JP2007197613A - Radiosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiosensitive resin composition having a chemically amplifying light-sensitive film to far-ultraviolet radiation with improved pattern form together with improved resolving performance, sensitivity and focal depth latitude. <P>SOLUTION: The radiosensitive resin composition includes a polymer comprising (1) a repetitive unit derived from a hydroxystyrene-based monomer, (2) a repetitive unit derived from an alkyloxyalkyloxystyrene-based monomer unit, (3) a repetitive unit derived from alkyloxyalkyloxystyrene-based monomer unit different from that described in the aforementioned (2), (4) a repetitive unit derived from o-butoxycarbonyloxystyrene-based monomer unit and (5) a repetitive unit derived from a (meth)acrylate-based monomer unit having a cyclopentyl substituent, and also a radiosensitive acid generator. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a radiation sensitive resin composition. More specifically, for example, as a chemically amplified resist sensitive to far ultraviolet rays typified by KrF excimer laser, ArF excimer laser, or F ₂ excimer laser, resolution performance is improved, sensitivity is improved, and depth of focus margin (process margin) is increased. It is related with the radiation sensitive resin composition which can improve a resist pattern shape with improvement.

In the field of microfabrication represented by the manufacture of integrated circuit elements, a lithography technique capable of microfabrication at a level of 0.15 μm or less is recently required to obtain a higher degree of integration. However, in the conventional lithography process, near ultraviolet rays such as i rays are generally used as radiation, and it is said that fine processing at the subquarter micron level is extremely difficult with this near ultraviolet rays. Therefore, in order to enable microfabrication at a level of 0.15 μm or less, use of radiation having a shorter wavelength is being studied.
Examples of such short-wavelength radiation include an emission line spectrum of a mercury lamp, far-ultraviolet rays typified by an excimer laser, an X-ray, an electron beam, and the like. Among these, a KrF excimer laser (wavelength 248 nm) is particularly preferable. ) Or ArF excimer laser (wavelength 193 nm) has been attracting attention. As a resist suitable for irradiation with such an excimer laser, a component having an acid-dissociable functional group and a component that generates acid upon irradiation with radiation (hereinafter referred to as “exposure”) (hereinafter referred to as “acid generator”). Many resists using the chemical amplification effect (hereinafter referred to as “chemically amplified resist”) have been proposed.
Examples of the chemically amplified resist include a resin in which an alkali affinity group in an alkali-soluble resin is protected with a t-butyl ester group or a t-butoxycarbonyl group (see Patent Document 1), or an alkali affinity group in an alkali-soluble resin. There is known a resist using a resin in which is protected with an acetal group (see Patent Documents 2 and 3).

However, the resolution of resist films using these compositions is not always sufficient, and further improvements in resolution have been desired.
Further, when these compositions are used, there is a problem that a so-called optical proximity effect is large, and a dimensional difference due to the density of the resist pattern or roundness at the end of the pattern is likely to occur. When the dimensional difference due to the density of the resist pattern is large, when the exposure is performed with the optimum exposure amount of the line and space pattern, a pattern with the designed dimension cannot be obtained with a narrow space pattern such as 5L / 1S. Due to the widespread use of media, it is not possible to satisfy the need for one-chip logic circuits and memory circuits.

  For this reason, in addition to the resolution and pattern shape of the line and space pattern, the optical proximity effect is small, and the 1L1S pattern is a narrow space pattern such as 5L / 1S regardless of the density of the resist pattern. Even so, a resist having excellent depth of focus has been demanded.

JP 59-45439 A JP-A-2-161436 JP-A-5-249682

The object of the present invention is, for example, as a chemically amplified resist sensitive to far ultraviolet rays typified by KrF excimer laser, ArF excimer laser or F ₂ excimer laser, along with improvement of resolution performance, sensitivity and depth of focus margin (process margin). An object of the present invention is to provide a radiation-sensitive resin composition capable of improving the resist pattern shape.

（式中、Ｒ^１は水素原子又はメチル基を示す。）

（式中、Ｒ^２は水素原子又はメチル基を示し、Ｒ^３は水素原子又はメチル基を示し、Ｒ^４は水素原子、メチル基又はエチル基を示す。）

（式中、Ｒ^５は水素原子又はメチル基を示し、Ｒ^６は水素原子又はメチル基を示し、Ｒ^７は炭素数２〜４のアルキル基を示し、Ｒ^８は水素原子、メチル基又はエチル基を示す。）

（式中、Ｒ^９は水素原子又はメチル基を示す。）

（式中、Ｒ^１０は水素原子又はメチル基を示し、Ｒ^１１はメチル基又はエチル基を示す。） As a means for achieving the above object, the invention of claim 1 includes (A) a polymer containing each repeating unit represented by the following formulas (1) to (5), and (B) a radiation-sensitive acid. A radiation-sensitive resin composition comprising a generator.

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

(Wherein R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom, a methyl group or an ethyl group.)

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkyl group having 2 to 4 carbon atoms, and R ⁸ represents a hydrogen atom, a methyl group or an ethyl group. Group.)

(In the formula, R ⁹ represents a hydrogen atom or a methyl group.)

(In the formula, R ¹⁰ represents a hydrogen atom or a methyl group, and R ¹¹ represents a methyl group or an ethyl group.)

The invention of claim 2
The radiation-sensitive resin composition according to claim 1, further comprising (C) an acid diffusion controller.

The invention of claim 3
The radiation sensitive resin composition according to claim 1, wherein the component (B) is a disulfonyldiazomethane compound and / or a sulfonium salt.

The invention of claim 4
The radiation sensitive resin composition according to claim 2 or 3, wherein the component (C) is an amine compound having a polyether group.

The invention of claim 5
The radiation sensitivity according to any one of claims 2 to 4, wherein bis (cyclohexyl) diazomethane is contained as the component (B), and tris (2-methoxymethoxyethyl) amine is contained as the component (C). It is a resin composition.

The invention of claim 6
The (A) component is a copolymer containing each repeating unit represented by the general formulas (1), (2) and (5), and the general formulas (1), (3) and (4). A radiation-sensitive resin composition according to any one of claims 1 to 5, comprising a copolymer containing each repeating unit represented.

The invention of claim 7
The (A) component is a copolymer containing each repeating unit represented by the general formulas (1), (2) and (4), and the general formulas (1), (3) and (5). A radiation-sensitive resin composition according to any one of claims 1 to 5, comprising a copolymer containing each repeating unit represented.

The invention of claim 8
The said (A) component is a copolymer containing each repeating unit represented by the said general formula (1), (2) and (3), and each represented by the said general formula (1) and (4) A radiation-sensitive resin composition according to any one of claims 1 to 5, comprising a copolymer containing a repeating unit.

The invention of claim 9
The (A) component is a copolymer containing each repeating unit represented by the general formulas (1), (2), (3) and (4), and the general formulas (1) and (5). A radiation-sensitive resin composition according to any one of claims 1 to 5, comprising a copolymer containing each repeating unit represented.

  The radiation-sensitive resin composition of the present invention is excellent not only in the depth of focus of the 1L / 1S line and space pattern but also in the depth of focus of the narrow space pattern (5L / 1S). Also, the pattern shape is excellent, and a fine pattern can be formed with high accuracy and stability for both the line-and-space pattern and the isolated pattern. Moreover, the radiation sensitive resin composition of the present invention is sensitive to various kinds of radiation such as ultraviolet rays, far ultraviolet rays, X-rays and electron beams. Therefore, the radiation-sensitive resin composition of the present invention can be used very suitably as a chemically amplified positive resist for the production of semiconductor devices that are expected to be further refined in the future.

Hereinafter, the present invention will be described in detail.
<Polymer (A)>
The polymer in the present invention includes a repeating unit represented by the above formula (1) (hereinafter referred to as “repeating unit (1)”) and a repeating unit represented by the above formula (2) (hereinafter referred to as “repeating unit ( 2) "), a repeating unit represented by the above formula (3) (hereinafter referred to as" repeating unit (3) "), a repeating unit represented by the above formula (4) (hereinafter referred to as" repeating unit (" 4) ") and a repeating unit represented by the above formula (5) (hereinafter referred to as" repeating unit (5) ").

