JP5029766B2 - Positive radiation sensitive resin composition - Google Patents

Description

  The present invention relates to a positive-type radiation-sensitive resin composition suitable for forming a fine pattern using an electron beam, X-rays, extreme ultraviolet rays or the like.

  In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration of integrated circuits, miniaturization of design rules in lithography is progressing rapidly, and microfabrication is performed stably. The development of lithography processes that can do this is strongly promoted. However, since it is difficult to form a fine pattern of 100 nm or less with high accuracy by the conventional method using KrF or ArF excimer laser, electron beam (hereinafter also referred to as “EB”), extreme ultraviolet (hereinafter referred to as “EUV”). An ultra-fine process using "also" is proposed.

  As a positive resist material (positive radiation sensitive resin composition) for EB or EUV used for such ultrafine processing, the following (1) methacrylic main chain cutting such as PMMA (polymethyl methacrylate) is shown. Type radiation-sensitive resin composition, (2) a polyhydroxystyrene-based resin (resin for KrF excimer) partially protected with an acid-dissociable functional group, a novolak (resin for i-line), and an acid generator Chemically amplified radiation sensitive resin compositions and the like have been proposed.

  The (1) methacrylic main chain-cutting radiation sensitive resin composition generally exhibits excellent resolution, but has problems such as insufficient etching resistance and sensitivity. As a related technique for solving such a problem, poly-t-butyl α-chloromethylstyrene (for example, refer to Patent Document 1) having an excellent balance between resolution and sensitivity, an atom (N, which is easily cleaved by an electron beam) O, S) introduced at the end of the resin (for example, see Patent Document 2). However, while the sensitivity is certainly improved, the level is not yet in practical use with the etching resistance.

  Moreover, said (2) chemical amplification type radiation sensitive resin composition is generally excellent in the balance of sensitivity, resolution, and etching resistance. Related prior art includes partially acetal-protected polyhydroxystyrene resin + acid generator (see, for example, Patent Document 3), various acid-dissociable partially-protected polyhydroxystyrene resins + fluorine-containing aromatic sulfonic acid-generating onium salt + fluorine system Or a silicon-based surfactant (for example, see Patent Document 4), an onium salt having at least one electron-withdrawing group (F, cyano group, nitro group) as a cation moiety substituent (for example, see Patent Document 5), di Examples thereof include a resin having a sulfonyl group (see, for example, Patent Document 6) and a resin having an N-oxyimidosulfonyl group (see, for example, Patent Document 7). However, even with the resins disclosed in these patent documents, the film surface roughness (hereinafter also referred to as “line roughness”), sensitivity, and resolution at the time of forming a fine pattern is still at a practical level. The current situation is not.

JP 2000-147777 A JP 11-29612 A JP-A-6-194842 JP 2000-187330 A JP 2001-075283 A JP 2002-072483 A JP 2002-107920 A

  The present invention has been made in view of such problems of the prior art, and the object is to stabilize line patterns, etching resistance, sensitivity, and resolution, and to stabilize highly accurate fine patterns. Another object of the present invention is to provide a positive-type radiation-sensitive resin composition that can be formed.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have used a predetermined onium salt as a radiation-sensitive acid generator, and the predetermined onium salt and an alkali-insoluble or hardly soluble predetermined resin component. It has been found that the above-mentioned problems can be achieved by the inclusion, and the present invention has been completed.

  That is, according to the present invention, the following positive radiation sensitive resin composition is provided.

[1] (A) As a radiation sensitive acid generator, an onium salt represented by the following general formula (1) and / or (2), and (B) an acid dissociable group, the acid dissociable group And an alkali-insoluble or hardly soluble resin component that becomes alkali-soluble when dissociated, and the resin component (B) contains the following repeating unit (i) and the following repeating unit (iii). A positive-type radiation-sensitive resin composition.
(I): Repeating unit represented by the following general formula (3) (iii): At least one repeating unit selected from the group consisting of the following general formulas (5-1) to (5-4)

（前記一般式（１）及び（２）中、Ｍ^＋は１価のオニウムカチオンであり、Ｙは一以上のフッ素原子で置換された炭素数２〜６のアルキレン基である。前記一般式（２）中、Ｒはフッ素置換されていてもよい炭素数１〜４のアルキル基、又はフッ素置換されていてもよい炭素数３〜６のシクロアルキル基であり、前記アルキル基及び前記シクロアルキル基中のアルキレン鎖には酸素原子が含まれていてもよい）

(In the general formulas (1) and (2), M ⁺ is a monovalent onium cation, and Y is a C 2-6 alkylene group substituted with one or more fluorine atoms. In 2), R is an alkyl group having 1 to 4 carbon atoms which may be fluorine-substituted, or a cycloalkyl group having 3 to 6 carbon atoms which may be fluorine-substituted, and the alkyl group and the cycloalkyl group The oxygen chain in the alkylene chain may be contained)

（前記一般式（３）中、Ｒ^１は水素原子又はメチル基であり、Ｒ^２は１価の有機基であり、ｐは０〜３の整数であり、ｑは１〜３の整数である。Ｒ^２が複数存在する場合には、複数のＲ^２は、相互に同一であっても異なっていてもよい）

(In the general formula (3), R ¹ is a hydrogen atom or a methyl group, R ² is a monovalent organic group, p is an integer of 0 to 3, and q is an integer of 1 to 3. When a plurality of R ² are present, the plurality of R ² may be the same or different from each other)

（前記一般式（５−１）中、Ｒ^６は水素原子又はメチル基であり、Ｒ^７は１価の有機基（但し、−ＯＲ^５に相当する基を除く。ここで、Ｒ^５は１−分岐アルキル基、トリオルガノシリル基、又はトリオルガノゲルミル基である）であり、ｔは０〜３の整数であり、Ｒ^７が複数存在する場合には、複数のＲ^７は、相互に同一であっても異なっていてもよい）

(In the general formula (5-1), R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a monovalent organic group (excluding a group corresponding to —OR ⁵ , where R ⁵ is 1 - branched alkyl group or a triorganosilyl group, or a triorganogermyl group), t is an integer from 0 to 3, when R ⁷ there is a plurality, the plurality of R ⁷ are identical to each other Or it may be different)

（前記一般式（５−２）中、Ｒ^８及びＲ^１０は水素原子又はメチル基であり、Ｒ^９は２価の酸解離性の有機基である。Ｒ^８及びＲ^１０は、相互に同一であっても異なっていてもよい）

(In the general formula (5-2), R ⁸ and R ¹⁰ are a hydrogen atom or a methyl group, and R ⁹ is a divalent acid-dissociable organic group. R ⁸ and R ¹⁰ are the same as each other. Or it may be different)

（前記一般式（５−３）中、Ｒ^１１は水素原子又はメチル基であり、Ｒ^１２は炭素数１〜４のアルキル基であり、Ｒ^１３は水素原子、メチル基、又はエチル基である）

(In the general formula (5-3), R ¹¹ is a hydrogen atom or a methyl group, R ¹² is an alkyl group having 1 to 4 carbon atoms, and R ¹³ is a hydrogen atom, a methyl group, or an ethyl group. )

（前記一般式（５−４）中、Ｒ^１４は水素原子又はメチル基であり、Ｒ^１５は３級アルキル基である）

(In the general formula (5-4), R ¹⁴ is a hydrogen atom or a methyl group, and R ¹⁵ is a tertiary alkyl group)

  [2] R in the general formula (2) is an alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom, or a cycloalkyl having 3 to 6 carbon atoms which may be substituted with a fluorine atom. The positive radiation sensitive resin composition according to [1], which is a group.

