JP4352831B2 - Radiation sensitive resin composition - Google Patents

Description

The present invention is a chemistry useful for microfabrication using various kinds of radiation such as deep ultraviolet rays such as KrF excimer laser, ArF excimer laser or F ₂ excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams. The present invention relates to a radiation sensitive resin composition that can be suitably used as an amplification resist.

In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration, recently, lithography technology capable of microfabrication at a level of 0.20 μm or less is required.
However, in the conventional photolithography process, near ultraviolet rays such as i rays are generally used as radiation, and it is said that fine processing at a sub-quarter micron level or less is extremely difficult with this near ultraviolet rays.
Therefore, in order to enable microfabrication at a level of 0.20 μm or less, use of radiation having a shorter wavelength is being studied. Examples of such short-wave radiation include far-ultraviolet rays such as an emission line spectrum of an mercury lamp and an excimer laser, an X-ray, an electron beam, etc. Among them, in particular, a KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) or F ₂ excimer laser (wavelength 157 nm) has attracted attention. As a radiation-sensitive resin composition suitable for these excimer lasers, a component having an acid-dissociable functional group and irradiation with radiation ( Hereinafter, many chemically amplified radiation-sensitive resin compositions utilizing a chemical amplification effect by a radiation-sensitive acid generator that generates an acid by “exposure” have been proposed.
This chemically amplified radiation sensitive resin composition itself is insoluble or hardly soluble in an alkaline developer, but uses a resin having an acid dissociable group that is dissociated by the action of an acid. Dissociated by the action of the acid generated from the radiation acid generator to form acidic functional groups such as carboxyl groups and phenolic hydroxyl groups. As a result, the exposed area of the resist film becomes soluble in an alkaline developer. Is.

  Recently, several chemically amplified radiation-sensitive resin compositions using two or more radiation-sensitive acid generators have been proposed. For example, Patent Document 1 discloses an ionic compound such as an iodonium salt compound and N-sulfonyl. A radiation-sensitive acid generator comprising a nonionic compound such as an oxyimide compound, and a copolymer of hydroxystyrenes and (meth) acrylic acid esters having an acid-sensitive moiety such as t-butyl (meth) acrylate In addition, Patent Document 2 discloses a component having a large effect of slowing the dissolution rate of an exposed portion such as a bis (triphenylsulfonium) sulfide salt compound, an N-sulfonyloxyimide compound, and diphenyliodonium. A radiation-sensitive acid generator comprising a component having a small effect of slowing the dissolution rate of an exposed part such as a salt compound And a positive photoresist composition containing a resin having an acid-dissociable group, such as a copolymer of hydroxystyrenes and t-butoxystyrenes, is disclosed in Patent Document 3 as an N-sulfonyloxyimide compound and hydroxystyrene. And a copolymer of styrenes having an acid-dissociable acetal group, and another radiation-sensitive acid generator such as an onium salt compound may be used in combination, and the copolymer may be t-butoxy. Radiation sensitive resin compositions that may contain styrenes are disclosed respectively.

JP 2000-147753 A JP-A-11-167199 Japanese Patent Laid-Open No. 11-352677

By the way, the recent photolithography process is rapidly miniaturized, and in particular, in the photolithography process using a KrF excimer laser, the limit resolution is approaching half or less of the light source wavelength. Therefore, the demand for a chemically amplified radiation-sensitive resin composition as a photoresist is becoming more and more severe, and particularly the demand for a depth of focus margin is severe.
However, in the field of integrated circuit elements, when a higher degree of integration is required than in the past, the conventional chemically amplified radiation-sensitive resin compositions including those in Patent Documents 1 to 3 have particularly a depth of focus margin. There is a problem that it is not enough.

An object of the present invention is to cope with such problems, and is a chemically amplified resist that is sensitive to far ultraviolet rays represented by actinic radiation, for example, KrF excimer laser, ArF excimer laser, or F ₂ excimer laser. An object of the present invention is to provide a radiation-sensitive resin composition that is excellent in basic physical properties such as sensitivity and pattern shape, and that is particularly excellent in focus depth margin.

The present invention
(A) An alkali-insoluble or hardly alkali-soluble resin having a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), A resin that becomes readily soluble in alkali when the -C (R ³ ) ₃ group is dissociated, and (B) an N-sulfonyloxyimide compound consisting of a compound represented by the following general formula (8) and the following general formula (9) A radiation-sensitive resin composition (hereinafter referred to as “radiation-sensitive resin composition [I]”) containing a radiation-sensitive acid generator containing a diphenyliodonium salt compound consisting of a compound represented by the formula: ).