Specific examples of the organic group [—O—CH (R ³ ) —O—CH ₂ R ⁴ ] in the repeating unit (2) include a methoxymethoxy group, an ethoxymethoxy group, an n-propoxymethoxy group, and 1-methoxyethoxy. Group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group and the like. Of these organic groups, methoxymethoxy group, ethoxymethoxy group, 1-methoxyethoxy group, 1-ethoxyethoxy group and the like are preferable.

Specific examples of the organic group [—O—C (R ⁶ ) (R ⁷ ) —O—CH ₂ R ⁸ ] in the repeating unit (3) include 1-methoxypropoxy group, 1-ethoxypropoxy group, 1- n-propoxypropoxy group, 1-methoxybutoxy group, 1-ethoxybutoxy group, 1-n-propoxybutoxy group, 1-methoxypentyloxy group, 1-ethoxypentyloxy group, 1-n-propoxypentyloxy group, 2 -Methoxy-2-butoxy group, 2-ethoxy-2-butoxy group, 2-n-propoxy-2-butoxy group, 2-methoxy-2-pentyloxy group, 2-ethoxy-2-pentyloxy group, 2- n-propoxy-2-pentyloxy group, 2-methoxy-2-hexyloxy group, 2-ethoxy-2-hexyloxy group, 2-n-propoxy-2 And a hexyl group and the like. Of these organic groups, 1-methoxypropoxy group, 1-ethoxypropoxy group and the like are preferable.

  In the polymer, specific examples of the repeating unit (1) include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene or p- Mention may be made of units derived from hydroxy-α-methylstyrene. Of these repeating units (1), units derived from p-hydroxystyrene, p-hydroxy-α-methylstyrene and the like are preferable.

  Specific examples of the repeating unit (2) include o-methoxymethoxystyrene, o-ethoxymethoxystyrene, on-propoxymethoxystyrene, o-1-methoxyethoxystyrene, o-1-ethoxyethoxystyrene, o. -1-n-propoxyethoxystyrene, m-methoxymethoxystyrene, m-ethoxymethoxystyrene, mn-propoxymethoxystyrene, m-1-methoxyethoxystyrene, m-1-ethoxyethoxystyrene, m-1-n -Propoxyethoxystyrene, p-methoxymethoxystyrene, p-ethoxymethoxystyrene, pn-propoxymethoxystyrene, p-1-methoxyethoxystyrene, p-1-ethoxyethoxystyrene, p-1-n-propoxyethoxystyrene , O-methoxy Toxi-α-methylstyrene, o-ethoxymethoxy-α-methylstyrene, on-propoxymethoxy-α-methylstyrene, o-1-methoxyethoxy-α-methylstyrene, o-1-ethoxyethoxy-α- Methylstyrene, o-1-n-propoxyethoxy-α-methylstyrene, m-methoxymethoxy-α-methylstyrene, m-ethoxymethoxy-α-methylstyrene, mn-propoxymethoxy-α-methylstyrene, m -1-methoxyethoxy-α-methylstyrene, m-1-ethoxyethoxy-α-methylstyrene, m-1-n-propoxyethoxy-α-methylstyrene, p-methoxymethoxy-α-methylstyrene, p-ethoxy Methoxy-α-methylstyrene, pn-propoxymethoxy-α-methylstyrene, p- - it can be exemplified units derived from methoxyethoxymethyl -α- methyl styrene, p-1-ethoxyethoxy -α- methyl styrene, the p-1-n-propoxyethoxy -α- methyl styrene. Of these repeating units (2), units derived from p-methoxymethoxystyrene, p-ethoxymethoxystyrene, p-1-methoxyethoxystyrene, p-1-ethoxyethoxystyrene and the like are preferable.

Moreover, as a specific example of the repeating unit (3),
o-1-methoxypropoxystyrene, o-1-ethoxypropoxystyrene, o-1-n-propoxypropoxystyrene, o-1-methoxybutoxystyrene, o-1-ethoxybutoxystyrene, o-1-n-propoxybutoxy Styrene, o-1-methoxypentyloxystyrene, o-1-ethoxypentyloxystyrene, o-1-n-propoxypentyloxystyrene, m-1-methoxypropoxystyrene, m-1-ethoxypropoxystyrene, m-1 -N-propoxypropoxystyrene, m-1-methoxybutoxystyrene, m-1-ethoxybutoxystyrene, m-1-n-propoxybutoxystyrene, m-1-methoxypentyloxystyrene, m-1-ethoxypentyloxystyrene , M-1-n-pro Xypentyloxystyrene, p-1-methoxypropoxystyrene, p-1-ethoxypropoxystyrene, p-1-n-propoxypropoxystyrene, p-1-methoxybutoxystyrene, p-1-ethoxybutoxystyrene, p-1 -N-propoxybutoxystyrene, p-1-methoxypentyloxystyrene, p-1-ethoxypentyloxystyrene, p-1-n-propoxypentyloxystyrene, p- (2-methoxy-2-butoxy) styrene, p -(2-ethoxy-2-butoxy) styrene, p- (2-methoxy-2-pentyloxy) styrene, p- (2-ethoxy-2-pentyloxy) styrene, p- (2-methoxy-2-hexyl) Oxy) styrene, p- (2-ethoxy-2-hexyloxy) styrene,

  o-1-methoxypropoxy-α-methylstyrene, o-1-ethoxypropoxy-α-methylstyrene, o-1-n-propoxypropoxy-α-methylstyrene, o-1-methoxybutoxy-α-methylstyrene, o-1-ethoxybutoxy-α-methylstyrene, o-1-n-propoxybutoxy-α-methylstyrene, o-1-methoxypentyloxy-α-methylstyrene, o-1-ethoxypentyloxy-α-methyl Styrene, o-1-n-propoxypentyloxy-α-methylstyrene, m-1-methoxypropoxy-α-methylstyrene, m-1-ethoxypropoxy-α-methylstyrene, m-1-n-propoxypropoxy- α-methylstyrene, m-1-methoxybutoxy-α-methylstyrene, m-1-ethoxybutoxy -Α-methylstyrene, m-1-n-propoxybutoxy-α-methylstyrene, m-1-methoxypentyloxy-α-methylstyrene, m-1-ethoxypentyloxy-α-methylstyrene, m-1- n-propoxypentyloxy-α-methylstyrene, p-1-methoxypropoxy-α-methylstyrene, p-1-ethoxypropoxy-α-methylstyrene, p-1-n-propoxypropoxy-α-methylstyrene, p -1-methoxybutoxy-α-methylstyrene, p-1-ethoxybutoxy-α-methylstyrene, p-1-n-propoxybutoxy-α-methylstyrene, p-1-methoxypentyloxy-α-methylstyrene, p-1-ethoxypentyloxy-α-methylstyrene, p-1-n-propoxypentyloxy-α Methyl styrene,

  p- (2-methoxy-2-butoxy) -α-methylstyrene, p- (2-ethoxy-2-butoxy) -α-methylstyrene, p- (2-methoxy-2-pentyloxy) -α-methyl Styrene, p- (2-Ethoxy-2-pentyloxy) -α-methylstyrene, p- (2-methoxy-2-hexyloxy) -α-methylstyrene, p- (2-ethoxy-2-hexyloxy) Examples include units derived from -α-methylstyrene. Of these repeating units (3), units derived from p-1-methoxypropoxystyrene, p-1-ethoxypropoxystyrene and the like are preferable.

Specific examples of the repeating unit (4) include units derived from p-tert-butoxycarbonyloxystyrene, p-tert-butoxycarbonyloxy-α-methylstyrene, and the like.
Of these repeating units (4), units derived from p-tert-butoxycarbonyloxystyrene are preferred.

Specific examples of the repeating unit (5) include units derived from 1-methylcyclopentyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, and the like.
Of these repeating units (5), units derived from 1-ethylcyclopentyl (meth) acrylate are preferred.

