It is not limited to this.

The weight average molecular weight of the high molecular compound ubiquitous on the coating film is preferably 1,000 to 50,000, more preferably 2,000 to 20,000. If it deviates from this range, surface modification effect may not be enough or a development defect may arise. In addition, the said weight average molecular weight shows the polystyrene conversion value by gel permeation chromatography (GPC).

Other components, such as a dissolution control agent, a carboxylic acid compound, an acetylene alcohol derivative, can also be further added to the resist material of this invention as an optional component as needed. In addition, the addition amount of an arbitrary component can be used as a normal amount in the range which does not prevent the effect of this invention.

As a dissolution control agent which can be added to the resist material of the present invention, the weight average molecular weight is 100 to 1,000, preferably 150 to 800, and the hydrogen of the phenolic hydroxyl group of the compound having two or more phenolic hydroxyl groups in the molecule. Substituting an atom with an acid labile group at an average of 0 to 100 mol% as a whole or replacing a hydrogen atom of the carboxyl group of a compound having a carboxyl group with an acid labile group at an average of 50 to 100 mol% as a whole with an acid labile group One compound may be blended.

In addition, the substitution rate of the hydrogen atom of the phenolic hydroxyl group by the acid labile group is 0 mol% or more, preferably 30 mol% or more of the whole phenolic hydroxyl group on average, The upper limit is 100 mol%, More preferably, 80 mol% to be. The substitution rate by the acid labile group of the hydrogen atom of a carboxy group is 50 mol% or more of the whole carboxy group on average, Preferably it is 70 mol% or more, and the upper limit is 100 mol%.

In this case, as a compound which has two or more such phenolic hydroxyl groups, or a compound which has a carboxyl group, what is represented by following General formula (D1)-(D14) is preferable.

In said formula, R <^201> and R <^202> represent a hydrogen atom or a C1-C8 linear or branched alkyl group or alkenyl group, respectively, For example, a hydrogen atom, a methyl group, an ethyl group, a butyl group, a propyl group, an eti A silyl group and a cyclohexyl group are mentioned.

R ²⁰³ is a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or-(R ²⁰⁷ ) _h COOH (wherein R ²⁰⁷ is a straight or branched alkylene having 1 to 10 carbon atoms) Group), and the same as R ²⁰¹ , R ²⁰² , or -COOH, -CH ₂ COOH.

R ²⁰⁴ represents-(CH ₂ ) _i- (i = 2 to 10), an arylene group, carbonyl group, sulfonyl group, oxygen atom or sulfur atom having 6 to 10 carbon atoms, for example, an ethylene group, a phenylene group, a carbonyl group, Sulfonyl group, an oxygen atom, a sulfur atom, etc. are mentioned.

R ²⁰⁵ represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom, or a sulfur atom, and examples thereof include the same as the methylene group or R ²⁰⁴ .

R ²⁰⁶ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a phenyl group or a naphthyl group in which at least one of each hydrogen atom is substituted with a hydroxyl group, for example, a hydrogen atom, a methyl group And an ethyl group, a butyl group, a propyl group, an ethynyl group, a cyclohexyl group, a phenyl group in which at least one of each hydrogen atom is substituted with a hydroxyl group, and a naphthyl group.

R ²⁰⁸ represents a hydrogen atom or a hydroxyl group.

j is an integer of 0-5. u, h is 0 or 1; s, t, s ', t', s '', t '' satisfy s + t = 8, s '+ t' = 5, s '' + t '' = 4, respectively, and each phenyl skeleton It is the number which has one or more hydroxyl groups in it. (alpha) is a number which makes the weight average molecular weight of the compound of general formula (D8) and (D9) 100-1,000.

As the acid labile group of the dissolution control agent, various kinds can be used. Specifically, the groups represented by the above formulas (L1) to (L4), a tertiary alkyl group having 4 to 20 carbon atoms, and each alkyl group having 1 to 6 carbon atoms Trialkyl silyl group, C4-C20 oxoalkyl group, etc. are mentioned. In addition, the specific example of each group is the same as that of the above description.

The compounding quantity of the said dissolution control agent is 0-50 mass parts with respect to 100 mass parts of base polymers in a resist material, Preferably it is 0-40 mass parts, More preferably, it is 0-30 mass parts, and mixes single or 2 types or more Can be used. When the compounding amount exceeds 50 parts by mass, the film decreases in the pattern, and the resolution may decrease.

In addition, such dissolution control agents are synthesized by introducing an acid labile group using an organic chemical formulation to a compound having a phenolic hydroxyl group or a carboxyl group.

As the carboxylic acid compound which can be added to the resist material of the present invention, for example, one or two or more compounds selected from the following [I group] and [II group] can be used, but not limited thereto. . By combining this component, the PED stability of the resist is improved, and the edge roughness on the nitride film substrate is improved.