〔一般式（１）において、Ｒ¹ は１価の有機基を表し、複数存在するＲ¹ は相互に同一でも異なってもよく、ｎは１〜３の整数であり、ｍは０〜２の整数である。〕

[In General Formula (1), R ¹ represents a monovalent organic group, a plurality of R ¹ may be the same or different from each other, n is an integer of 1 to 3, and m is 0 to 2. It is an integer. ]

〔一般式（２）において、Ｒ² は水素原子またはメチル基を表し、各Ｒ³ は相互に独立に炭素数１〜４の飽和炭化水素基を表す。〕

〔一般式（８）において、Ｒ ⁷ は２価の有機基を示し、Ｒ ⁸ は１価の有機基を示す。〕

〔一般式（９）において、Ｘ ^- は１価のアニオンを表す。〕

[In General formula (2), R < ² > represents a hydrogen atom or a methyl group, and each R < ³ > represents a C1-C4 saturated hydrocarbon group mutually independently. ]

[In General Formula (8), R ⁷ represents a divalent organic group, and R ⁸ represents a monovalent organic group. ]

[In the general formula (9), X ⁻ represents a monovalent anion. ]

Hereinafter, the present invention will be described in detail.
The component (A) in the component (A) radiation-sensitive resin composition [I] is a repeating unit represented by the general formula (1) (hereinafter referred to as “repeating unit (1)”) and the general formula (1). 2) an alkali-insoluble or hardly alkali-soluble resin having a repeating unit represented by 2) (hereinafter referred to as “repeating unit (2)”), and —C (R ³ ) _{3 in the} general formula (2) It consists of a resin (hereinafter referred to as “resin (A)”) that becomes readily soluble in alkali when the group is dissociated.
The term “alkali insoluble or hardly soluble in alkali” as used herein refers to the alkali development conditions employed when a resist pattern is formed from a resist film formed using a radiation-sensitive resin composition containing the resin (A). Thus, when a film using only the resin (A) is developed instead of the resist film, it means that 50% or more of the initial film thickness of the film remains after development.

In the general formula (1), examples of the monovalent organic group represented by R ¹ include a linear or branched alkyl group having 1 to 12 carbon atoms and a linear or branched halogen group having 1 to 12 carbon atoms. An alkyl group, a linear or branched alkoxyl group having 1 to 12 carbon atoms, a linear or branched halogenated alkoxyl group having 1 to 12 carbon atoms, and the like.

Preferred examples of the repeating unit (1) include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-methyl-3-hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3- Examples of units in which a polymerizable unsaturated bond is cleaved such as hydroxystyrene, 2-methyl-4-hydroxystyrene, 3-methyl-4-hydroxystyrene, 3,4-dihydroxystyrene, 2,4,6-trihydroxystyrene be able to.
Of these repeating units (1), a unit in which the polymerizable unsaturated bond of p-hydroxystyrene is cleaved is particularly preferable.
In the resin (A), the repeating unit (1) can be present alone or in combination of two or more.

Preferred examples of the repeating unit (2) include pt-butoxystyrene, pt-butoxy-α-methylstyrene, p- (2-ethyl-2-propoxy) styrene, and p- (2-ethyl). And a unit in which a polymerizable unsaturated bond such as 2-propoxy) -α-methylstyrene is cleaved.
Among these repeating units (2), a unit in which a polymerizable unsaturated bond of pt-butoxystyrene is cleaved is particularly preferable.
In the resin (A), the repeating unit (2) may be present alone or in combination of two or more.

The resin (A) can have a repeating unit other than the repeating unit (1) and the repeating unit (2) (hereinafter referred to as “other repeating unit (a)”).
As other repeating units (a), for example,
i-propyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, cyclohexyl ( (Meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, di Cyclopentenyl (meth) acrylate, adamantane-1-yl (meth) acrylate, 2-methyladamantan-2-yl (meth) acrylate, 2-ethyladamantan-2-yl Meth) acrylate, tetrahydrofuranyl (meth) acrylate, a polymerizable unsaturated bond such as tetrahydropyranyl (meth) acrylate is cleaved (meth) acrylic ester units;

Polymerization failure such as t-butoxycarbonyloxystyrene, pt-butoxycarbonylmethyloxystyrene, p- (2-t-butoxycarbonylethyloxy) styrene, p-tetrahydrofuranyloxystyrene, p-tetrahydropyranyloxystyrene, etc. In addition to units containing acid-dissociable groups such as vinyl aromatic units with saturated bonds cleaved,

Styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, o -Vinyl aromatic compounds such as methoxystyrene, m-methoxystyrene, p-methoxystyrene;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, adamantylmethyl (meth) acrylate, Phenyl (meth) acrylate, phenethyl (meth) acrylate,

（式中、ａは１〜６の整数である。）、 Monomer represented by the following formula (5)

(Wherein, a is an integer of 1 to 6),

（式中、ｂは１〜６の整数である。）、 Monomer represented by the following formula (6)

(Wherein b is an integer of 1 to 6),

（式中、各ｃはそれぞれ１〜６の整数である。）
等の他の（メタ）アクリル酸エステル類； Monomer represented by the following formula (7)

(In the formula, each c is an integer of 1 to 6)
Other (meth) acrylic acid esters, etc .;

〔一般式（３）において、Ｒ⁴ は水素原子またはメチル基を表し、各Ｒ⁵ は相互に独立に水素原子または炭素数１〜４の飽和炭化水素基を表す。〕； Unsaturated amide compound represented by the following general formula (3)

[In General formula (3), R < ⁴ > represents a hydrogen atom or a methyl group, and each R < ⁵ > represents a hydrogen atom or a C1-C4 saturated hydrocarbon group mutually independently. ];

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid;
Unsaturated polycarboxylic anhydrides such as maleic anhydride and itaconic anhydride;
Carboxyalkyl esters of unsaturated carboxylic acids such as 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate;
Unsaturated nitrile compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile;
Unsaturated imide compounds such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
N-vinyl-ε-caprolactam, N-vinyl pyrrolidone, 2-vinyl pyridine, 3-vinyl pyridine, 4-vinyl pyridine, 2-vinyl imidazole, other nitrogen-containing vinyl compounds such as 4-vinyl imidazole, etc. Examples include units in which a saturated bond is cleaved.