  [3] The positive radiation sensitive resin composition according to [1] or [2], wherein the (A) onium salt is a sulfonium salt or an iodonium salt.

  [4] The positive radiation sensitive resin composition according to any one of [1] to [3], which is patterned by an electron beam or extreme ultraviolet rays.

  The positive-type radiation-sensitive resin composition of the present invention is excellent in line roughness, etching resistance, sensitivity, and resolution, and has an effect that a highly accurate fine pattern can be stably formed.

It is a schematic diagram which shows a line pattern.

  Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments, and based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. It should be understood that modifications, improvements, and the like appropriately added to the embodiments described above fall within the scope of the present invention.

  One embodiment of the positive radiation sensitive resin composition of the present invention is (A) an onium salt represented by the general formula (1) and / or (2) (hereinafter referred to as “a radiation sensitive acid generator”). (A) component ”) and (B) an alkali-insoluble or sparingly soluble resin component (hereinafter referred to as“ (B) The component (B) contains the following repeating unit (i) and the following repeating unit (iii). The details will be described below.

(I) The repeating unit represented by the general formula (3) (iii) At least one repeating unit selected from the group consisting of the general formulas (5-1) to (5-4)

(A) Onium salt:
The component (A) contained in the positive radiation sensitive resin composition of the present embodiment is an onium salt represented by the general formula (1) and / or (2). This component (A) is a compound capable of generating an acid upon irradiation with actinic rays or radiation, and is a component contained as a radiation-sensitive acid generator.

In the general formulas (1) and (2), M ⁺ is a monovalent onium cation. Preferable examples of the monovalent onium cation include onium cations such as O, S, Se, N, P, As, Sb, Cl, Br, and I. Of these, S and I onium cations are more preferred.

In the general formulas (1) and (2), specific examples of the monovalent onium cation represented by M ⁺ include those represented by the following general formula (6) or (7).

In said general formula (6), R <^16> , R <^17> and R <^18> are mutually independent substituted or unsubstituted C1-C10 linear or branched alkyl groups, or substituted or unsubstituted And an aryl group having 6 to 18 carbon atoms. Two or more of R ¹⁶ , R ¹⁷ , and R ¹⁸ may be bonded to each other to form a ring together with the sulfur atom in the formula.

In the general formula (7), R ¹⁹ and R ²⁰ are each independently substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or substituted or unsubstituted carbon number 6 Is an aryl group of ˜18. R ¹⁹ and R ²⁰ may be bonded to each other to form a ring together with the iodine atom in the formula.

In the general formulas (1) and (2), the monovalent onium cation moiety represented by M ⁺ is described in, for example, Advances in Polymer Sciences, Vol. 62, p. 1-48 (1984). As more preferable specific examples of the monovalent onium cation, a sulfonium cation represented by the following formulas (6-1) to (6-64) and a formula represented by the following formulas (7-1) to (7-39) And iodonium cations.

  Among the above monovalent onium cations, the formula (6-1), the formula (6-2), the formula (6-6), the formula (6-8), the formula (6-13), the formula (6- 19), formula (6-25), formula (6-27), formula (6-29), formula (6-30), formula (6-31), formula (6-51), formula (6-54) ) Sulfonium cation represented by formula (6-62), formula (6-63); represented by formula (7-1), formula (7-11), formula (7-40), formula (7-41) More preferred are iodonium cations.

  In the general formulas (1) and (2), Y is an alkylene group substituted with one or more fluorine atoms, preferably an alkylene group having 2 to 4 carbon atoms, preferably a carbon atom optionally substituted with a fluorine atom. They are a C1-C4 alkyl group or a C3-C6 cycloalkyl group optionally substituted by a fluorine atom. The alkylene chain may contain an oxygen atom. Y in the general formulas (1) and (2) is more preferably a C 2-4 perfluoroalkylene group, and is a tetrafluoroethylene group, a hexafluoropropylene group, or an octafluorobutylene group. It is particularly preferred.

  In said general formula (2), R is a C1-C4 alkyl group or a C3-C6 cycloalkyl group. The alkylene chain in the alkyl group and cycloalkyl group may contain an oxygen atom. The alkyl group having 1 to 4 carbon atoms is preferably a fluorine-substituted alkyl group, and more preferably a perfluoroalkyl group. More specifically, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and a perfluoroethoxyethyl group can be exemplified. Further, the cycloalkyl group having 3 to 6 carbon atoms is preferably a fluorine-substituted cycloalkyl group, more preferably a cyclopentyl group or a cyclohexyl group.

  The proportion of the component (A) contained in the positive radiation sensitive resin composition of the present embodiment is 0.1 to 30 parts by mass with respect to 100 parts by mass of the acid dissociable group-containing resin (B). It is more preferable that it is 0.1-20 mass parts, and it is especially preferable that it is 0.1-15 mass parts. When the content ratio of the component (A) is less than 0.1 parts by mass with respect to 100 parts by mass of the acid-dissociable group-containing resin (B), sensitivity and developability tend to decrease. On the other hand, if it exceeds 30 parts by mass, the pattern shape, heat resistance and the like tend to decrease.

(Other radiation-sensitive acid generators)
The positive radiation-sensitive resin composition of the present embodiment contains a radiation-sensitive acid generator other than the above-mentioned (A) onium salt (hereinafter also referred to as “other acid generators”) as necessary. Can be made. Examples of other acid generators include sulfonimide compounds, sulfone compounds, sulfonic acid ester compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, onium salts other than the component (A), and the like. Can be mentioned.

  Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl). Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) ) Naphthylimide, N- (10-camphorsulfonyloxy) s Synimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) Bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (10-camphorsulfonyloxy) naphthylimide, N-[(5-methyl-5-carboxymethylbicyclo [ 2.2.1] heptan-2-yl) sulfonyloxy] succinimide,

  N- (n-octylsulfonyloxy) succinimide, N- (n-octylsulfonyloxy) phthalimide, N- (n-octylsulfonyloxy) diphenylmaleimide, N- (n-octylsulfonyloxy) bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (n-octylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (n-octylsulfonyloxy) naphthylimide, N- (4- Methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) phthalimide, N- (4 Methylphenylsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6- Oxy-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) naphthylimide,

  N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoro Methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide N- (2-trifluoromethylphenylsulfonyloxy) naphthylimi N- (4-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-trifluoromethylphenylsulfonyloxy) phthalimide, N- (4-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-tri Fluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide, N- (4-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxy Imido, N- (4-trifluoromethylphenylsulfonyloxy) naphthyl Bromide,

  N- (perfluorophenylsulfonyloxy) succinimide, N- (perfluorophenylsulfonyloxy) phthalimide, N- (perfluorophenylsulfonyloxy) diphenylmaleimide, N- (perfluorophenylsulfonyloxy) bicyclo [2.2.1] ] Hept-5-ene-2,3-dicarboximide, N- (perfluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (perfluorophenylsulfonyloxy) naphthylimide, N- (1- Naphthylsulfonyloxy) succinimide, N- (1-naphtho) Rusulfonyloxy) phthalimide, N- (1-naphthylsulfonyloxy) diphenylmaleimide, N- (1-naphthylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N -(1-naphthylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthylsulfonyloxy) bicyclo [2.2.1 ] Heptane-5,6-oxy-2,3-dicarboximide, N- (1-naphthylsulfonyloxy) naphthylimide,

  N- (nonafluoro-n-butylsulfonyloxy) succinimide, N- (nonafluoro-n-butylsulfonyloxy) phthalimide, N- (nonafluoro-n-butylsulfonyloxy) diphenylmaleimide, N- (nonafluoro-n-butylsulfonyloxy) ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5 Ene-2,3-dicarboximide, N- (nonafluoro-n-butylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (nonafluoro- n-butylsulfonyloxy) naphthylimide, N- (perfluoro-n-octylsulfo) Ruoxy) succinimide, N- (perfluoro-n-octylsulfonyloxy) phthalimide, N- (perfluoro-n-octylsulfonyloxy) diphenylmaleimide, N- (perfluoro-n-octylsulfonyloxy) bicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- (perfluoro-n-octylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (perfluoro-n-octyl) Sulfonyloxy) naphthylimide,

  N- (phenylsulfonyloxy) succinimide, N- (phenylsulfonyloxy) phthalimide, N- (phenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- (phenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (phenylsulfonyloxy) bicyclo [2 2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (phenylsulfonyloxy) naphthylimide and the like.

  Among these sulfonimide compounds, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (nonafluoro-n-butylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (phenylsulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-[(5-methyl-5-carboxymethylbicyclo [2.2.1] heptan-2-yl) Sulfonyloxy] succinimide is preferred. In addition, a sulfonimide compound can be used individually by 1 type or in combination of 2 or more types.

  Examples of the “onium salt” include sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts, and the like.

  Specific examples of onium salts other than component (A) include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium pyrenesulfonate, triphenylsulfonium pyrenesulfonate, Phenylsulfonium n-dodecylbenzenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium n-octanesulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium Phenylsulfonium 4-trifluoromethylbenzenesulfonate, Phenylsulfonium 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) diph Nylsulfonium benzenesulfonate, (4-t-butylphenyl) diphenylsulfonium 10-camphorsulfonate, (4-t-butylphenyl) diphenylsulfonium n-octanesulfonate, (4-t-butylphenyl) diphenylsulfonium 2-trifluoromethyl Benzenesulfonate, (4-t-butylphenyl) diphenylsulfonium 4-trifluoromethanebenzenesulfonate, (4-t-butylphenyl) diphenylsulfonium perfluorobenzenesulfonate,

  (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-hydroxyphenyl) diphenylsulfonium n-dodecylbenzenesulfonate, (4-hydroxyphenyl) diphenylsulfonium p-toluenesulfonate, (4-hydroxyphenyl) diphenylsulfoniumbenzenesulfonate, (4-hydroxyphenyl) diphenyl Sulfonium 10-camphorsulfonate, (4-hydroxyphenyl) diphenylsulfate Ni-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) Eniru) sulfonium 2-trifluoromethylbenzenesulfonate, tris (4-methoxyphenyl) sulfonium 4-trifluoromethylbenzenesulfonate, tris (4-methoxyphenyl) sulfonium perfluoro sulfonate,

  Bis (4-methoxyphenyl) p-toluylsulfonium 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-methoxyphenyl) 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-methoxyphenyl) p-toluylsulfonium perfluorobenzenesulfonate,

  (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-camphor sulfonate, tris (4-fluorophenyl) sulfonium p-toluenesulfonate, 2,4 , 6-Trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfoniu 2,4-difluoro benzenesulfonate, 2,4,6-trimethylphenyl sulfonium p- toluenesulfonate,

  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, diphenyliodonium 4-trifluoromethylbenzenesulfonate, diphenyliodonium perfluorobenzenesulfonate, di (p-toluene) L) iodonium trifluoromethanesulfonate, di (p-toluyl) iodonium nonafluoro-n-butanesulfonate, di (p-toluyl) iodonium perfluoro-n-octanesulfonate, di (p-toluyl) iodonium pyrenesulfonate, di (p -Toluyl) iodonium n-dodecylbenzenesulfonate, di (p-toluyl) iodonium p-toluenesulfonate, di (p-toluyl) iodoniumbenzenesulfonate, di (p-toluyl) iodonium 10-camphorsulfonate, di (p-toluyl) Iodonium n-octanesulfonate, di (p-toluyl) iodonium 2-trifluoromethylbenzenesulfonate, di (p-toluyl) iodonium 4-trifluoromethylbenzenesulfone Over DOO, di (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-dodecylbenzenesulfonate, bis (3,4-dimethylphenyl) iodonium p-toluenesulfonate, bis (3,4- Dimethylphenyl) iodoniumbenzenesulfonate, bis (3,4-dimethylphenyl) iodonium 10-camphorsulfonate, bis (3,4-dimethylphenyl) iodonium n-octanesulfonate, bi (3,4-dimethylphenyl) iodonium 2-trifluoromethylbenzene sulfonate, bis (3,4-dimethylphenyl) iodonium 4-trifluoromethyl benzenesulfonate, bis (3,4-dimethylphenyl) iodonium perfluoro sulfonate,

  (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) Phenyl iodonium 2-trifluoromethylbenzene sulfonate, (4-nitrophenyl) iodonium 4-trifluoromethyl benzenesulfonate, (4-nitrophenyl) iodonium perfluoro sulfonate,