[Group I]

Some or all of the hydrogen atoms of the phenolic hydroxyl groups of the compounds represented by the formulas (A1) to (A10) are substituted by -R ⁴⁰¹ -COOH (R ⁴⁰¹ is a linear or branched alkylene group having 1 to 10 carbon atoms). And a molar ratio between the phenolic hydroxyl group (C) in the molecule and the group (D) represented by ≡C-COOH is C / (C + D) = 0.1 to 1.0.

[Group II]

Compounds represented by the following formulas (A11) to (A15).

In the formula, R ⁴⁰² and R ⁴⁰³ each represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms. R ⁴⁰⁴ represents a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or a-(R ⁴⁰⁹ ) _{h 1} -COOR 'group (R' represents a hydrogen atom or -R ⁴⁰⁹ -COOH).

R ⁴⁰⁵ represents-(CH ₂ ) _i- (i = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom.

R ⁴⁰⁶ represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom.

R ⁴⁰⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group.

R ⁴⁰⁸ represents a hydrogen atom or a methyl group.

R ⁴⁰⁹ represents a straight or branched alkylene group having 1 to 10 carbon atoms.

R ⁴¹⁰ is a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or -R ⁴¹¹ -COOH group (wherein R ⁴¹¹ is a straight or branched alkylene group having 1 to 10 carbon atoms) Indicated).

R ⁴¹² represents a hydrogen atom or a hydroxyl group.

j is a number from 0 to 3, and s1, t1, s2, t2, s3, t3, s4, t4 represent s1 + t1 = 8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4 = 6 It is a number which has one or more hydroxyl groups in each phenyl skeleton, while satisfying.

s5 and t5 are s5≥0 and t5≥0, and are the numbers which satisfy s5 + t5 = 5.

u1 is a number satisfying 1 ≦ u1 ≦ 4, and h1 is a number satisfying 0 ≦ h1 ≦ 4.

κ is a number having a compound of formula (A6) having a weight average molecular weight of 1,000 to 5,000.

λ is a number having a compound of formula (A7) having a weight average molecular weight of 1,000 to 10,000.

As this component, although the compound specifically, shown by following formula (AI-1)-(AI-14) and (AII-1)-(AII-10) is mentioned, It is not limited to this.

(Wherein, R '' represents a hydrogen atom or a CH ₂ COOH group, and in each compound, 10 to 100 mol% of R '' is a CH ₂ COOH group. Κ and λ represent the same meaning as above.)

Further, the amount of the compound having a group represented by ≡C-COOH in the molecule is 0 to 5 parts by mass, preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the base polymer, More preferably, it is 0.1-2 mass parts. When more than 5 mass parts, the resolution of a resist material may fall.

As an acetylene alcohol derivative which can be added to the resist material of this invention, what is represented by following General formula (S1), (S2) can be used preferably.

(In the formula, R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , R ⁵⁰⁵ are each a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, X, Y represents 0 or positive number, The following values are satisfied: 0≤X≤30, 0≤Y≤30, and 0≤X + Y≤40.)

As an acetylene alcohol derivative, Preferably, safinol 61, safinol 82, safinol 104, safinol 104E, safinol 104H, safinol 104A, safinol TG, safinol PC, safinol 440, safinol 465, safinol 485 (manufactured by Air Products and Chemicals Inc.), saffinol E1004 (manufactured by Nisshin Chemical Industries, Ltd.), and the like.

The amount of the acetylene alcohol derivative added is 0 to 2 parts by mass, more preferably 0.01 to 2 parts by mass, still more preferably 0.02 to 1 part by mass based on 100 parts by mass of the base polymer of the resist composition. When more than 2 mass parts, the resolution of a resist material may fall.

Pattern formation using the resist material of this invention can be performed using a well-known lithography technique, and is achieved through each process of application | coating, heat processing (prebaking), exposure, heat processing (post-exposure baking, PEB), and image development. . You can add some more processes as needed.