Among these other repeating units (a), polymerizability such as styrene, α-methylstyrene, a monomer represented by the formula (5), and an unsaturated amide compound represented by the general formula (3). A unit in which an unsaturated bond is cleaved is preferred.
In the resin (A), other repeating units (a) may be present alone or in combination of two or more.

  In the resin (A), the content of the repeating unit (1) is usually 50 to 90 mol%, preferably 60 to 80 mol%, particularly preferably 65 to 75 mol%, based on all repeating units. The content of the repeating unit (2) is usually 10 to 40 mol%, preferably 15 to 35 mol%, particularly preferably 20 to 30 mol%, based on all repeating units, and other repeating units (a ) Is usually 20 mol% or less, preferably 10 mol% or less, based on all repeating units, and the content of repeating units having an acid dissociable group is usually based on all repeating units. , 10 to 40 mol%, preferably 15 to 35 mol%.

  In this case, if the content of the repeating unit (1) is less than 50 mol%, the adhesion of the resist pattern to the substrate tends to be reduced, whereas if it exceeds 90 mol%, the resolution tends to be reduced. In addition, when the content of the repeating unit (2) is less than 10 mol%, the resolution tends to decrease, and when it exceeds 40 mol%, the adhesion of the resist pattern to the substrate tends to decrease. Moreover, when the content rate of another repeating unit (a) exceeds 20 mol%, there exists a tendency for the resolution to fall. Furthermore, if the content of the repeating unit having an acid dissociable group is less than 10 mol%, the resolution tends to be lowered, whereas if it exceeds 40 mol%, the adhesion of the resist pattern to the substrate tends to be lowered. .

The polystyrene-reduced weight molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC) of the resin (A) is usually 1,000 to 150,000, preferably 3,000 to 100,000. It is.
Moreover, the ratio (Mw / Mn) of Mw of the resin (A) and polystyrene-reduced number molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC) is usually 1 to 10, preferably Is 1-5.
In the radiation sensitive resin composition [I], the resin (A) can be used alone or in admixture of two or more.

Resin (A) is, for example,
In the copolymer obtained after copolymerizing acetoxystyrene or a nucleus-substituted derivative thereof and a monomer giving the repeating unit (2), optionally together with a monomer giving another repeating unit (a) A method for selectively hydrolyzing the acetoxy group of
A method of substituting part of the hydrogen atoms of the phenolic hydroxyl group in the precursor resin containing a phenolic hydroxyl group with an acid-dissociable group containing a -C (R ³ ) ₃ group;
A monomer that gives the repeating unit (1) and a monomer that gives the repeating unit (2) may be produced by a method such as copolymerization with a monomer that gives another repeating unit (a). it can.

The component (B) in the component (B) radiation-sensitive resin composition [I] is N-sulfonyl composed of a compound represented by the general formula (8) (hereinafter referred to as “acid generator (B1)”). It consists of a radiation-sensitive acid generator containing a diphenyliodonium salt compound consisting of an oxyimide compound and a compound represented by the general formula (9) (hereinafter referred to as “acid generator (B2)”) as an essential component.

In the general formula (8), examples of the divalent organic group represented by R ⁷ include a methylene group, a linear or branched alkylene group having 2 to 20 carbon atoms, an aralkylene group having 2 to 20 carbon atoms, and difluoromethylene. A divalent group having a group, a linear or branched perfluoroalkylene group having 2 to 20 carbon atoms, a cyclohexylene group, a phenylene group or a norbornane skeleton, or an aryl group or carbon having 6 or more carbon atoms. Examples thereof include a group substituted with an alkoxyl group having a number of 1 or more.

Examples of the monovalent organic group represented by R ⁸ include a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, and carbon. Examples include a perfluorocycloalkyl group having 3 to 10 carbon atoms, a monovalent hydrocarbon group having 7 to 15 carbon atoms having a bicyclo ring, an aryl group having 6 to 12 carbon atoms, and the like, and a hydrocarbon having the bicyclo ring The group and the aryl group may each be substituted with a halogen atom or an oxo group.

As a specific example of a preferable acid generator (B1),
N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (benzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) ) Succinimide, N- (10-camphorsulfonyloxy) succinimide and the like.
Of these acid generators (B1), N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide is particularly preferable.
In the present invention, the N-sulfonyloxyimide compounds can be used alone or in admixture of two or more.

In the general formula (9), as the monovalent anion of X ⁻ , for example, MX _i (where M represents a boron atom, phosphorus atom, arsenic atom or antimony atom, X represents a halogen atom, i represents And an anion of 4 to 6.), a halogen anion, a sulfonic acid anion having 1 to 20 carbon atoms, a carboxylic acid anion having 1 to 20 carbon atoms, and the like. It may be substituted with a halogen atom or an oxo group.

As the acid generator (B2) in the present invention, a compound in which X ⁻ is the sulfonate anion is preferable, and specific examples thereof include:
Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium p-tri Fluoromethylbenzene sulfonate, diphenyl iodonium perfluorobenzene sulfonate, etc. can be mentioned.
Of these acid generators (B2), diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium 10-camphorsulfonate, and the like are particularly preferable.
In the present invention, the diphenyliodonium salt compounds can be used alone or in admixture of two or more.