  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-nitrophenyl) iodoniumbenzenesulfonate, bis (3-nitrophenyl) Iodonium 10-camphorsulfonate, bis (3-nitrophenyl) iodonium n-octanesulfonate, bis (3-nitrophenyl) iodonium 2-trifluorome Le benzenesulfonate, bis (3-nitrophenyl) iodonium 4-trifluoromethyl benzenesulfonate, bis (3-nitrophenyl) iodonium perfluoro sulfonate,

  (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) iodonium 2-trifluoromethylbenzene sulfonate, (4-methoxyphenyl) iodonium 4-trifluoromethyl benzenesulfonate, (4-methoxyphenyl) iodonium perfluoro sulfonate,

  (4-fluorophenyl) phenyliodonium 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) iodoniumbenzenesulfonate, di (1-naphthyl) iodonium 10-camphorsulfonate, di (1 1-naphthyl) iodonium n-octanesulfonate, di (1-naphthyl) iodonium 2-trifluoromethylbenzenesulfonate, di (1-naphthyl) iodonium 4-trifluoromethylbenzene Zen sulfonate, and di (1-naphthyl) iodonium perfluoro benzene sulfonates.

  Among these onium salts, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-butanesulfonate, 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-tri Fluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium 2,4-difluorobenzenesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluoro n-butanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4-trifluorobenzenesulfonate, triphenylsulfonium 2,4-difluoro Methylbenzenesulfonate, 4,6-trimethylphenyldiphenylsulfonium 2,4-difluorobenzenesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium 4-trifluoromethylbenzenesulfonate,

  Diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium perfluorooctanesulfonate, diphenyliodonium 10-camphorsulfonate, triphenylsulfonium perfluorooctanesulfonate, tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tris (4 -Methoxyphenyl) sulfonium 10-camphorsulfonate, tris (4-fluorophenyl) sulfonium trifluoromethanesulfonate, tris (4-fluorophenyl) sulfonium p-toluenesulfonate, (4-fluorophenyl) diphenylsulfonium trifluoromethanesulfonate, (4- Fluorophenyl) Nyliodonium 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 is preferred. In addition, onium salts other than (A) component can be used individually by 1 type or in combination of 2 or more types.

  Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof. Further specific examples of the sulfone compound include phenacylphenylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, 4-trisphenacylsulfone, and the like.

  Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Further specific examples of the sulfonate compound include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), pyrogallol tris (nonafluoro-n-butylsulfonate), pyrogallol tris (methylsulfonate), nitrobenzyl-9, Examples include 10-diethoxyanthracene-2-sulfonate, α-methylol benzoin tosylate, α-methylol benzoin trifluoromethane sulfonate, α-methylol benzoin n-octane sulfonate, α-methylol benzoin n-dodecane sulfonate, and the like.

  As said disulfonyl diazomethane compound, the compound represented by following General formula (8) can be mentioned, for example.

（前記一般式（８）中、それぞれのＲ^２１は、相互に独立してアルキル基、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価の基である）

(In the general formula (8), each R ²¹ is independently a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, 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, bis (2,4 -Dimethylbenzenesulfonyl) diazomethane, bis (4-t-butylphenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, (methylsulfonyl) 4-methylphenylsulfonyldiazomethane, (cyclohexylsulfonyl) 4-methylphenylsulfonyldiazomethane, (Cyclohexylsulfonyl) 1,1-dimethylethylsulfonyldiazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bi (1-methylethylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] decane-7 -Sulfonyl) diazomethane, bis (4-t-butylsulfonyl) diazomethane, and the like.

  Among these disulfonyldiazomethane compounds, bis (cyclohexylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8- Sulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] undecan-7-sulfonyl) diazomethane, and bis (4-t-butylsulfonyl) diazomethane are preferred. In addition, a disulfonyl diazomethane compound can be used individually by 1 type or in combination of 2 or more types.

  As said disulfonylmethane compound, the compound represented by following General formula (9) can be mentioned, for example.

In the general formula (9), each R ²² independently represents a linear or branched monovalent aliphatic hydrocarbon group, cycloalkyl group, aryl group, aralkyl group, or hetero atom. And other monovalent organic groups. V and W are each independently an aryl group, a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group, or another monovalent organic group having a hetero atom. In addition, V and W in the said General formula (9) satisfy | fill the conditions in any one of (1)-(3) shown below.
(1): At least one of V and W is an aryl group.
(2): V and W are connected to each other to form a carbon monocyclic structure or a carbon polycyclic structure having at least one unsaturated bond.
(3): V and W are connected to each other to form a group represented by the following general formula (10).

  In the general formula (10), V ′ and W ′ are independent of each other (provided that when a plurality of V ′ and W ′ are present, the plurality of V ′ and W ′ are the same as each other). Or a hydrogen atom, a halogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and r is an integer of 2 to 10. Note that V ′ and W ′ bonded to the same or different carbon atoms may be connected to each other to form a carbon monocyclic structure. In addition, a disulfonylmethane compound can be used individually by 1 type or in combination of 2 or more types.

  As said oxime sulfonate compound, the compound represented by the following general formula (11-1) or (11-2) can be mentioned, for example.

In the general formulas (11-1) and (11-2), R ²³ and R ²⁴ are each independently a monovalent organic group. In the general formulas (11-1) and (11-2), preferred examples of R ²³ include a methyl group, an ethyl group, an n-propyl group, a phenyl group, a tosyl group, a trifluoromethyl group, and pentafluoro. An ethyl group etc. can be mentioned. Further, preferred examples of R ^24, there can be mentioned a phenyl group, tosyl group, a 1-naphthyl group.

  Specific examples of the hydrazine sulfonate compound include bis (phenylsulfonyl) hydrazine, bis (4-methylphenylsulfonyl) hydrazine, bis (trifluoromethylsulfonyl) hydrazine, bis (pentafluoroethylsulfonyl) hydrazine, and bis (n-propyl). Sulfonyl) hydrazine, phenylsulfonylhydrazine, 4-methylphenylsulfonylhydrazine, trifluoromethylsulfonylhydrazine, pentafluoroethylsulfonylhydrazine, n-propylsulfonylhydrazine, (trifluoromethylsulfonyl), 4-methylphenylsulfonylhydrazine, etc. Can do. In addition, a hydrazine sulfonate compound can be used individually by 1 type or in combination of 2 or more types.

  The usage-amount of other acid generators is 50 mass parts or less normally with respect to 100 mass parts of (A) component, Preferably it is 30 mass parts or less. When the usage ratio of the other acid generator is more than 30 parts by mass with respect to 100 parts by mass of the component (A), the effect of the positive radiation-sensitive resin composition of the present invention tends to be impaired.