In the radiation-sensitive resin composition of the present invention, only one kind of this polymer may be used, or two or more kinds may be mixed and used. Further, the polymer (A) in the present invention may be a copolymer as long as it contains the above repeating units (1) to (5), and a homopolymer and / or a copolymer are blended. It may be. In the above polymer, each of the repeating units (1) to (5) may be present alone or in combination of two or more.
Preferred polymers in the present invention include, for example, <1> a copolymer containing each of the repeating units (1), (2) and (5), and the general formulas (1), (3) and A copolymer containing each repeating unit of (4), a polymer containing <2> a copolymer containing each repeating unit of the above general formulas (1), (2) and (4), and the above general A copolymer containing each repeating unit of the formulas (1), (3) and (5), <3> each repeating unit of the above general formulas (1), (2) and (3) A polymer containing a copolymer containing each of the repeating units of the above general formulas (1) and (4), <4> the above general formulas (1), (2), (3 And a copolymer containing each repeating unit of (4) and a copolymer containing each repeating unit of the above general formulas (1) and (5). Coalescence, and the like.

In the polymer, the total content of the repeating units (1) to (5) is preferably 80 mol% or more, more preferably 90 to 100, based on all repeating units in the polymer (A). Mol%. When the total content of the repeating units (1) to (5) is 80 mol% or more, a sufficient line and space pattern resolution can be obtained.
Moreover, the content rate of a repeating unit (1) is 60-90 mol% with respect to all the repeating units, The content rate of a repeating unit (2) is 3-30 mol% with respect to all the repeating units, and a repeating unit. The content of (3) is 3 to 30 mol% with respect to all repeating units, the content of the repeating unit (4) is 3 to 30 mol% with respect to all repeating units, and the repeating unit (5) The content is preferably 3 to 30 mol% with respect to all repeating units. More preferably, the content of the repeating unit (1) is 60 to 80 mol% with respect to all the repeating units, the content of the repeating unit (2) is 3 to 20 mol% with respect to all the repeating units, The content of the repeating unit (3) is 3 to 20 mol% with respect to all the repeating units, the content of the repeating unit (4) is 3 to 20 mol% with respect to all the repeating units, and the repeating unit (5 ) Is 3 to 20 mol% with respect to all repeating units. When the content of each repeating unit is in the above range, the heat resistance as a resist is improved and the resolution of the line and space pattern is improved. Furthermore, the film surface roughness of the pattern can be suppressed.

The polymer (A) in the present invention may optionally contain one or more repeating units other than the above repeating units (1) to (5) (hereinafter referred to as “other repeating units”).
Examples of the monomer giving the other repeating unit include styrenes such as styrene, α-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonyloxystyrene; Unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid, crotonic acid, mesaconic acid, citraconic acid, itaconic acid, maleic anhydride, and methyl maleic anhydride or acid anhydrides thereof; methyl of the above unsaturated carboxylic acid Ester, ethyl ester, n-propyl ester, i-propyl ester, n-butyl ester, i-butyl ester, sec-butyl ester, t-butyl ester, n-amyl ester, 2-hydroxyethyl ester, 2,2- Dimethyl-3-hydroxypropyl ester, benzyl ester, isovo Esters such as nyl ester, adamantyl ester, tricyclodecanyl ester, tetracyclodecanyl ester; unsaturated nitriles such as (meth) acrylonitrile, maleinonitrile, fumaronitrile, mesaconnitrile, citracononitrile, itaconnitrile; Unsaturated amides such as acrylamide, crotonamide, maleinamide, fumaramide, mesaconamide, citraconamide, itaconamide; unsaturated imides such as maleimide and N-phenylmaleimide; unsaturated alcohols such as (meth) allyl alcohol; Mention may be made of other vinyl compounds such as vinylanilines, vinylpyridines, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, N-vinylimidazole, N-vinylcarbazole and the like. These monomers can be used alone or in admixture of two or more. Among the monomers giving the other repeating units, styrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonyloxystyrene, t-butyl (meth) acrylate, (meth) acrylic acid Isobornyl, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, (meth) acrylonitrile and the like are preferable.
The content of other repeating units is preferably 20 mol% or less, more preferably 15 mol% or less, based on all repeating units in the polymer (A).

Moreover, the polystyrene conversion weight average molecular weight (henceforth "Mw") by the gel permeation chromatography (henceforth "GPC") of a polymer (A) is 1000-100000 normally, It is 3000-40000. It is preferable, More preferably, it is 3000-30000. In this case, when the Mw of the polymer is less than 1000, the sensitivity and heat resistance when the resist is formed tend to decrease, and when it exceeds 100,000, the solubility in the developer tends to decrease.
The ratio (Mw / Mn) of the polymer Mw to the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) by GPC is usually 1.0 to 10.0, preferably 1.0 to 5 .0.

<Radiation sensitive acid generator (B)>
The radiation-sensitive acid generator (hereinafter simply referred to as “acid generator”) in the present invention generates an acid upon exposure. This acid generator dissociates the acid-dissociable group present in the above-mentioned polymer by the action of the acid generated by exposure, and as a result, the exposed portion of the resist film becomes readily soluble in an alkali developer, and a positive type It has a function of forming a resist pattern.
Examples of the acid generator in the present invention include onium salt compounds, disulfonyldiazomethane compounds, sulfone compounds, sulfonimide compounds, sulfonic acid ester compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, and the like. . Of these, onium salt compounds and disulfonyldiazomethane compounds are preferred. In addition, these acid generators can be used individually or in mixture of 2 or more types.

Examples of the onium salt compounds include sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts, and the like. Of these, sulfonium salts are preferred.
Specific examples of the onium salt compounds include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium pyrenesulfonate, triphenylsulfonium n-dodecyl. Benzenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium n-octanesulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4-tri Fluoromethylbenzenesulfonate, triphenyl Rufonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium perfluorobenzenesulfonate, (4-t-butylphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-t-butylphenyl) diphenylsulfonium nonafluoro-n- Butanesulfonate, (4-t-butylphenyl) diphenylsulfonium perfluoro-n-octanesulfonate, (4-t-butylphenyl) diphenylsulfonium pyrenesulfonate, (4-t-butylphenyl) diphenylsulfonium n-dodecylbenzenesulfonate, (4-t-butylphenyl) diphenylsulfonium p-toluenesulfonate, (4-t-butylphenyl) diphenylsulfate Nitrobenzenesulfonate, (4-tert-butylphenyl) diphenylsulfonium 10-camphorsulfonate, (4-tert-butylphenyl) diphenylsulfonium n-octanesulfonate, (4-tert-butylphenyl) diphenylsulfonium 2-trifluoromethylbenzene Sulfonate, (4-t-butylphenyl) diphenylsulfonium 4-trifluoromethanebenzene sulfonate, (4-t-butylphenyl) diphenylsulfonium perfluorobenzene sulfonate,

  (4-t-butoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-t-butoxyphenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, (4-t-butoxyphenyl) diphenylsulfonium perfluoro-n-octanesulfonate, (4-t-butoxyphenyl) diphenylsulfonium pyrenesulfonate, (4-t-butoxyphenyl) diphenylsulfonium n-dodecylbenzenesulfonate, (4-t-butoxyphenyl) diphenylsulfonium p-toluenesulfonate, (4-t-butoxy Phenyl) diphenylsulfonium benzenesulfonate, (4-t-butoxyphenyl) diphenylsulfonium 10-camphorsulfonate, (4-t-butoxypheny ) Diphenylsulfonium n-octanesulfonate, (4-t-butoxyphenyl) diphenylsulfonium 2-trifluoromethylbenzenesulfonate, (4-t-butoxyphenyl) diphenylsulfonium 4-trifluoromethylbenzenesulfonate, (4-t-butoxy) Phenyl) diphenylsulfonium perfluorobenzenesulfonate, (4-hydroxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, (4-hydroxyphenyl) diphenylsulfonium perfluoro-n- Octanesulfonate, (4-hydroxyphenyl) diphenylsulfonium pyrenesulfonate, (4-hydroxyphene L) Diphenylsulfonium n-dodecylbenzenesulfonate, (4-hydroxyphenyl) diphenylsulfonium p-toluenesulfonate, (4-hydroxyphenyl) diphenylsulfoniumbenzenesulfonate, (4-hydroxyphenyl) diphenylsulfonium 10-camphorsulfonate, (4- Hydroxyphenyl) diphenylsulfonium n-octanesulfonate, (4-hydroxyphenyl) diphenylsulfonium 2-trifluoromethylbenzenesulfonate, (4-hydroxyphenyl) diphenylsulfonium 4-trifluoromethylbenzenesulfonate, (4-hydroxyphenyl) diphenylsulfonium Perfluorobenzenesulfonate,

  Tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tris (4-methoxyphenyl) sulfonium nonafluoro-n-butanesulfonate, tris (4-methoxyphenyl) sulfonium perfluoro-n-octanesulfonate, tris (4-methoxyphenyl) ) Sulfonium pyrenesulfonate, tris (4-methoxyphenyl) sulfonium n-dodecylbenzenesulfonate, tris (4-methoxyphenyl) sulfonium p-toluenesulfonate, tris (4-methoxyphenyl) sulfoniumbenzenesulfonate, tris (4-methoxyphenyl) Sulfonium 10-camphorsulfonate, tris (4-methoxyphenyl) sulfonium n-octanesulfonate, tris (4-methoxy) Enyl) sulfonium 2-trifluoromethylbenzenesulfonate, tris (4-methoxyphenyl) sulfonium 4-trifluoromethylbenzenesulfonate, tris (4-methoxyphenyl) sulfonium perfluorobenzenesulfonate, bis (4-methoxyphenyl) p-toluyl Sulfonium trifluoromethanesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium nonafluoro-n-butanesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium perfluoro-n-octanesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium pyrenesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium n-dodecylbenzenesulfonate, bis (4-methoate) Ciphenyl) p-toluylsulfonium p-toluenesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium benzenesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium 10-camphorsulfonate, bis (4-methoxyphenyl) p- Toluylsulfonium n-octanesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium 2-trifluoromethylbenzenesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium 4-trifluoromethylbenzenesulfonate, bis (4-methoxy Phenyl) p-toluylsulfonium perfluorobenzenesulfonate,

(4-fluorophenyl) diphenylsulfonium trifluoromethanesulfonate, (4-fluorophenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) diphenylsulfonium 10-camphorsulfonate,
Tris (4-fluorophenyl) sulfonium trifluoromethanesulfonate, tris (4-fluorophenyl) sulfonium nonafluoro-n-butanesulfonate, tris (4-fluorophenyl) sulfonium 10-camphor sulfonate, tris (4-fluorophenyl) Sulfonium p-toluenesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium 2,4-difluorobenzenesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium p- Toluene sulfonate,

  Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate Diphenyliodonium 10-camphorsulfonate, diphenyliodonium n-octanesulfonate, diphenyliodonium 2-trifluoromethylbenzenesulfonate, diphenyliodonium4-trifluoromethylbenzenesulfonate, diphenyliodonium perfluorobenzenesulfonate, bis (p-to Yl) iodonium trifluoromethanesulfonate, bis (p-toluyl) iodonium nonafluoro-n-butanesulfonate, bis (p-toluyl) iodonium perfluoro-n-octanesulfonate, bis (p-toluyl) iodonium pyrenesulfonate, bis (p -Toluyl) iodonium n-dodecylbenzenesulfonate, bis (p-toluyl) iodonium p-toluenesulfonate, bis (p-toluyl) iodoniumbenzenesulfonate, bis (p-toluyl) iodonium 10-camphorsulfonate, bis (p-toluyl) Iodonium n-octanesulfonate, bis (p-toluyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (p-toluyl) iodonium 4-trifluoro Methylbenzenesulfonate, bis (p- tolyl) iodonium perfluoro sulfonate,

  Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (4-t-butylphenyl) iodonium pyrenesulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t- Butylphenyl) iodonium benzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium n-octanesulfonate, bis (4-t-butyl) Enyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium perfluorobenzenesulfonate, bis (4-t- Butylphenyl) iodonium 2,4-difluorobenzenesulfonate, bis (3,4-dimethylphenyl) iodonium trifluoromethanesulfonate, bis (3,4-dimethylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (3,4 Dimethylphenyl) iodonium perfluoro-n-octanesulfonate, bis (3,4-dimethylphenyl) iodonium pyrenesulfonate, bis (3,4-dimethylphenyl) iodonium n-do Silbenzene sulfonate, bis (3,4-dimethylphenyl) iodonium p-toluenesulfonate, bis (3,4-dimethylphenyl) iodonium benzenesulfonate, bis (3,4-dimethylphenyl) iodonium 10-camphorsulfonate, bis (3 , 4-Dimethylphenyl) iodonium n-octanesulfonate, bis (3,4-dimethylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (3,4-dimethylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis ( 3,4-dimethylphenyl) iodonium perfluorobenzenesulfonate,

  (4-nitrophenyl) phenyliodonium trifluoromethanesulfonate, (4-nitrophenyl) phenyliodonium nonafluoro-n-butanesulfonate, (4-nitrophenyl) phenyliodonium perfluoro-n-octanesulfonate, (4-nitrophenyl) Phenyliodonium pyrenesulfonate, (4-nitrophenyl) phenyliodonium n-dodecylbenzenesulfonate, (4-nitrophenyl) phenyliodonium p-toluenesulfonate, (4-nitrophenyl) phenyliodoniumbenzenesulfonate, (4-nitrophenyl) phenyl Iodonium 10-camphorsulfonate, (4-nitrophenyl) phenyliodonium n-octanesulfonate, (4-nitrophenyl) Phenyliodonium 2-trifluoromethylbenzenesulfonate, (4-nitrophenyl) phenyliodonium 4-trifluoromethylbenzenesulfonate, (4-nitrophenyl) phenyliodonium perfluorobenzenesulfonate, bis (3-nitrophenyl) iodonium trifluoromethanesulfonate Bis (3-nitrophenyl) iodonium nonafluoro-n-butanesulfonate, bis (3-nitrophenyl) iodonium perfluoro-n-octanesulfonate, bis (3-nitrophenyl) iodonium pyrenesulfonate, bis (3-nitrophenyl) ) Iodonium n-dodecylbenzenesulfonate, bis (3-nitrophenyl) iodonium p-toluenesulfonate, bis (3-nitrofe) L) iodonium benzene sulfonate, bis (3-nitrophenyl) iodonium 10-camphor sulfonate, bis (3-nitrophenyl) iodonium n-octane sulfonate, bis (3-nitrophenyl) iodonium 2-trifluoromethylbenzene sulfonate, bis ( 3-nitrophenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis (3-nitrophenyl) iodonium perfluorobenzenesulfonate,

  (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, (4-methoxyphenyl) phenyliodonium nonafluoro-n-butanesulfonate, (4-methoxyphenyl) phenyliodonium perfluoro-n-octanesulfonate, (4-methoxyphenyl) Phenyliodonium pyrenesulfonate, (4-methoxyphenyl) phenyliodonium n-dodecylbenzenesulfonate, (4-methoxyphenyl) phenyliodonium p-toluenesulfonate, (4-methoxyphenyl) phenyliodoniumbenzenesulfonate, (4-methoxyphenyl) phenyl Iodonium 10-camphorsulfonate, (4-methoxyphenyl) phenyliodonium n-octanesulfonate, ( -Methoxyphenyl) phenyliodonium 2-trifluoromethylbenzenesulfonate, (4-methoxyphenyl) phenyliodonium 4-trifluoromethylbenzenesulfonate, (4-methoxyphenyl) phenyliodonium perfluorobenzenesulfonate, (4-fluorophenyl) phenyl Iodonium trifluoromethanesulfonate, (4-fluorophenyl) phenyliodonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) phenyliodonium 10-camphorsulfonate,