  In the radiation-sensitive resin composition [I], the diphenyliodonium salt compound has a higher radiation transmittance than the triphenylsulfonium salt, bis (t-butyl) iodonium salt, and the like. Deterioration of pattern shape and variation in pattern line width are small, so that it shows the action of increasing the depth of focus margin, and this diphenyliodoiodonium salt compound is used in combination with an N-sulfonyloxyimide compound having a strong dissolution inhibiting effect. As a result, a larger depth of focus margin can be achieved.

In the radiation sensitive resin composition [I], a radiation sensitive acid generator other than the N-sulfonyloxyimide compound and the diphenyliodonium salt compound (hereinafter referred to as “other acid generator”) should be used. You can also.
Examples of other acid generators include onium salt compounds such as iodonium salts and sulfonium salts, organic halogen compounds, and sulfone compounds such as disulfones and disulfonyldiazomethanes.

Preferred other acid generators include, for example,
Bis (pt-butylphenyl) iodonium trifluoromethanesulfonate, bis (pt-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (pt-butylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (pt-butylphenyl) iodonium p-toluenesulfonate, bis (pt-butylphenyl) iodonium 10-camphorsulfonate, bis (pt-butylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis ( pt-butylphenyl) iodonium perfluorobenzenesulfonate,
Bis (p-fluorophenyl) iodonium trifluoromethanesulfonate, bis (p-fluorophenyl) iodonium nonafluoro-n-butanesulfonate, bis (p-fluorophenyl) iodonium perfluoro-n-octanesulfonate, bis (p-fluorophenyl) ) Iodonium 10-camphorsulfonate;
(P-fluorophenyl) (phenyl) iodonium trifluoromethanesulfonate, (p-fluorophenyl) (phenyl) iodonium nonafluoro-n-butanesulfonate, (p-fluorophenyl) (phenyl) iodonium perfluoro-n-octanesulfonate, (P-fluorophenyl) (phenyl) iodonium 10-camphorsulfonate,

Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, triphenylsulfonium 10-camphorsulfonate , Triphenylsulfonium p-trifluoromethylbenzenesulfonate, triphenylsulfonium perfluorobenzenesulfonate,
Tris (p-methoxyphenyl) sulfonium trifluoromethanesulfonate, tris (p-methoxyphenyl) sulfonium nonafluoro-n-butanesulfonate, tris (p-methoxyphenyl) sulfonium perfluoro-n-octanesulfonate, tris (p-methoxyphenyl) ) Sulfonium p-toluenesulfonate, tris (p-methoxyphenyl) sulfonium benzenesulfonate, tris (p-methoxyphenyl) sulfonium 10-camphorsulfonate, tris (p-methoxyphenyl) sulfonium p-trifluoromethylbenzenesulfonate, tris (p -Methoxyphenyl) sulfonium perfluorobenzenesulfonate,

Tris (p-fluorophenyl) sulfonium trifluoromethanesulfonate, tris (p-fluorophenyl) sulfonium p-toluenesulfonate,
(P-hydroxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-hydroxyphenyl) diphenylsulfonium p-toluenesulfonate,
Onium salt compounds such as (p-fluorophenyl) diphenylsulfonium trifluoromethanesulfonate and (p-fluorophenyl) diphenylsulfonium p-toluenesulfonate;
Disulfonyldiazomethanes such as bis (cyclohexylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, etc. be able to.
In the present invention, other acid generators can be used alone or in admixture of two or more.

  In the radiation sensitive resin composition [I], the amount of the radiation sensitive acid generator used is preferably 0.1 with respect to 100 parts by weight of the total resin component from the viewpoint of ensuring the sensitivity and developability as a resist. -20 parts by weight, more preferably 0.1-15 parts by weight. In this case, if the amount of the radiation-sensitive acid generator used is less than 0.1 parts by weight, the sensitivity and developability tend to decrease. It tends to be difficult to obtain a resist pattern.

  The weight ratio of the N-sulfonyloxyimide compound to the diphenyliodonium salt compound (N-sulfonyloxyimide compound / diphenyliodonium salt compound) is preferably 99/1 to 5/95, more preferably 95/5 to 40. / 60, particularly preferably 92/8 to 50/50. In this case, even if the weight ratio exceeds 99/1 or less than 5/95, the pattern shape tends to be impaired, or the effect of improving the depth of focus margin tends to decrease.

  Moreover, the usage-amount of another acid generator is 30 weight% or less normally with respect to all the radiation sensitive acid generators, Preferably it is 10 weight% or less. In this case, if the use ratio of the other acid generator exceeds 30% by weight, the intended effect of the present invention may be insufficient.

Polymer (C)
The radiation sensitive resin composition [I] is a unit in which a polymerizable unsaturated bond of the unsaturated amide compound represented by the general formula (3) (hereinafter referred to as “unsaturated amide compound (3)”) is cleaved. And / or a polymer having a unit in which a polymerizable unsaturated bond of diacetone (meth) acrylamide is cleaved (hereinafter referred to as “polymer (C)”).