((B) resin component)
The component (B) contained in the positive radiation sensitive resin composition of the present embodiment is an alkali-insoluble or hardly soluble resin component. This component (B) has an acid-dissociable group, and becomes alkali-soluble only when the acid-dissociable group is dissociated. The component itself is an alkali-insoluble or hardly soluble resin component.

  Here, the term “alkali insoluble or hardly soluble” as used in the present specification means that a resist pattern is formed from a resist film formed using a positive radiation sensitive resin composition containing this component (B). When developing a film using only the component (B) in place of the resist film under the alkali development conditions employed for the film, it means that 50% or more of the initial film thickness of the film remains after development. . This component (B) includes a repeating unit (i) and a repeating unit (iii). Moreover, (B) component may further contain repeating unit (ii).

(Repeating unit (i), repeating unit (ii))
The repeating unit (i) is a repeating unit represented by the general formula (3). In the general formula (3), R ¹ is a hydrogen atom or a methyl group, R ² is a monovalent organic group, p is an integer of 0 to 3, and q is an integer of 1 to 3. In the case where R ² there are a plurality, the plurality of R ² may be different even mutually identical. The repeating unit (ii) is a repeating unit represented by the following general formula (4).

In the general formula (4), R ³ is a hydrogen atom or a methyl group, R ⁴ is a monovalent organic group (excluding a group corresponding to —OR ⁵ ), and R ⁵ is a 1-branched alkyl group. A monovalent acid dissociable group selected from the group consisting of a group, a triorganosilyl group, and a triorganogermyl group, r is an integer of 0 to 3, and s is an integer of 1 to 3. When the R ⁴ and R ⁵ are present in plural, the plurality of R ⁴ and R ^5, respectively, may be the same or different from each other.

Examples of the monovalent organic group represented by R ² in the general formula (3) and R ⁴ in the general formula (4) include, for example, straight-chain, branched, Examples thereof include a cyclic alkyl group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent oxygen atom-containing organic group, and a monovalent nitrogen atom-containing organic group.

  Examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, cyclopentyl, and cyclohexyl. Groups and the like.

  Examples of the monovalent aromatic hydrocarbon group include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, 2,6-xylyl group, 3,5- A xylyl group, a mesityl group, an o-cumenyl group, an m-cumenyl group, a p-cumenyl group, a benzyl group, a phenethyl group, a 1-naphthyl group, a 2-naphthyl group, and the like can be given.

  Examples of the monovalent oxygen atom-containing organic group include, for example, carboxyl group; hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group. 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 3-hydroxycyclopentyl group, 4-hydroxycyclohexyl group, etc. Or a cyclic hydroxyalkyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group, C1-C8 linear, branched, or cyclic alky such as cyclohexyloxy group Xyl group; linear alkoxycarbonyloxy group having 2 to 9 carbon atoms such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, n-butoxycarbonyloxy group; (1-methoxyethoxy) methyl Group, (1-ethoxyethoxy) methyl group, (1-n-propoxyethoxy) methyl group, (1-n-butoxyethoxy) methyl group, (1-cyclopentyloxyethoxy) methyl group, (1-cyclohexyloxyethoxy) A linear, branched or cyclic (1-alkoxyalkoxy) alkyl group having 3 to 11 carbon atoms such as methyl group, (1-methoxypropoxy) methyl group, (1-ethoxypropoxy) methyl group, ethoxyethyl group, etc. Methoxycarbonyloxymethyl group, ethoxycarbonyloxymethyl group 3 carbon atoms such as n-propoxycarbonyloxymethyl group, i-propoxycarbonyloxymethyl group, n-butoxycarbonyloxymethyl group, t-butoxycarbonyloxymethyl group, cyclopentyloxycarbonyloxymethyl group, cyclohexyloxycarbonyloxymethyl group, etc. -10 linear, branched, or cyclic alkoxycarbonyloxyalkyl groups.

  Examples of the monovalent nitrogen atom-containing organic group include cyano group; cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group, 1-cyanopropyl group, 2-cyanopropyl group, 3-cyanopropyl group, 1- C2-C9 linear, branched or cyclic cyanoalkyl groups such as cyanobutyl group, 2-cyanobutyl group, 3-cyanobutyl group, 4-cyanobutyl group, 3-cyanocyclopentyl group and 4-cyanocyclohexyl group Etc.

Examples of the 1-branched alkyl group represented by R ⁵ in the general formula (4) include i-propyl group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl. Group, 1,1-dimethylbutyl group and the like.

Examples of the triorganosilyl group represented by R ⁵ in the general formula (4) include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, and methyldi-i. -Propylsilyl group, tri-i-propylsilyl group, t-butyldimethylsilyl group, methyldi-t-butylsilyl group, tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, triphenylsilyl group, etc. Can be mentioned.

Examples of the triorganogermyl group represented by R ⁵ in the general formula (4) include a trimethylgermyl group, an ethyldimethylgermyl group, a methyldiethylgermyl group, a triethylgermyl group, and an isopropyldimethylgermyl group. Methyldi-i-propylgermyl group, tri-i-propylgermyl group, t-butyldimethylgermyl group, methyldi-t-butylgermyl group, tri-t-butylgermyl group, phenyldimethylgermyl group, methyldiphenylgel Examples thereof include a mil group and a triphenylgermyl group.

  Specific examples of suitable repeating unit (i) include 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-hydroxy-α-methylstyrene, 3-hydroxy-α-methylstyrene, 4-hydroxy- α-methylstyrene, 2-methyl-3-hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 2-methyl-4-hydroxystyrene, 3-methyl-4-hydroxystyrene, Examples thereof include a repeating unit in which a polymerizable unsaturated bond is cleaved such as 3,4-dihydroxystyrene and 2,4,6-trihydroxystyrene. In addition, 2 or more types of repeating units (i) may be contained in (B) component.

  Specific examples of suitable repeating unit (ii) include repeating units in which a polymerizable unsaturated bond is cleaved such as 4-t-butoxystyrene and 4-t-butoxy-α-methylstyrene. In addition, (B) component may contain 2 or more types of repeating units (ii).

(Repeating unit (iii))
The repeating unit (iii) is at least one repeating unit selected from the group consisting of the general formulas (5-1) to (5-4). In the general formula (5-1), R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a monovalent organic group (excluding a group corresponding to —OR ⁵ , where R ⁵ is 1- branched alkyl group or a triorganosilyl group, or a triorganogermyl group), t is an integer from 0 to 3, when R ⁷ there is a plurality, the plurality of R ⁷ are mutually the same It may or may not be.

Examples of the organic group represented by R ⁷ in the general formula (5-1) include a methyl group, an ethyl group, a tert-butyl group, an isopropyl group, and a methoxy group.