  Bis (4-fluorophenyl) iodonium trifluoromethanesulfonate, bis (4-fluorophenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-fluorophenyl) iodonium 10-camphorsulfonate, bis (4-chlorophenyl) iodonium trifluoromethane Sulfonate, bis (4-chlorophenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-chlorophenyl) iodonium perfluoro-n-octanesulfonate, bis (4-chlorophenyl) iodonium pyrenesulfonate, bis (4-chlorophenyl) iodonium n -Dodecylbenzenesulfonate, bis (4-chlorophenyl) iodonium p-toluenesulfonate, bis (4-chlorophenyl) iodo Donium benzene sulfonate, bis (4-chlorophenyl) iodonium 10-camphor sulfonate, bis (4-chlorophenyl) iodonium n-octane sulfonate, bis (4-chlorophenyl) iodonium 2-trifluoromethylbenzene sulfonate, bis (4-chlorophenyl) Iodonium 4-trifluoromethylbenzenesulfonate, bis (4-chlorophenyl) iodonium perfluorobenzenesulfonate,

  Bis (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, bis (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-trifluoromethylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (4-trifluoromethylphenyl) iodonium pyrenesulfonate, bis (4-trifluoromethylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, bis (4-trifluoro Methylphenyl) iodonium benzenesulfonate, bis (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate, bis (4-trifluoromethyl) Ruphenyl) iodonium n-octanesulfonate, bis (4-trifluoromethylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (4-trifluoromethylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis (4-trifluoro Methylphenyl) iodonium perfluorobenzenesulfonate, di (1-naphthyl) iodonium trifluoromethanesulfonate, di (1-naphthyl) iodonium nonafluoro-n-butanesulfonate, di (1-naphthyl) iodonium perfluoro-n-octanesulfonate, Di (1-naphthyl) iodonium pyrenesulfonate, di (1-naphthyl) iodonium n-dodecylbenzenesulfonate, di (1-naphthyl) iodonium p-toluenesulfonate, di (1-naphthyl) iodonium benzenesulfonate, di (1-naphthyl) iodonium 10-camphorsulfonate, di (1-naphthyl) iodonium n-octanesulfonate, di (1-naphthyl) iodonium 2-trifluoro Examples thereof include methylbenzene sulfonate, di (1-naphthyl) iodonium 4-trifluoromethylbenzenesulfonate, and di (1-naphthyl) iodonium perfluorobenzenesulfonate.

  As said disulfonyl diazomethane compound, the compound represented by following General formula (6) can be mentioned, for example.

〔一般式（６）において、各Ｒ^１２は相互に独立にアルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を示す。）

[In General Formula (6), each R ¹² independently represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group. )

  Specific examples of the disulfonyldiazomethane compound include bis (trifluoromethanesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, and bis (2,6-dimethyl). Phenylsulfonyl) diazomethane, bis (3,5-dimethylphenylsulfonyl) diazomethane, bis (4-t-butylphenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, (methylsulfonyl) 4-methylphenylsulfonyldiazomethane, (Cyclohexylsulfonyl) 4-methylphenylsulfonyldiazomethane, bis (t-butylsulfonyl) diazomethane, (cyclohexylsulfonyl) 1,1-dimethyl Ethylsulfonyldiazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (1-methylethylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) Examples thereof include diazomethane and bis (1,4-dioxaspiro [4.5] decan-7-sulfonyl) diazomethane.

  Examples of the preferred acid generator in the present invention include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, and triphenylsulfonium p-toluenesulfonate. , Triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4-trifluorobenzenesulfonate, triphenylsulfonium 2,4-difluoromethylbenzenesulfonate, tris (4-methoxyphenyl) sulfonium Trifluoromethanesulfonate, tris (4-methoxyphenyl) sulfonium nonafluo -N-butanesulfonate, tris (4-methoxyphenyl) sulfonium 10-camphorsulfonate, (4-t-butoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-t-butoxyphenyl) diphenylsulfonium nonafluoro-n-butanesulfonate ,

  (4-fluorophenyl) diphenylsulfonium trifluoromethanesulfonate, (4-fluorophenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) diphenylsulfonium 10-camphor sulfonate, tris (4-fluorophenyl) sulfonium trifluoro Lomethanesulfonate, tris (4-fluorophenyl) sulfonium nonafluoro-n-butanesulfonate, tris (4-fluorophenyl) sulfonium 10-camphorsulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 2,4, 6-trimethylphenyldiphenylsulfonium p-toluenesulfonate, 2,4,6-trimethylphenyldiphenyl Sulfonium 2,4-difluoro benzenesulfonate,

  Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 10-camphorsulfonate, bis (p-toluyl) iodonium trifluoromethanesulfonate, bis (p-toluyl) ) Iodonium nonafluoro-n-butanesulfonate, bis (p-toluyl) iodonium 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n -Butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4 t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (4-t- Butylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium 2,4-difluorobenzenesulfonate,

  (4-fluorophenyl) phenyliodonium trifluoromethanesulfonate, (4-fluorophenyl) phenyliodonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) phenyliodonium 10-camphorsulfonate, bis (4-fluorophenyl) iodonium trifluoro Lomethanesulfonate, bis (4-fluorophenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-fluorophenyl) iodonium 10-camphorsulfonate, bis (cyclohexylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane Bis (2,6-dimethylphenylsulfonyl) diazomethane, bis (3,5-dimethylphenylsulfonyl) diazomethane, bi (T-Butylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] undecane-7- And sulfonyl) diazomethane.

  In this invention, it is preferable that the usage-amount of an acid generator (B) is 0.1-20 mass parts when a polymer (A) is 100 mass parts, More preferably, it is 0.5-15. Part by mass. In this case, if the total amount used is less than 0.1 parts by mass, the sensitivity and developability tend to decrease, while if it exceeds 20 parts by mass, the pattern shape, heat resistance and the like tend to decrease.

<Acid diffusion controller (C)>
The radiation-sensitive resin composition of the present invention has an action of controlling a diffusion phenomenon in a resist film of an acid generated from an acid generator (B) by exposure and suppressing an undesirable chemical reaction in a non-exposed region. It is preferable to mix an acid diffusion controller.
The acid diffusion controller is a component having an action of controlling a diffusion phenomenon in a resist film of an acid generated from an acid generator by exposure and suppressing an undesirable chemical reaction in a non-exposed region. By blending such an acid diffusion controller, the storage stability of the resulting radiation-sensitive resin composition is improved, the resolution as a resist is further improved, and the process from exposure to heat treatment after exposure is improved. A change in the line width of the resist pattern due to fluctuations in the placement time (PED) can be suppressed, and a composition having extremely excellent process stability can be obtained.

  As the acid diffusion controller, an amine compound having a polyether group is preferable. Specific examples include the following compounds (C-1) to (C-8). Among these, (C-1) [Tris (2-methoxymethoxyethyl) amine], (C-2) [Tris (2- (2-methoxyethoxy) methoxyethyl) amine], (C-4) [ Tris (2-methoxyethoxyethyl) amine] is preferred. These acid diffusion control agents can be used alone or in admixture of two or more.

<Additives>
Various additives, such as surfactant and a sensitizer, can be mix | blended with the radiation sensitive resin composition of this invention as needed.
The said surfactant is a component which shows the effect | action which improves the applicability | paintability of a composition, striation, the developability as a resist, etc.
Examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenol ether, polyoxyethylene n-nonylphenol ether, polyethylene glycol dilaurate, polyethylene Glycol distearate and the like can be mentioned, and as commercial products, for example, Ftop EF301, EF303, EF352 (above, manufactured by Tochem Products), Megafax F171, F173 (above) Dainippon Ink & Chemicals, Inc.), Florad FC430, FC431 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, C102, the SC103, the SC104, the SC105, the SC106 (manufactured by Asahi Glass Co., Ltd.), KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.). These surfactants can be used alone or in admixture of two or more.
Moreover, the compounding quantity of this surfactant is 2 mass parts or less normally, when a polymer (A) is 100 mass parts.

The sensitizer absorbs radiation energy and transmits the energy to the acid generator (B), thereby increasing the amount of acid produced. The radiation-sensitive resin composition It has the effect of improving the apparent sensitivity.
Examples of such sensitizers include acetophenones, benzophenones, naphthalenes, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines, carbazoles and the like. These sensitizers can be used alone or in admixture of two or more.
The amount of the sensitizer is usually 50 parts by mass or less when the polymer (A) is 100 parts by mass.