Hereinafter, the unsaturated amide compound (3) and diacetone (meth) acrylamide are collectively referred to as “specific amide monomer”, and the unit in which the polymerizable unsaturated bond of the specific amide monomer is cleaved is referred to as “specific amide monomer”. System repeat unit ".
Preferred unsaturated amide compounds (3) in the present invention include, for example, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and Ni-propyl (meth) acrylamide. Nt-butyl (meth) acrylamide and the like.
In the present invention, as the specific amide monomer, N, N-dimethyl (meth) acrylamide and the like are particularly preferable.

Although a polymer (C) can also consist only of a specific amide type repeating unit, it is preferable to have at least the said repeating unit (1) from a compatible viewpoint with resin (A).
In the polymer (C), the repeating unit (1) is particularly preferably a unit in which the polymerizable unsaturated bond of p-hydroxystyrene is cleaved.

The polymer (C) can also have a repeating unit other than the specific amide-based repeating unit and the repeating unit (1) (hereinafter referred to as “other repeating unit (c)”).
Examples of the other repeating unit (c) include the units exemplified for the repeating unit (2) and the other repeating unit (a) in the resin (A) (however, the polymerizable unsaturated unsaturated amide compound (3)). The same as the above can be mentioned.
Among these other repeating units (c), a unit in which a polymerizable unsaturated bond such as pt-butoxystyrene or styrene is cleaved is particularly preferable.
In the polymer (C), other repeating units (c) may be present alone or in combination of two or more.

  In the polymer (C), the content of the specific amide-based repeating unit is usually 0.1 mol% or more, preferably 1 to 40 mol%, particularly preferably 2 to 20 mol%, based on all repeating units. The content of the repeating unit (1) is usually 90 mol% or less, preferably 50 to 80 mol%, particularly preferably 60 to 80 mol%, based on all repeating units, and other repeating units ( The content of c) is usually 40 mol% or less, preferably 35 mol% or less, based on all repeating units.

  In this case, when the content of the specific amide repeating unit is less than 0.1 mol%, the effect of improving the depth of focus margin tends to be reduced. Moreover, when the content rate of a repeating unit (1) exceeds 90 mol%, there exists a tendency for the solubility to the solvent used for the composition solution mentioned later to fall. Moreover, when the content rate of another repeating unit (c) exceeds 40 mol%, there exists a tendency for compatibility with resin (A) to fall.

In the radiation sensitive resin composition [I], when the resin (A) has a repeating unit derived from the unsaturated amide compound (3), the desired effect can be obtained even if the polymer (C) is not contained. However, when the resin (A) does not contain a repeating unit derived from the unsaturated amide compound (3), it is preferable to contain the polymer (C).
In this latter case, the amount of the polymer (C) used is such that the content of the specific amide repeating unit containing the repeating unit derived from the unsaturated amide compound (3) in the resin (A) is the same as that of the resin (A). It is preferably adjusted to 0.01 to 5 parts by weight, more preferably 0.1 to 5 parts by weight per 100 parts by weight in total with the polymer (C).

The Mw of the polymer (C) is usually 1,000 to 150,000, preferably 3,000 to 100,000.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the polymer (C) is usually 1 to 10, preferably 1 to 5.
In the radiation sensitive resin composition [I], the polymer (C) can be used alone or in admixture of two or more.

The polymer (C) is, for example,
After copolymerizing a specific amide monomer and acetoxystyrene or a nucleus-substituted derivative thereof together with a monomer that optionally gives another repeating unit (c), an acetoxy group in the obtained copolymer A method of selective hydrolysis;
The specific amide monomer may be produced by a method of polymerizing, for example, in the presence of a monomer that gives the repeating unit (1), optionally together with a monomer that gives another repeating unit (c). it can.

The acid diffusion control agent radiation sensitive resin composition [I] controls the diffusion phenomenon in the resist film of the acid generated from the radiation sensitive acid generator by exposure, and suppresses undesired chemical reactions in non-exposed areas. It is preferable to add an acid diffusion control agent having the function of By using such an acid diffusion control agent, the storage stability of the composition is improved, the resolution is improved as a resist, and due to fluctuations in the holding time (PED) from exposure to heat treatment after exposure. Changes in the line width of the resist pattern can be suppressed, and the process stability is extremely excellent.

As the acid diffusion controller, a nitrogen-containing organic compound whose basicity does not change by exposure or heat treatment in the resist pattern forming step is preferable.
Examples of such a nitrogen-containing organic compound include a compound represented by the following general formula (4) (hereinafter referred to as “nitrogen-containing compound (α)”), a compound represented by the following general formula (10) ( Hereinafter, referred to as “nitrogen-containing compound (β)”), diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (γ)”), diamino polymer having three or more nitrogen atoms (Hereinafter referred to as “nitrogen-containing compound (δ)”), amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.