In the general formula (5-2), R ⁸ and R ¹⁰ are a hydrogen atom or a methyl group, and R ⁹ is a divalent acid-dissociable organic group. R ⁸ and R ¹⁰ may be the same or different from each other. Examples of the organic group represented by R ⁹ in the general formula (5-2) include 2,3-dimethyl-2,3-butanediyl group, 2,3-diethyl-2,3-butanediyl group, 2 , 3-Di-n-propyl-2,3-butanediyl group, 2,3-diphenyl-2,3-butanediyl group, 2,4-dimethyl-2,4-pentanediyl group, 2,4-diethyl-2, 4-pentanediyl group, 2,4-di-n-propyl-2,4-pentanediyl group, 2,4-diphenyl-2,4-pentanediyl group, 2,5-dimethyl-2,5-hexanediyl group, 2 , 5-diethyl-2,5-hexanediyl group, 2,5-di-n-propyl-2,5-hexanediyl group, 2,5-diphenyl-2,5-hexanediyl group, 2,6-dimethyl -2,6-heptanediyl group, 2,6-di Ethyl-2,6-heptanediyl group, 2,6-di-n-propyl-2,6-heptanediyl group, 2,6-diphenyl-2,6-heptanediyl group, 2,4-dimethyl-3- (2- Hydroxypropyl-2,4-pentanediyl group, 2,4-diethyl-3- (2-hydroxypropyl) -2,4-pentanediyl group, 2,5-dimethyl-3- (2-hydroxypropyl) -2,5 -Hexanediyl group, 2,5-diethyl-3- (2-hydroxypropyl) -2,5-hexanediyl group, 2,4-dimethyl-3,3-di (2-hydroxypropyl) -2,4- Pentanediyl group, 2,4-diethyl-3,3-di (2-hydroxypropyl) -2,4-pentanediyl group, 2,5-dimethyl-3,4-di (2-hydroxypropyl) -2,5- Heki Njiiru group, 2,5-diethyl-3,4-di (2-hydroxypropyl) -2,4-hexanediyl group, and 2,7-dimethyl-2,7-Okutanjiru group, and

  Functional groups represented by the following formulas (12-1) to (12-3) can be given.

In the general formula ^{(5-3), R 11} is a hydrogen atom or a methyl ^{group, R 12} is an alkyl group having 1 to 4 carbon ^{atoms, R 13} is a hydrogen atom, a methyl group, or ethyl group.

In the general formula (5-4), R ¹⁴ is a hydrogen atom or a methyl group, and R ¹⁵ is a tertiary alkyl group. Examples of the tertiary alkyl group represented by R ¹⁵ in the general formula (5-14) include a t-butyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, and a 2-methyl-2-adamantyl group. 2-ethyl-2-adamantyl group, 8-methyl-8-tricyclodecyl group, 8-ethyl-8-tricyclodecyl group, 3-methyl-3-tetracyclododecenyl group, 3-ethyl- A 3-tetracyclododecenyl group etc. can be mentioned.

  Specific examples of suitable repeating unit (iii) include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, vinyl aromatic compounds such as p-methoxymethoxystyrene, p-ethoxymethoxystyrene, p-1-methoxyethoxystyrene, p-1-ethoxyethoxystyrene, p-1-methoxypropoxystyrene, p-1-ethoxypropoxystyrene; Tert-butyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl (meth) acrylate 2-Adamantyl (meth) acrylic acid 8-me -8-tricyclodecyl, 8-ethyl-8-tricyclodecyl (meth) acrylate, 3-methyl-3-tetracyclododecenyl (meth) acrylate, 3-ethyl (meth) acrylate 3-tetracyclododecenyl, 2,5-dimethylhexane-2,5-di (meth) acrylate 2,6-dimethylheptane-2,6-diacrylate, 2,7-dimethyloctane-2,7- And (meth) acrylic acid esters such as diacrylate; a repeating unit in which a polymerizable unsaturated bond is cleaved. In addition, (B) component may contain 2 or more types of repeating units (iii).

  The component (B) may contain components other than the above repeating units (i) to (iii). For example, vinyl aromatic compounds such as 4- (2-t-butoxycarbonylethyloxy) styrene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid i-propyl, n-butyl (meth) acrylate, 2-methylpropyl (meth) acrylate, 1-methylpropyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, ( N-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-n-propyl (meth) acrylate, 3-hydroxy-n (meth) acrylate -Propyl, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid, crotonic acid, Unsaturated carboxylic acids (anhydrides) such as oleic acid, maleic anhydride, fumaric acid and cinnamic acid; 2-carboxyethyl (meth) acrylate, 2-carboxy-n-propyl (meth) acrylate, (meta ) Carboxyalkyl esters of unsaturated carboxylic acids such as 3-carboxy-n-propyl acrylate; unsaturated nitrile compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile; (meth) acrylamide , N, N-dimethyl (meth) acrylamide, unsaturated amide compounds such as crotonamide, maleamide and fumaramide; unsaturated imide compounds such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; N-vinyl-ε-caprolactam N-vinylpyrrolidone 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-vinylimidazole, may be mentioned nitrogen-containing vinyl compounds such as 4-vinyl imidazole.

  Preferred range of introduction ratio of acid-dissociable groups to component (B) (ratio of the number of acid-dissociable groups to the total number of unprotected acidic functional groups and acid-dissociable groups in component (B)) Is unconditionally dependent on the acid-dissociable group and the type of alkali-soluble resin into which the acid-dissociable group is introduced, but is preferably 10 to 100%, preferably 15 to 100%. More preferably it is.

  The proportion of the repeating unit (i) contained in the component (B) is preferably 60 to 80 mol%, and preferably 65 to 75 mol% when the total of all repeating units is 100 mol%. Is more preferable. If it is less than 60 mol%, the adhesion of the resist pattern to the substrate tends to be reduced. On the other hand, if it exceeds 80 mol%, the contrast after development tends to decrease.

  The proportion of the repeating unit (ii) contained in the component (B) is preferably 10 to 50 mol%, preferably 15 to 35 mol%, when the total of all repeating units is 100 mol%. Is more preferable. If it is less than 10 mol%, the resolution tends to decrease. On the other hand, if it exceeds 50 mol%, the adhesion of the resist pattern to the substrate tends to be lowered.

  The proportion of the repeating unit (iii) contained in the component (B) is about 1 to about the repeating unit represented by the general formula (5-1) when the total of all the repeating units is 100 mol%. It is preferably 30 mol%, more preferably 5 to 25 mol%. If it is less than 30 mol%, the resolution tends to decrease. On the other hand, if it exceeds 1 mol%, the dry etching resistance tends to be insufficient. In addition, the repeating units represented by the general formulas (5-2) to (5-4) are each preferably 3 to 40 mol%, and more preferably 3 to 35 mol%. If it is less than 3 mol%, the resolution tends to decrease. On the other hand, if it exceeds 40 mol%, the dry etching resistance tends to be insufficient.