In addition, by blending dyes and / or pigments, the latent image of the exposed area can be visualized, and the influence of halation during exposure can be reduced. By blending an adhesion aid, adhesion to the substrate is further improved. can do.
Furthermore, as additives other than those described above, an antihalation agent such as 4-hydroxy-4′-methylchalcone, a shape improver, a storage stabilizer, an antifoaming agent, and the like can be blended.

<Preparation of composition solution>
The radiation-sensitive resin composition of the present invention is usually uniform in the solvent so that the concentration of the total solid content is usually 0.1 to 50% by mass, preferably 1 to 40% by mass, when used. After dissolution, the composition solution is prepared by, for example, filtering with a filter having a pore size of about 0.2 μm.
Examples of the solvent used for the preparation of the composition solution include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate and the like. Glycol monoalkyl ether acetates; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; propylene glycol dimethyl ether, propylene glycol diethyl Ether, propylene glycol di-n-propyl ether, propylene Propylene glycol dialkyl ethers such as recall di-n-butyl ether; propylene glycol monoalkyl such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate Ether acetates;

N-amyl formate, i-amyl formate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, i-propyl propionate Aliphatic carboxylic acid esters such as n-butyl propionate and i-butyl propionate; lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate and i-propyl lactate; ethyl hydroxyacetate, 2-hydroxy- Ethyl 2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate , Other esters such as 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate; toluene, xylene Aromatic hydrocarbons such as methyl ethyl ketone, 2-pentanone, 2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone and the like; N-methylformamide, N, N-dimethylformamide, N- Examples thereof include amides such as methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; lactones such as γ-butyrolacun.
These solvents can be used alone or in admixture of two or more.

<Method for forming resist pattern>
When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the composition solution prepared as described above is applied by appropriate coating means such as spin coating, cast coating, roll coating, etc. A resist film is formed by coating on a substrate such as a silicon wafer or a wafer coated with aluminum, and in some cases, a heat treatment (hereinafter referred to as “PB”) is performed at a temperature of about 70 to 160 ° C. in advance. After that, exposure is performed through a predetermined mask pattern. As the radiation used for exposure, for example, far ultraviolet rays such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm) are preferable. In this case, the exposure conditions such as the exposure amount are appropriately selected according to the composition of the radiation-sensitive resin composition, the type of each additive, and the like.
In the present invention, in order to stably form a fine resist pattern with high accuracy, heat treatment (hereinafter referred to as “PEB”) is performed at a temperature of 70 to 160 ° C. for 30 seconds or longer after exposure. preferable. In this case, when the temperature of the PEB is less than 70 ° C., there is a possibility that the variation in sensitivity depending on the type of the substrate spreads.

Thereafter, using an alkali developer, development is usually performed at 10 to 50 ° C. for 10 to 200 seconds, preferably at 15 to 30 ° C. for 15 to 100 seconds, particularly preferably at 20 to 25 ° C. for 15 to 90 seconds. Thus, a predetermined resist pattern is formed.
Examples of the alkali developer include alkali metal hydroxide, aqueous ammonia, mono-, di- or tri-alkylamines, mono-, di- or tri-alkanolamines, heterocyclic amines, and tetraalkyl. Alkaline compounds such as ammonium hydroxides, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene are usually used. An alkaline aqueous solution dissolved so as to have a concentration of 1 to 10% by mass, preferably 1 to 5% by mass, particularly preferably 1 to 3% by mass is used.
In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline aqueous solution.
In forming the resist pattern, a protective film can be provided on the resist film in order to prevent the influence of basic impurities contained in the environmental atmosphere.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Here, the part is based on mass unless otherwise specified.

Each measurement and evaluation in each of the following synthesis examples was performed in the following manner.
(1) Mw and Mn
Gel permeation based on monodisperse polystyrene using GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation under the analysis conditions of flow rate 1.0 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. It was measured by an association chromatography (GPC). Further, the degree of dispersion Mw / Mn was calculated from the measurement results.
⁽²⁾ 13 C-NMR analysis of ¹³ C-NMR analysis the polymer, using a Nippon Denshi Co. "JNM-EX270", was performed using CDCL ₃ as measurement solvent.

Hereinafter, each synthesis example will be described.
<Synthesis Example 1>
24 g of poly (p-hydroxystyrene) having an Mw of 12000 was dissolved in 100 g of dioxane, and then bubbled with nitrogen gas for 30 minutes. Thereafter, 3 g of ethyl vinyl ether, 3 g of ethyl-1-propenyl ether and 1 g of p-toluenesulfonic acid pyridinium salt as a catalyst were added to this solution and reacted at room temperature for 12 hours. Next, the reaction solution was dropped into a 1000 g aqueous solution of 1% by mass ammonia to precipitate a polymer, filtered, and then dried overnight in a vacuum dryer at 50 ° C.
This polymer has Mw of 15000 and Mw / Mn of 1.6. As a result of ¹³ C-NMR analysis, 20% of hydrogen atoms in the phenolic hydroxyl group in poly (p-hydroxystyrene) are 1-ethoxyethyl. The structure was substituted with a group and 15% was substituted with a 1-ethoxypropyl group. That is, it is a polymer containing repeating units corresponding to the repeating units (1), (2) and (3). This polymer is referred to as “resin (A-1)”.

<Synthesis Example 2>
To a solution of 120 g of poly (p-hydroxystyrene) having an Mw of 12,000 and 15 g of triethylamine in 500 g of dioxane, 20 g of di-t-butyl carbonate was added with stirring, and the mixture was further stirred at room temperature for 6 hours. 20 g of oxalic acid was added to neutralize the triethylamine. Next, the reaction solution was dropped into 200 g of water to coagulate the polymer, the coagulated polymer was washed several times with pure water, filtered, and dried overnight in a vacuum dryer at 50 ° C.
The obtained polymer had Mw of 8900 and Mw / Mn of 2.8, and as a result of ¹³ C-NMR analysis, 9% of hydrogen atoms in the phenolic hydroxyl group in poly (p-hydroxystyrene) was t- It had a structure substituted with a butoxycarbonyl group.
Next, the polymer was dissolved in 100 g of dioxane, and then bubbled with nitrogen gas for 30 minutes. Thereafter, 2 g of ethyl vinyl ether, 2 g of ethyl-1-propenyl ether, and 1 g of p-toluenesulfonic acid pyridinium salt as a catalyst were added to this solution and reacted at room temperature for 12 hours. Thereafter, the reaction solution was dropped into a 1% by mass aqueous ammonia solution to precipitate a polymer, filtered, and dried overnight in a vacuum dryer at 50 ° C.
This polymer has Mw of 11000 and Mw / Mn of 2.8. As a result of ¹³ C-NMR analysis, 14% of hydrogen atoms in the phenolic hydroxyl group in poly (p-hydroxystyrene) are 1-ethoxyethyl. And 11% substituted with a 1-ethoxypropyl group and 9% substituted with a t-butoxycarbonyl group. That is, it is a polymer containing repeating units corresponding to the repeating units (1), (2), (3) and (4). This polymer is referred to as “resin (A-2)”.

<Synthesis Example 3>
To a solution of 120 g of poly (p-hydroxystyrene) having an Mw of 12,000 and 15 g of triethylamine in 500 g of dioxane, 20 g of di-t-butyl carbonate was added with stirring, and the mixture was further stirred at room temperature for 6 hours. 20 g of oxalic acid was added to neutralize the triethylamine. Next, the reaction solution was dropped into 200 g of water to coagulate the polymer, the coagulated polymer was washed several times with pure water, filtered, and dried overnight in a vacuum dryer at 50 ° C.
The obtained polymer had Mw of 8900 and Mw / Mn of 2.8, and as a result of ¹³ C-NMR analysis, 9% of hydrogen atoms in the phenolic hydroxyl group in poly (p-hydroxystyrene) was t- It had a structure substituted with a butoxycarbonyl group.
Next, the polymer was dissolved in 100 g of dioxane, and then bubbled with nitrogen gas for 30 minutes. Thereafter, 2 g of ethyl-1-propenyl ether and 1 g of p-toluenesulfonic acid pyridinium salt as a catalyst were added to this solution and reacted at room temperature for 12 hours. Thereafter, the reaction solution was dropped into a 1% by mass aqueous ammonia solution to precipitate a polymer, filtered, and dried overnight in a vacuum dryer at 50 ° C.
This polymer has Mw of 11000 and Mw / Mn of 2.8. As a result of ¹³ C-NMR analysis, 11% of hydrogen atoms in the phenolic hydroxyl group in poly (p-hydroxystyrene) is 1-ethoxypropyl. And 9% of the group was substituted with a t-butoxycarbonyl group. That is, it is a polymer containing repeating units corresponding to the repeating units (1), (3) and (4). This polymer is referred to as “resin (A-3)”.