〔一般式（４）において、各Ｒ⁶ は相互に独立に１価の有機基を表すか、あるいは２つのＲ⁶ が相互に結合して式中の窒素原子と共に環を形成している。〕

[In the general formula (4), each R ⁶ independently represents a monovalent organic group, or two R ⁶ are bonded to each other to form a ring together with the nitrogen atom in the formula. ]

〔一般式（１０）において、各Ｒ⁹ は相互に独立に水素原子、炭素数１〜１０の直鎖状もしくは分岐状のアルキル基、炭素数３〜１０のシクロアルキル基、炭素数６〜２０のアリール基または炭素数７〜１８のアラルキル基を示し、これらのアルキル基、アリール基およびアラルキル基はそれぞれヒドロキシ基等の官能基で置換されていてもよい。〕

[In General Formula (10), each R ⁹ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or 6 to 20 carbon atoms. An aryl group or an aralkyl group having 7 to 18 carbon atoms, and these alkyl group, aryl group and aralkyl group may each be substituted with a functional group such as a hydroxy group. ]

In the general formula (4), examples of the monovalent organic group represented by R ⁶ include a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 6 to 6 carbon atoms. 20 aryl groups or aralkyl groups having 7 to 18 carbon atoms, and these alkyl groups, aryl groups and aralkyl groups may each be substituted with a functional group such as a hydroxy group.
In addition, examples of the ring formed by combining two R ⁶ together with the nitrogen atom in the formula include a 5- to 6-membered ring, and these rings are further added with a nitrogen atom, an oxygen atom, or the like. One or more of these hetero atoms may be contained.

  Examples of the nitrogen-containing compound (α) include N- (t-butoxycarbonyl) piperidine, N- (t-butoxycarbonyl) imidazole, N- (t-butoxycarbonyl) benzimidazole, N- (t-butoxycarbonyl). 2-phenylbenzimidazole, N- (t-butoxycarbonyl) di-n-octylamine, N- (t-butoxycarbonyl) diethanolamine, N- (t-butoxycarbonyl) dicyclohexylamine, N- (t-butoxycarbonyl ) Diphenylamine and the like.

  Examples of the nitrogen-containing compound (β) include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; di-n-butylamine, di-n- Dialkylamines such as pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine; triethylamine, tri-n-propylamine, Trialkylamines such as tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine Aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methyl Ruanirin, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, aromatic amines such as 1-naphthylamine; can be mentioned monoethanolamine, diethanolamine, alkanolamines such as triethanolamine and the like.

Examples of the nitrogen-containing compound (γ) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ′ tetrakis (2-hydroxypropyl) ethylenediamine, tetramethylenediamine, hexa Methylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2′-bis (4-aminophenyl) propane, 2 -(3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4 -Hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene Zen, 1,3-bis can be mentioned [1- (4-aminophenyl) -1-methylethyl] benzene, and the like.
Examples of the nitrogen-containing compound (δ) include polyethyleneimine, polyallylamine, N- (2-dimethylaminoethyl) acrylamide polymer, and the like.

Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. Can be mentioned.
Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea and the like. be able to.
Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, and 2-phenylbenzimidazole; pyridine, 2-methylpyridine, 4-methyl Such as pyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, acridine, etc. In addition to pyridines, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, etc. To list It can be.

Of these nitrogen-containing organic compounds, nitrogen-containing compounds (α), nitrogen-containing heterocyclic compounds and the like are preferable, and in particular, N- (t-butoxycarbonyl) 2-phenylbenzimidazole, N- (t-butoxycarbonyl) dicyclohexylamine. Also preferred are imidazoles.
In the radiation sensitive resin composition [I] and the radiation sensitive resin composition [II], the acid diffusion control agent can be used alone or in admixture of two or more.

  The compounding amount of the acid diffusion controller is usually 15 parts by weight or less, preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight per 100 parts by weight of the total resin components. In this case, when the compounding amount of the acid diffusion controller exceeds 15 parts by weight, the sensitivity as a resist and the developability of the exposed part tend to be lowered. In addition, if the compounding quantity of an acid diffusion control agent is less than 0.001 weight part, there exists a possibility that the pattern shape and dimension fidelity as a resist may fall depending on process conditions.

Moreover, various additives, such as surfactant and a sensitizer, can be mix | blended with radiation sensitive resin composition [I] as needed.
The surfactant is a component that exhibits an effect of improving coatability, striation, developability as a resist, and the like.
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, and commercially available products include, for example, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products); Megafax F171, F173 (above, large) Nippon Ink Chemical Co., Ltd.); Fluorad FC430, FC431 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC1 2, the SC103, the SC104, the SC 105, the SC 106 (manufactured by Asahi Glass Co., Ltd.); KP341 (manufactured by Shin-Etsu Chemical Co.), Polyflow No. 75, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).
The compounding amount of the surfactant is preferably 2 parts by weight or less per 100 parts by weight of the total resin components.

Examples of the sensitizer include benzophenones, rose bengals, anthracene and the like.
The blending amount of the sensitizer is preferably 50 parts by weight or less per 100 parts by weight of the total resin components. 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 mitigated. 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.

The composition solution radiation-sensitive resin composition [I] is usually a solvent so that, when used, the concentration of the total solid content is usually 0.1 to 50% by weight, preferably 1 to 40% by weight. Then, it is prepared as a composition solution 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 monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl Propylene glycol monoalkyl ethers such as 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 glycol di-n -Propylene glycol such as butyl ether Dialkyl ethers; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono -n- propyl ether acetate, propylene glycol monoalkyl ether acetates such as propylene glycol monobutyl -n- butyl ether acetate;

Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate; formate esters such as n-amyl formate and i-amyl formate; ethyl acetate, n-propyl acetate, i-acetate Acetic esters such as propyl, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate; i-propyl propionate, propionate Propionic acid esters such as n-butyl acid, i-butyl propionate, 3-methyl-3-methoxybutyl propionate; ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, 2-hydroxy-3- Methyl methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxy Other esters such as ethyl lopionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate Aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, 2-pentanone, 2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; N-methylformamide, N, N-dimethyl Examples include amides such as formamide, N-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.