  The polystyrene-converted weight molecular weight (hereinafter also referred to as “Mw”) of the component (B) measured by gel permeation chromatography (GPC) is preferably 1,000 to 150,000, and preferably 3,000 to 100,000. Is more preferably 5,000, particularly preferably 5,000 to 30,000. In addition, the ratio (Mw / Mn) of the component (B) between the Mw and the polystyrene-equivalent molecular weight (hereinafter also referred to as “Mn”) measured by gel permeation chromatography (GPC) is usually 1 to 10. , Preferably 1-5. In addition, (B) component can be used individually by 1 type or in combination of 2 or more types.

(Other ingredients)
The positive radiation sensitive resin composition of the present embodiment can contain components such as an alkali solubility control agent, an acid diffusion control agent, a surfactant, a sensitizer, and a solvent as necessary. Details of these components will be described below.

(Alkali dissolution control agent)
Examples of the alkali dissolution control agent include compounds in which a hydrogen atom of an acidic functional group such as a phenolic hydroxyl group or a carboxyl group is substituted with an acid dissociable group or a t-butoxycarbonylmethyl group.

  Examples of the acid dissociable group include a substituted methyl group, 1-substituted ethyl group, 1-substituted n-propyl group, 1-branched alkyl group, silyl group, germyl group, alkoxycarbonyl group, acyl group, and cyclic group. Examples include acid dissociable groups. Preferred examples of the alkali dissolution control agent include steroids (bile acids) such as cholic acid, deoxycholic acid, and lithocholic acid, or alicyclic rings or aromatic rings such as adamantane carboxylic acid and adamantane dicarboxylic acid. The compound etc. which substituted the hydrogen atom of the carboxyl group in a carboxylic acid compound with the said acid dissociable group or t-butoxycarbonylmethyl group can be mentioned.

  The use ratio of the alkali dissolution control agent is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, and 2 to 20 parts by mass with respect to 100 parts by mass of the component (B). It is particularly preferable that In addition, an alkali dissolution control agent can be used individually by 1 type or in combination of 2 or more types.

(Acid diffusion control agent)
It is preferable to mix | blend an acid diffusion control agent with the positive radiation sensitive resin composition of this embodiment as needed. By adding this acid diffusion control agent, the diffusion phenomenon in the resist film of the acid generated from the acid generator by EB, X-ray or EUV irradiation is controlled, and undesirable chemical reaction in the non-irradiated region is suppressed. can do. Furthermore, by adding an acid diffusion control agent, the storage stability of the resulting positive-type radiation-sensitive resin composition is improved and the resolution is improved as a resist, and the holding time from irradiation to heat treatment after irradiation is increased. It is possible to suppress a change in the line width of the resist pattern due to the fluctuation of (PED). Therefore, the process stability is extremely excellent.

  Preferable examples of the acid diffusion controlling agent include nitrogen-containing organic compounds whose basicity is hardly changed by radiation irradiation or heat treatment during the resist pattern forming process. Examples of such nitrogen-containing organic compounds include compounds represented by the following general formula (13) (hereinafter referred to as “nitrogen-containing compound (α)”), diamino compounds having two nitrogen atoms in the same molecule ( (Hereinafter referred to as “nitrogen-containing compound (β)”), diamino polymer having 3 or more nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (γ)”), amide group-containing compound, urea compound, A nitrogen heterocyclic compound etc. can be mentioned.

（前記一般式（１３）中、それぞれのＲ^２５は、相互に独立して、水素原子、アルキル基、アリール基、又はアラルキル基である。なお、これらの基は、例えばヒドロキシ基等の官能基で置換されていてもよい）

(In the general formula (13), each R ²⁵ is independently a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. These groups are functional groups such as a hydroxy group, for example. May be substituted)

  Examples of the nitrogen-containing compound (α) include linear, branched or cyclic monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and cyclohexylamine. Di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, methyl Linear, branched or cyclic dialkylamines such as cyclohexylamine and dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri -N-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri- -Linear, branched or cyclic trialkylamines such as decylamine, cyclohexyldimethylamine, methyldicyclohexylamine and tricyclohexylamine; linear, branched or cyclic alkanols such as ethanolamine, diethanolamine and triethanolamine Amines: aromatics such as aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, 1-naphthylamine Examples include amines.

  Examples of the nitrogen-containing compound (β) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, tetramethylenediamine, Hexamethylenediamine, 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-methyl Ethyl] benzene, and 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and the like.

  Examples of the nitrogen-containing compound (γ) include polymers of polyethyleneimine, polyallylamine, dimethylaminoethylacrylamide, 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, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole; pyridine, 2-methylpyridine, 4-methyl. Such as pyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-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, phenanthroli And the like can be given.

  Moreover, the nitrogen-containing compound which has an acid dissociable group can also be used as a nitrogen-containing organic compound. Examples of the nitrogen-containing compound having an acid dissociable group include N- (t-butoxycarbonyl) piperidine, N- (t-butoxycarbonyl) imidazole, N- (t-butoxycarbonyl) benzimidazole, N- (t -Butoxycarbonyl) 2-phenylbenzimidazole, N- (t-butoxycarbonyl) dioctylamine, N- (t-butoxycarbonyl) diethanolamine, N- (t-butoxycarbonyl) dicyclohexylamine, N- (t-butoxycarbonyl) Examples include diphenylamine.

  Among these nitrogen-containing organic compounds, nitrogen-containing compounds (α), nitrogen-containing compounds (β), nitrogen-containing heterocyclic compounds, nitrogen-containing compounds having an acid dissociable group, and the like are particularly preferable. An acid diffusion control agent can be used individually by 1 type or in combination of 2 or more types.

  The compounding amount of the acid diffusion controller is usually 15 parts by mass or less, preferably 0.001 to 10 parts by mass, more preferably 0.005 to 5 parts by mass per 100 parts by mass of the acid dissociable group-containing resin (B). It is. In this case, when the compounding amount of the acid diffusion controller is larger than a predetermined value, the sensitivity as a resist and the developability of the exposed portion tend to be lowered. In addition, if the compounding quantity of an acid diffusion control agent is less than 0.001 mass part, there exists a possibility that the pattern shape and dimension fidelity as a resist may fall depending on process conditions.

(Surfactant)
It is preferable to add a surfactant to the positive radiation sensitive resin composition of the present embodiment, if necessary. By blending this surfactant, coatability, striation, developability as a resist, and the like can be improved.