When performing pattern formation, first, the resist material of the present invention is placed on a substrate (Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflection film, Cr, CrO, CrON, MoSi, etc.) for integrated circuit manufacturing. By a suitable coating method such as spin coating, roll coating, flow coating, immersion coating, spray coating, doctor coating, etc., so that the coating film thickness is 0.01 to 2.0 μm, and then applied on a hot plate at 60 to 150 ° C. for 1 to 10 minutes. Prebaking is preferably performed at 80 to 140 ° C. for 1 to 5 minutes. Due to the thinning of the resist and processing of the substrate to be etched, the processing becomes more stringent, and a silicon-containing intermediate film is placed under the resist, a lower layer film having high carbon density and high etching resistance under the resist, and a substrate to be processed thereunder. A three-layer process was reviewed. The etching selectivity between the silicon-containing intermediate film and the underlayer film using oxygen gas, hydrogen gas, ammonia gas, etc. is high, and the silicon-containing intermediate film can be thinned. The etching selectivity between the single layer resist and the silicon-containing intermediate layer is also relatively high, and the single layer resist can be thinned. In this case, as a method of forming an underlayer film, the method by coating and baking and the method by CVD are mentioned. In the case of an application | coating type | mold, resin which superposed | polymerized the olefin which has novolak resin, condensed ring, etc. is used, and gas, such as butane, ethane, propane, ethylene, acetylene, is used for CVD film manufacture. Also in the case of the silicon-containing intermediate layer, a coating type and a CVD type can be cited. Examples of the coating type include silsesquioxane and cage oligosilsesquioxane (POSS), and the like. Can be. The silicon-containing intermediate layer may have an antireflection function having light absorption, or may be a light absorber such as a phenyl group or a SiON film. An organic film may be formed between the silicon-containing intermediate film and the photoresist film, and the organic film in this case may be an organic antireflection film. After the photoresist film is formed, pure water rinsing (post soaking) may be performed to extract an acid generator or the like from the surface of the film, or to wash away the particles or to apply a protective film.

Subsequently, exposure is performed through a predetermined mask for forming a desired pattern using a light source selected from ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, gamma rays, synchrotron radiation and the like. Exposure dose is preferably about 1 to 200 mJ / cm ^2, more preferably in particular from 10 to 100 mJ / cm ² or so. Next, post-exposure baking (PEB) is carried out on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably at 80 to 120 ° C. for 1 to 3 minutes. Further, 0.1 to 5% by mass, preferably 2 to 3% by mass of a developing solution of an aqueous alkali solution such as tetramethylammonium hydroxide (TMAH), for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, soaking ( By developing using conventional methods such as the dip method, the puddle method, and the spray method, a desired pattern is formed on the substrate. Further, the resist material of the present invention is preferably far ultraviolet rays having a wavelength of 254 to 193 nm, vacuum ultraviolet rays having a wavelength of 157 nm, electron beams, soft X-rays, X-rays, excimer lasers, gamma rays, synchrotron radiation, and more preferably. Preferably fine patterning by high energy radiation in the wavelength range of 180 to 200 nm.

It is also possible to apply the resist material of the present invention to immersion lithography. In ArF immersion lithography, a liquid having a refractive index of at least 1 and low absorption of exposure light, such as pure water or alkanes, is used as the immersion solvent. In immersion lithography, pure water or other liquid is inserted between the resist film after the prebaking and the projection lens. This enables lens design with NA of 1.0 or more, and enables finer pattern formation. Immersion lithography is an important technique for extending ArF lithography to 45 nm nodes, and development is accelerating. In the case of immersion exposure, pure water rinse (post soak) after exposure for removing residual water droplets remaining on the resist film may be performed, to prevent eluate from the resist, and to increase the myeloid property of the film surface. For this purpose, a protective film may be formed on the resist film after preliminary baking. As a resist protective film used for immersion lithography, for example, based on a high molecular compound insoluble in water and having a 1,1,1,3,3,3-hexafluoro-2-propanol residue dissolved in an alkaline developer, The material dissolved in a C4 or more alcohol solvent, a C8-C12 ether solvent, and these mixed solvents is preferable.

Moreover, the double patterning method can be mentioned as an extension technique up to 32 nm of ArF lithography. In the double patterning method, the base of the 1: 3 trench pattern is processed by the first exposure and etching, the position is changed, and the 1: 3 trench pattern is formed by the second exposure to form a 1: 1 pattern. A second process in which the first substrate of the 1: 3 isolation pattern is processed by the trench method to be formed, the first exposure and the etching, the position is shifted, and the 1: 3 isolation pattern is formed below the first substrate by the second exposure. The line method which processes a ground and forms the pattern of 1: 1 with a half pitch is mentioned.

<Example>

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to a following example.

Preparation of Resist Materials

After mixing and dissolving the polymer compound, the acid generator, the basic compound and the solvent in the composition shown in Table 1 below, these were filtered through a Teflon (registered trademark) filter (pore size of 0.2 µm) to obtain a resist material. In addition, all the solvents used were 0.01 mass% of KH-20 (Asahi Glass Co., Ltd. product) as surfactant. Similarly, a comparative resist material was prepared with the composition shown in Table 2 below.

In Tables 1 and 2, numerical values in parentheses indicate mass parts. The basic compound and the solvents 1 and 2 shown by the symbol are as follows.

Base-1: tri (2-methoxymethoxyethyl) amine

Base-2: 1- [2- {2- (2-methoxyethoxy) ethoxy} ethyl] benzimidazole

PGMEA: acetic acid 1-methoxyisopropyl

CyHO: cyclohexanone

Resin shown by symbol is a high molecular compound shown to Tables 3-8, respectively.