Formation method of resist pattern When forming a resist pattern from the radiation-sensitive resin composition [I], the composition solution prepared as described above is applied to an appropriate solution such as spin coating, cast coating, roll coating, etc. For example, a resist film is formed by coating on a substrate such as a silicon wafer or a wafer coated with aluminum by a coating means. In some cases, a heat treatment (hereinafter referred to as “PB And then exposing through a predetermined mask pattern.
The radiation used for the exposure is, for example, a far-field such as a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), or an F ₂ excimer laser (wavelength 157 nm) depending on the type of the radiation-sensitive acid generator. Charged particle beams such as ultraviolet rays and synchrotron radiation such as X-rays and electron beams can be appropriately selected and used, but far ultraviolet rays such as KrF excimer laser (wavelength 248 nm) are preferred.
Moreover, exposure conditions, such as exposure amount, are suitably selected according to the compounding composition of radiation sensitive resin composition [I], the kind of each additive, etc.

In the present invention, in order to stably form a high-precision fine pattern, it is preferable to perform a heat treatment (hereinafter referred to as “PEB”) for 30 seconds or longer after exposure, preferably at a temperature of about 70 to 160 ° C. . In this case, if 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 is spread.
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. The resist pattern is formed.
As the alkali developer, for example, an alkaline compound such as tetraalkylammonium hydroxide is usually dissolved so as to have a concentration of 1 to 10% by weight, preferably 1 to 5% by weight, particularly preferably 1 to 3% by weight. Alkaline aqueous solution is used.
In addition, for example, a water-soluble organic solvent such as methanol or ethanol or a surfactant can be appropriately added to the developer composed of 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.

The radiation sensitive resin composition [I] of the present invention is a chemical amplification resist sensitive to far ultraviolet rays typified by, for example, KrF excimer laser, ArF excimer laser or F ₂ excimer laser, and has basic physical properties such as sensitivity and pattern shape. In particular, it is excellent in the depth of focus margin, and can be used very suitably for the manufacture of integrated circuit elements that are expected to be further miniaturized in the future.

Synthesis Example 1 (Production of resin (A))
101 g of p-acetoxystyrene, 5 g of styrene, 42 g of p-t-butoxystyrene, 6 g of azobisisobutyronitrile (AIBN) and 1 g of t-dodecyl mercaptan were dissolved in 160 g of propylene glycol monomethyl ether, and then reacted in a nitrogen atmosphere. Polymerization was performed for 16 hours while maintaining the temperature at 70 ° C. After the polymerization, the reaction solution was dropped into a large amount of n-hexane to coagulate and purify the resulting resin.
Next, 150 g of propylene glycol monomethyl ether was added to the purified resin, 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, then dropped into a large amount of water to solidify, and the resulting white powder was filtered and dried at 50 ° C. under reduced pressure overnight. did.
The obtained resin has Mw of 16,000 and Mw / Mn of 1.7. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of p-hydroxystyrene, styrene and pt-butoxystyrene is as follows. 72: 5: 23. This resin is referred to as “resin (A-1)”.

  The measurement of Mw and Mn of the resin (A-1) and the resin (A-2) and polymer (C-1) described below was carried out using GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation. Measurement was performed by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of a flow rate of 1.0 ml / min, an elution solvent tetrahydrofuran, and a column temperature of 40 ° C.

Synthesis Example 2 (Production of resin (A))
Propylene glycol monomethyl ether containing 71.5 g of p-acetoxystyrene, 3.2 g of styrene, 24.6 g of pt-butoxystyrene, 0.6 g of N, N-dimethylacrylamide, 4.1 g of AIBN and 0.6 g of t-dodecyl mercaptan It melt | dissolved in 160g and superposed | polymerized for 16 hours, hold | maintaining reaction temperature at 70 degreeC by nitrogen atmosphere. After the polymerization, the reaction solution was dropped into a large amount of n-hexane to coagulate and purify the resulting resin.
Next, 150 g of propylene glycol monomethyl ether was added to the purified resin, 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, then dropped into a large amount of water to solidify, and the resulting white powder was filtered and dried at 50 ° C. under reduced pressure overnight. did.
The obtained resin had Mw of 16,000 and Mw / Mn of 1.7. As a result of ¹³ C-NMR analysis, p-hydroxystyrene, styrene, pt-butoxystyrene, and N, N-dimethylacrylamide were obtained. Copolymerization molar ratio was 71: 5: 23: 1. This resin is referred to as “resin (A-2)”.