<Synthesis Example 4>
To a solution of 12 g of poly (p-hydroxystyrene) having an Mw of 12000 and 5 g of triethylamine in 50 g of dioxane, 7.0 g of di-t-butyl carbonate was added with stirring, and the mixture was further stirred at room temperature for 6 hours. Thereafter, 20 g of oxalic acid was added to neutralize triethylamine. Next, the reaction solution was dropped into 2000 g of water to coagulate the polymer, and the coagulated polymer was washed several times with pure water, filtered, and dried overnight in a vacuum dryer at 50 ° C.
This polymer has Mw of 9200 and Mw / Mn of 2.8. As a result of ¹³ C-NMR analysis, 30% of the hydrogen atoms in the phenolic hydroxyl group in poly (p-hydroxystyrene) are tert-butoxycarbonyl. It had a structure substituted with a group. That is, it is a polymer containing repeating units corresponding to the repeating units (1) and (4). This polymer is referred to as “resin (A-4)”.

<Synthesis Example 5>
24 g of poly (p-hydroxystyrene) having an Mw of 12000 was dissolved in 100 g of dioxane, and then bubbled with nitrogen gas for 30 minutes. Thereafter, 5 g of ethyl vinyl ether and 1 g of p-toluenesulfonic acid pyridinium salt as a catalyst were added to this solution and reacted at room temperature for 12 hours. Next, the reaction solution was dropped into a 1% by mass aqueous ammonia solution to precipitate a polymer, filtered, and dried overnight in a vacuum dryer at 50 ° C.
This polymer has Mw of 15000 and Mw / Mn of 1.7. As a result of ¹³ C-NMR analysis, 35% of the hydrogen atoms in the phenolic hydroxyl group in poly (p-hydroxystyrene) are 1-ethoxyethyl. It had a structure substituted with a group. That is, it is a polymer containing repeating units corresponding to the repeating units (1) and (2). This polymer is referred to as “resin (A-5)”.

<Synthesis Example 6>
After dissolving 101 g of p-acetoxystyrene, 45 g of 1-ethylcyclopentyl acrylate, 6 g of azobisisobutyronitrile, and 1 g of t-dodecyl mercaptan in 160 g of propylene glycol monomethyl ether, the reaction temperature is maintained at 70 ° C. in a nitrogen atmosphere. For 16 hours. After the polymerization, the reaction solution was dropped into 2000 g of n-hexane to coagulate and purify the resulting resin.
Next, 150 g of propylene glycol monomethyl ether was added to the resin again, and then 300 g of methanol, 80 g of triethylamine, and 15 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting resin was dissolved in acetone and then dropped into 2000 g of water to solidify. The resulting white powder was filtered and dried at 50 ° C. under reduced pressure overnight. did.
The obtained resin had Mw of 16000 and Mw / Mn of 1.9. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of p-hydroxystyrene and 1-ethylcyclopentyl acrylate was 70:30. It was. That is, it is a polymer containing repeating units corresponding to the repeating units (1) and (5). This resin is referred to as “resin (A-6)”.

<Synthesis Example 7>
After dissolving 106 g of p-acetoxystyrene, 12 g of 1-ethylcyclopentyl acrylate, 6 g of azobisisobutyronitrile and 1 g of t-dodecyl mercaptan in 160 g of propylene glycol monomethyl ether, the reaction temperature is maintained at 70 ° C. in a nitrogen atmosphere. For 16 hours. After the polymerization, the reaction solution was dropped into 1000 g of n-hexane to coagulate and purify the resulting resin.
Next, 150 g of propylene glycol monomethyl ether was added to the resin again, and then 300 g of methanol, 80 g of triethylamine, and 15 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting resin was dissolved in acetone and then dropped into 2000 g of water to solidify. The resulting white powder was filtered and dried at 50 ° C. under reduced pressure overnight. did.
The obtained resin had an Mw of 14000 and an Mw / Mn of 1.7. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of p-hydroxystyrene and 1-ethylcyclopentyl acrylate was 90:10. It was. 25 g of the obtained p-hydroxystyrene / 1-ethylcyclopentyl acrylate copolymer was dissolved in 100 g of n-butyl acetate, and after bubbling with nitrogen gas for 30 minutes, 3.3 g of ethyl vinyl ether was added to the catalyst. 1 g of p-toluenesulfonic acid pyridinium salt was added and reacted at room temperature for 12 hours. Thereafter, the reaction solution was dropped into a 2000 g solution of 1% by mass ammonia water to solidify the resin, filtered, and dried overnight at 50 ° C. under reduced pressure.
As a result of ¹³ C-NMR analysis, the obtained resin has a structure in which 23 mol% of hydrogen atoms in the phenolic hydroxyl group in poly (p-hydroxystyrene) are substituted with ethoxyxyethyl groups. The copolymerization molar ratio of the site | part by which the hydrogen atom of -hydroxystyrene and p-hydroxystyrene was substituted with ethoxyethyl, and 1-ethylcyclopentyl acrylate was 67:23:10. That is, it is a polymer containing repeating units corresponding to the repeating units (1), (2) and (5). This resin is referred to as “resin (A-7)”.

<Synthesis Example 8>
To a solution of 120 g of poly (p-hydroxystyrene) having an Mw of 12000 and 15 g of triethylamine in 500 g of dioxane, 20 g of di-t-butyl carbonate was added with stirring, and the mixture was further stirred at room temperature for 6 hours. 20 g of acid was added to neutralize the triethylamine. Next, the reaction solution was dropped into 200 g of water to coagulate the polymer, the coagulated polymer was washed several times with pure water, filtered, and dried overnight in a vacuum dryer at 50 ° C.
The obtained polymer has Mw of 8,900 and Mw / Mn of 2.8. As a result of ¹³ C-NMR analysis, 9% of hydrogen atoms in the phenolic hydroxyl group in poly (p-hydroxystyrene) It had a structure substituted with a t-butoxycarbonyl group.
Next, the polymer was dissolved in 100 g of dioxane, and then bubbled with nitrogen gas for 30 minutes. Thereafter, 1.7 g of ethyl vinyl ether and 1 g of p-toluenesulfonic acid pyridinium salt as a catalyst were added to this solution and reacted at room temperature for 12 hours. Thereafter, the reaction solution was dropped into a 1% by mass aqueous ammonia solution to precipitate a polymer, filtered, and dried overnight in a vacuum dryer at 50 ° C.
This polymer has Mw of 10500 and Mw / Mn of 2.8. As a result of ¹³ C-NMR analysis, 11% of the hydrogen atoms in the phenolic hydroxyl group in poly (p-hydroxystyrene) are 1-ethoxyethyl. And 9% of the group was substituted with a t-butoxycarbonyl group. That is, it is a polymer containing repeating units corresponding to the repeating units (1), (2) and (4). This polymer is referred to as “resin (A-8)”.