Introduction ratio represents molar ratio.

In Tables 1 and 2, acid generators represented by symbols are sulfonium salt compounds shown in Table 9, respectively.

Resolution of resolution

[Examples 1 to 17 and Comparative Examples 1 to 5]

The resist material (R-01 to 17) and the comparative resist material (R-18 to 22) of the present invention were coated on a silicon wafer coated with an antireflection film (Nissan Chemical Industries, Ltd., ARC29A, 78 nm). It was apply | coated by rotation and heat-processed for 100 degreeC and 60 second, and the resist film of thickness 150nm was formed. This was exposed using an ArF excimer laser stepper (manufactured by Nikon Corporation, NA = 0.85) and subjected to heat treatment (PEB) for 60 seconds, followed by 30 seconds using a 2.38% by mass aqueous tetramethylammonium hydroxide solution. The puddle development was performed to form a 1: 1 line and space pattern and an isolated line pattern of 1:10. In PEB, the temperature optimized for each resist material was applied. The exposure dose for observing the manufactured pattern-mounted wafer with a scanning electron microscope (scanning electron microscope) and resolving a line and space of 1: 1 at 80 nm in 1: 1 is called an optimal exposure dose (mJ / cm ² ). The minimum dimension of the 1: 1 line-and-space pattern separated and resolved at the exposure dose was called limit resolution (dimension on the mask, 5 nm engraving, the better the smaller the dimension). In addition, 1:10 isolated line patterns were also observed at the optimum exposure dose, and the actual size on the wafer of the isolated line pattern having a dimension of 140 nm on the mask was measured, which was called mask fidelity (the larger the dimension on the wafer, the better the dimension). . In addition, the roughness of the pattern (LER = line edge roughness) was observed and judged as three-step evaluation (good, possible, or poor).

Table 10 shows the evaluation results (limit resolution, mask fidelity, LER, pattern shape) of the resist material of the present invention, and the evaluation results (limit resolution, mask fidelity, LER, pattern shape) of the comparative resist material. 11 is shown respectively.

From the results in Table 10, it was confirmed that the resist material (Examples 1 to 17) of the present invention had excellent resolution performance and LER was well suppressed. On the other hand, in Comparative Examples 3 to 5 in Table 11, it was evident that the resolution performance was poor or LER was not suppressed when the conventional resin was used. In Comparative Examples 1 and 2 shown in Table 11, even when the resin of the present invention is used, when combined with a conventional acid generator, it is difficult to derive its advantages, and in particular, it has not been improved from conventional products in resolution performance. Could know.

As mentioned above, the resist performance of this invention using the high molecular compound which has a specific repeating unit as a base resin, and combining the special acid generator which the diffusibility of the generated acid was suppressed compared with what was built by the prior art is the resolution performance. Improved, mask fidelity is also good. It was confirmed that the LER was reduced.

Claims (4)

A resin component (A) which is soluble in an alkaline developer by the action of an acid, and a compound (B) which generates an acid in response to actinic radiation or radiation, wherein the resin component (A) is represented by the following formula (1) A positive resist material, wherein the compound (B) generating a acid is a sulfonium salt compound represented by the following formula (2). <Formula 1>

(Wherein R ¹ each independently represents a hydrogen atom or a methyl group. R ² represents a fluorine-containing substituent having 1 to 15 carbon atoms. N is 1 or 2. a, b, c, and d are each a repeating unit. A, b, c, and d are 0.01 or more and less than 1, respectively, and a + b + c + d = 1.) <Formula 2>

(In formula, R <^3> , R <^4> , R <^5> represents a C1-C20 linear, branched or cyclic monovalent hydrocarbon group which may respectively contain a hydrogen atom or a hetero atom independently. R <^6> is hetero C7-C30 linear, branched or cyclic monovalent hydrocarbon group which may contain an atom.) The process of apply | coating the resist material of Claim 1 on a board | substrate, the process of exposing with high energy rays or an electron beam through a photomask after heat processing, and the process of developing using a developing solution after heat processing, It characterized by the above-mentioned. Pattern formation method. The pattern forming process which includes the process of apply | coating the resist material of Claim 1 on a board | substrate, the process of exposing with a high energy ray or an electron beam through a photomask after heat processing, and the process of developing using a developing solution after heat processing. In which a liquid having a refractive index of at least 1 is interposed between the resist coating film and the projection lens to perform liquid immersion exposure. The pattern forming process which includes the process of apply | coating the resist material of Claim 1 on a board | substrate, the process of exposing with a high energy ray or an electron beam through a photomask after heat processing, and the process of developing using a developing solution after heat processing. In which a protective film is further applied on the resist coating film, and a liquid immersion exposure is performed by interposing a liquid having a refractive index of 1 or more between the protective film and the projection lens.