Synthesis Example 3 (Production of polymer (C))
64.7 g of p-acetoxystyrene, 3.4 g of styrene, 25.5 g of pt-butoxystyrene, 6.4 g of N, N-dimethylacrylamide, 4 g of AIBN and 0.6 g of t-dodecyl mercaptan are added to 100 g of propylene glycol monomethyl ether. After dissolution, polymerization was carried out for 16 hours under a nitrogen atmosphere while maintaining the reaction temperature at 70 ° C. After the polymerization, the reaction solution was dropped into a large amount of n-hexane, and the resulting polymer was coagulated and purified.
Next, 150 g of propylene glycol monomethyl ether was added to the purified polymer 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 polymer was dissolved in acetone, then dripped into a large amount of water to solidify, and the resulting white powder was filtered and filtered under reduced pressure at 50 ° C. overnight. Dried.
The obtained polymer had Mw of 15,000 and Mw / Mn of 1.6. As a result of ¹³ C-NMR analysis, p-hydroxystyrene, styrene, pt-butoxystyrene, and N, N-dimethyl were obtained. The copolymerization molar ratio of acrylamide was 62: 5: 23: 10. This polymer is referred to as “polymer (C-1)”.

Examples 1-8 and Comparative Examples 1-3
Each component shown in Table 1 (parts are based on weight) was mixed to obtain a uniform solution, and then filtered through a membrane filter having a pore size of 0.2 μm to prepare a composition solution. Then, after spin-coating DUV42 (composition for antireflection film) manufactured by Brewer Science Co., Ltd. so as to have a film thickness of 600 Å, each composition solution was spin-coated on a silicon wafer baked at 205 ° C. for 60 seconds. PB was performed at 130 ° C. for 90 seconds to form a resist film having a thickness of 0.4 μm.
Next, using a Stepper S203B (numerical aperture: 0.68) manufactured by Nikon Corporation, exposure was performed with a KrF excimer laser, and then PEB was performed at 130 ° C. for 90 seconds. Thereafter, a 2.38 wt% tetramethylammonium hydroxide aqueous solution was used and developed by the paddle method at 23 ° C. for 1 minute, and then washed with pure water and dried to form a resist pattern. Table 2 shows the evaluation results of each resist.

Here, each resist was evaluated in the following manner.
sensitivity:
The resist film formed on the silicon wafer is exposed to a different exposure amount and then immediately exposed to PEB, developed, washed with water, and dried to form a resist pattern. The exposure amount for forming the space pattern (1L1S) with a one-to-one line width was set as the optimum exposure amount, and the sensitivity was evaluated based on the optimum exposure amount.
Pattern shape:
A square cross section of a line and space pattern (1L1S) having a line width of 0.13 μm was observed and evaluated with a scanning electron microscope.
Depth of focus margin:
It was formed when exposure was performed by changing the depth of focus from -1.0 μm to +1.0 μm in increments of 0.1 μm through an optimum exposure dose through a line and space pattern (1L1S) mask with a design line width of 0.13 μm. The focal depth range from the resist pattern line width from 0.117 μm (−10%) to 0.143 μm (+ 10%) was defined as the focal depth margin.

Components other than resin (A-1), resin (A-2) and polymer (C-1) in Table 1 are as follows.
Acid generator (B1):
B1-1: N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide B1-2: N- (nonafluoro-n-butanesulfonyloxy) bicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximidic acid generator (B2):
B2-1: Diphenyliodonium 10-camphorsulfonate B2-2: Diphenyliodonium trifluoromethanesulfonate B2-3: Diphenyliodonium nonafluoro-n-butanesulfonate Other acid generators:
b-1: triphenylsulfonium trifluoromethanesulfonate

Acid diffusion control agent:
D-1: 2-phenylbenzimidazole D-2: Nt-butoxycarbonyl-2-phenylbenzimidazole solvent:
S-1: ethyl lactate S-2: ethyl 3-ethoxypropionate S-3: propylene glycol monomethyl ether acetate S-4: 2-heptanone

Claims (4)

(A) An alkali-insoluble or hardly alkali-soluble resin having a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), A resin that becomes readily soluble in alkali when the -C (R ³ ) ₃ group is dissociated, and (B) an N-sulfonyloxyimide compound consisting of a compound represented by the following general formula (8) and the following general formula (9) A radiation-sensitive resin composition comprising a radiation-sensitive acid generator containing a diphenyliodonium salt compound consisting of a compound represented by formula (I ) as an essential component.

[In General Formula (1), R ¹ represents a monovalent organic group, a plurality of R ¹ may be the same or different from each other, n is an integer of 1 to 3, and m is 0 to 2. It is an integer. ]

[In General formula (2), R < ² > represents a hydrogen atom or a methyl group, and each R < ³ > represents a C1-C4 saturated hydrocarbon group mutually independently. ]

[In General Formula (8), R ⁷ represents a divalent organic group, and R ⁸ represents a monovalent organic group. ]

[In the general formula (9), X ⁻ represents a monovalent anion. ] And (C) a polymer having a unit in which the polymerizable unsaturated bond of the monomer represented by the following general formula (3) is cleaved and / or a unit in which the polymerizable unsaturated bond of diacetone (meth) acrylamide is cleaved. The radiation sensitive resin composition of Claim 1 to contain.

[In General formula (3), R < ⁴ > represents a hydrogen atom or a methyl group, and each R < ⁵ > represents a hydrogen atom or a C1-C4 saturated hydrocarbon group mutually independently. ]   The radiation sensitive resin composition according to claim 1 or 2, further comprising (D) an acid diffusion controller. The radiation sensitive resin composition according to claim 3, wherein (D) the acid diffusion controller comprises a compound represented by the following general formula (4).

[In the general formula (4), each R ⁶ independently represents a monovalent organic group, or two R ⁶ are bonded to each other to form a ring together with the nitrogen atom in the formula. ]