<Synthesis Example 9>
After dissolving 106 g of p-acetoxystyrene, 12 g of 1-ethylcyclopentyl acrylate, 6 g of azobisisobutyronitrile and 1 g of t-dodecyl mercaptan in 160 g of propylene glycol monomethyl ether, the reaction temperature is maintained at 70 ° C. in a nitrogen atmosphere. For 16 hours. After the polymerization, the reaction solution was dropped into 1000 g of n-hexane to coagulate and purify the resulting resin.
Next, 150 g of propylene glycol monomethyl ether was added to the resin again, and then 300 g of methanol, 80 g of triethylamine, and 15 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting resin was dissolved in acetone and then dropped into 2000 g of water to solidify. The resulting white powder was filtered and dried at 50 ° C. under reduced pressure overnight. did.
The obtained resin had an Mw of 14000 and an Mw / Mn of 1.7. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of p-hydroxystyrene and 1-ethylcyclopentyl acrylate was 90:10. It was. 25 g of the obtained p-hydroxystyrene / 1-ethylcyclopentyl acrylate copolymer was dissolved in 100 g of n-butyl acetate, and after bubbling with nitrogen gas for 30 minutes, 4.0 g of ethyl-1-propenyl ether was obtained. And 1 g of p-toluenesulfonic acid pyridinium salt was added as a catalyst and reacted at room temperature for 12 hours. Thereafter, the reaction solution was dropped into a 2000 g solution of 1% by mass ammonia water to solidify the resin, filtered, and dried overnight at 50 ° C. under reduced pressure.
As a result of ¹³ C-NMR analysis, the obtained resin has a structure in which 23 mol% of hydrogen atoms in the phenolic hydroxyl group in poly (p-hydroxystyrene) are substituted with 1-ethoxypropyl group, The copolymerization molar ratio of 1-ethylcyclopentyl acrylate to the site where the hydrogen atom of p-hydroxystyrene and p-hydroxystyrene was substituted with 1-ethoxypropyl was 67:23:10. That is, it is a polymer containing repeating units corresponding to the repeating units (1), (3) and (5). This resin is referred to as “resin (A-9)”.

<< Evaluation of radiation sensitive resin composition >>
Examples 1-4 and Comparative Examples 1-7
Each component shown in Table 1 (where “part” is based on mass) was mixed to obtain a uniform solution, and then filtered through a membrane filter having a pore size of 200 nm to prepare each composition solution.
Thereafter, “DUV44” manufactured by Brewer Science Co., Ltd. was spin-coated to a film thickness of 80 nm, and baked at 225 ° C. for 60 seconds, on a “Clean Track ACT-8” manufactured by Tokyo Electron Ltd. After spin-coating each composition solution, PB was performed under the conditions shown in Table 1 to form a resist film having a thickness of 400 nm.
Next, using a Nikon scanner “NSR-S203B” (numerical aperture = 0.68, σ = 0.75), exposure was performed through a binary mask, and then PEB was performed under the conditions shown in Table 1. . Thereafter, a 2.38 mass% tetramethylammonium hydroxide aqueous solution was used and developed by a paddle method using an LD nozzle at 23 ° C. for 30 seconds, followed by washing with pure water and drying to form a resist pattern. .
Each resist was evaluated in the following manner, and the results are shown in Table 2.

Each evaluation method is as follows.
(1) Sensitivity:
After exposing the resist film formed on the silicon wafer, PEB is performed immediately, and then developed, washed with water, and dried to form a resist pattern. When a resist pattern is formed, a line-and-space pattern (1L1S) having a line width of 130 nm is formed. The exposure amount formed in a one-to-one line width was set as the optimum exposure amount, and the sensitivity was evaluated based on this optimum exposure amount.

(2) Depth of focus margin [DOF (1L / 1S)]:
A 130 nm line-and-space pattern (1L1S) is exposed with an optimal exposure amount and a focal depth of −1.0 μm to +1.0 μm in increments of 100 nm, and the line width is 117 nm (−10%) to 143 nm (+ 10%). ) Range (nm) was defined as the depth of focus margin.

(3) Depth of focus margin [DOF (5L / 1S)]:
A 150nm narrow space pattern (5L / 1S) is exposed with an optimal exposure amount and a depth of focus of -1.0 to +1.0 μm in 100 nm increments, and the line width is 135 nm (−10%) to 165 nm (+ 10%). The range (nm) to be is defined as the depth of focus margin.

(4) Pattern shape:
The pattern shape was evaluated by observing the edge portion at the pattern top of the 130 nm 1L1S pattern at the optimal exposure amount using a CD-SEM (manufactured by Hitachi High-Technologies Corporation, “S-9220”). FIG. 1A shows a schematic diagram for explaining a cross section of the resist pattern, and FIG. 1B shows a schematic diagram for explaining the upper surface side of the resist pattern.
The evaluation of the pattern shape will be described in detail. As shown in FIG. 1A, the edge portion 2a of the resist pattern is round, and when observed by CD-SEM, the edge portion 2a is white with a width d. Visible (hereinafter, the edge portion that looks white is called “white edge”). In the resist pattern, it is preferable that the width of the white edge is as short as possible, and it can be said that the pattern shape is good. Therefore, the pattern shape was evaluated with the width d of the white edge.

Moreover, components other than resin shown in Table 1 are as follows.
<Acid generator (B)>
(B-1): Triphenylsulfonium trifluoromethanesulfonate (B-2): Bis (cyclohexylsulfonyl) diazomethane (B-3): Bis (2,6-dimethylphenylsulfonyl) diazomethane
<Acid diffusion inhibitor (C)>
(C-1): Tris (2-methoxymethoxyethyl) amine (C-2): Tris (2- (2-methoxyethoxy) methoxyethyl) amine (C-3): Tri-n-octylamine
<Solvent (D)>
(D-1): Ethyl lactate (D-2): Ethyl 3-ethoxypropionate (D-3): Propylene glycol monomethyl ether acetate

  As is apparent from Table 2, when the radiation-sensitive resin composition of the present invention was used, not only the focal depth of the 1L / 1S line and space pattern but also the focal point of the narrow space pattern (5L / 1S). It turns out that it is excellent also in depth. It was also found that the width of the white edge is short, the pattern shape is excellent, and a fine pattern can be formed with high accuracy and stability for both the line and space pattern and the narrow space pattern.

It is a schematic diagram explaining the cross section and upper surface shape of a resist pattern.

Explanation of symbols

  1; substrate, 2; resist pattern.

Claims (9)

(A) A repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3), and a repeating unit represented by the following formula (4) And a polymer containing a repeating unit represented by the following formula (5):
(B) A radiation sensitive resin composition comprising a radiation sensitive acid generator.

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

(Wherein R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom, a methyl group or an ethyl group.)

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkyl group having 2 to 4 carbon atoms, and R ⁸ represents a hydrogen atom, a methyl group or an ethyl group. Group.)

(In the formula, R ⁹ represents a hydrogen atom or a methyl group.)

(In the formula, R ¹⁰ represents a hydrogen atom or a methyl group, and R ¹¹ represents a methyl group or an ethyl group.)   The radiation sensitive resin composition according to claim 1, further comprising (C) an acid diffusion controller.   The radiation sensitive resin composition according to claim 1, wherein the component (B) is a disulfonyldiazomethane compound and / or a sulfonium salt.   The radiation sensitive resin composition according to claim 2 or 3, wherein the component (C) is an amine compound having a polyether group.   The radiation sensitivity according to any one of claims 2 to 4, wherein bis (cyclohexyl) diazomethane is contained as the component (B), and tris (2-methoxymethoxyethyl) amine is contained as the component (C). Resin composition. The component (A) is
A copolymer containing each repeating unit represented by the general formulas (1), (2) and (5);
The radiation sensitive resin composition in any one of Claims 1 thru | or 5 containing the copolymer containing each repeating unit represented by the said General formula (1), (3) and (4). The component (A) is
A copolymer containing each repeating unit represented by the general formulas (1), (2) and (4);
The radiation sensitive resin composition in any one of Claims 1 thru | or 5 containing the copolymer containing each repeating unit represented by the said General formula (1), (3) and (5). The component (A) is
A copolymer containing each repeating unit represented by the general formulas (1), (2) and (3);
The radiation sensitive resin composition in any one of Claims 1 thru | or 5 containing the copolymer containing each repeating unit represented by the said General formula (1) and (4). The component (A) is
A copolymer containing each repeating unit represented by the general formulas (1), (2), (3) and (4);
The radiation sensitive resin composition in any one of Claims 1 thru | or 5 containing the copolymer containing each repeating unit represented by the said General formula (1) and (5).

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