  Preferred examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenol ether, polyoxyethylene n-nonylphenol ether, polyethylene glycol dilaurate, polyethylene glycol diacrylate. Examples include stearate. Commercially available products include, for example, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), Megafax F171, F173 (above, manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC104, SC105 (above, manufactured by Asahi Glass), KP341 (Shin-Etsu Chemical Co., Ltd.) Manufactured), Polyflow No. 75, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

  Surfactant can be used individually by 1 type or in combination of 2 or more types. It is preferable that the compounding quantity of surfactant shall be 2 mass parts or less with respect to 100 mass parts of (B) component.

(Sensitizer)
Examples of the sensitizer include carbazoles, benzophenones, rose bengals, anthracene and the like. These sensitizers can be used individually by 1 type or in combination of 2 or more types. The blending amount of the sensitizer is preferably 50 parts by mass or less with respect to 100 parts by mass of the component (B).

(solvent)
The positive radiation sensitive resin composition of the present embodiment, when used, is uniformly in the solvent so that the concentration of the total solid content is usually 0.1 to 50% by mass, preferably 1 to 30% by mass. 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 preparing this composition solution include ethylene glycol such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate. 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; lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate; n-amyl formate, i-amyl formate, ethyl acetate, n-propyl acetate, i-propyl acetate, Aliphatic carboxylates such as n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, i-propyl propionate, n-butyl propionate and i-butyl propionate Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl Other esters such as butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4 -Ketones such as heptanone and cyclohexanone; Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; Lactones such as γ-butyrolacun Can be mentioned. These solvents can be used singly or in combination of two or more.

(Formation of resist pattern)
In order to form a resist pattern using the positive radiation sensitive resin composition of the present embodiment, the composition solution prepared as described above is applied appropriately by spin coating, cast coating, roll coating, or the like. By means, for example, it is applied onto a substrate such as a silicon wafer or a wafer coated with aluminum. Next, if necessary, a heat treatment (hereinafter also referred to as “PB”) is performed in advance at a temperature of about 70 ° C. to 160 ° C. to form a resist film, and then drawing is performed by irradiation with radiation and EB. The drawing conditions are appropriately selected according to the composition of the positive radiation sensitive resin composition, the types of various additives, and the like.

  In order to stably form a high-precision fine pattern, a heat treatment (hereinafter also referred to as “PEB”) is usually performed at a temperature of 50 to 200 ° C., preferably 70 to 160 ° C. for 30 seconds or more after irradiation. Is preferred. In addition, when the temperature of PEB is less than 50 ° C., variations in sensitivity depending on the type of substrate tend to spread. Then, a predetermined resist pattern can be formed by developing with an alkali developer usually at 10 to 50 ° C. for 10 to 200 seconds, preferably at 15 to 30 ° C. for 15 to 100 seconds.

  Examples of the alkali developer include alkali metal hydroxide, aqueous ammonia, mono-, di-, or tri-alkylamines, mono-, di-, or tri-alkanolamines, heterocyclic amines, Alkaline compounds such as tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene, Usually, an alkaline aqueous solution dissolved so as to have a concentration of 1 to 10% by mass, preferably 1 to 5% by mass, and more preferably 1 to 3% by mass is used. Further, a water-soluble organic solvent such as methanol or ethanol or a surfactant can be appropriately added to the developer composed of such an alkaline aqueous solution. In forming the resist pattern, a protective film or an antistatic film can be provided on the resist film in order to prevent the influence of basic impurities contained in the environmental atmosphere and the charge in the film.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Moreover, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below. The solvent used was refluxed for 6 hours in the presence of sodium metal and then distilled under a nitrogen atmosphere. The monomer used was distilled after bubbling with dry nitrogen for 1 hour.

  [Weight average molecular weight (Mw), number average molecular weight (Mn)]: Tosoh GPC columns (trade name “G2000HXL”, trade name “G3000HXL”, trade name “G4000HXL”) are used. , Flow rate: 1.0 ml / min, elution solvent: tetrahydrofuran, column temperature: measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under analysis conditions of 40 ° C.

(Synthesis Example 1: Resin (B-1))
101 g of p-acetoxystyrene, 5 g of styrene, 42 g of pt-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. The temperature was maintained at 70 ° C. and polymerization was performed for 16 hours. After the polymerization, the reaction solution was dropped into 2000 g of n-hexane to coagulate and purify the produced resin. Next, 150 g of 150 g of propylene glycol monomethyl ether was added again to the coagulated and 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 hydrolysis reaction, the solvent and triethylamine were distilled off under reduced pressure to obtain a resin. The obtained resin was redissolved in acetone so that the solid content concentration was 20%, and then dropped into 2000 g of water to be solidified. The produced white powder was filtered and dried at 50 ° C. under reduced pressure overnight to obtain a resin as a final product. Mw of the obtained resin was 16000 and Mw / Mn was 1.7. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of p-hydroxystyrene (1), styrene (2), and pt-butoxystyrene (3) was (1) :( 2) :( 3 ) = 72: 5: 23. This resin was designated as “resin (B-1)”.

(Synthesis Example 2: Resin (B-2))
100 g of p-acetoxystyrene, 25 g of t-butyl acrylate, 18 g of styrene, 6 g of AIBN and 1 g of t-dodecyl mercaptan were dissolved in 230 g of propylene glycol monomethyl ether, and the reaction temperature was maintained at 70 ° C. for 16 hours under a nitrogen atmosphere. Polymerized. After the polymerization, the reaction solution was dropped into 2000 g of n-hexane to coagulate and purify the produced resin. Next, 150 g of propylene glycol monomethyl ether was added again to the coagulated and 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 hydrolysis reaction, the solvent and triethylamine were distilled off under reduced pressure to obtain a resin. The obtained resin was redissolved in acetone so that the solid content concentration was 20%, and then dropped into 2000 g of water to be solidified. The produced white powder was filtered and dried at 50 ° C. under reduced pressure overnight to obtain a resin as a final product. Mw of the obtained resin was 11500 and Mw / Mn was 1.6. Moreover, as a result of ¹³ C-NMR analysis, the copolymerization molar ratio of p-hydroxystyrene (1), t-butyl acrylate (2) and styrene (3) was (1) :( 2) :( 3). = 61:19:20. This resin was designated as “resin (B-2)”.

(Synthesis Example 5: Resin (B-5))
After 106 g of pt-butoxystyrene, 4 g of AIBN, and 0.6 g of t-dodecyl mercaptan were dissolved in 110 g of propylene glycol monomethyl ether, the polymerization was carried out for 16 hours while maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. After the polymerization, the reaction solution was dropped into a large amount of n-hexane, and the produced polymer was coagulated and purified. After the coagulated and purified polymer is dissolved in acetone, the solution is dripped into a large amount of water to coagulate, and the resulting white powder is filtered and dried overnight at 50 ° C. under reduced pressure to obtain a polymer (poly (pt-t -Butoxystyrene)). Mw of the obtained poly (pt-butoxystyrene) was 13000, and Mw / Mn was 1.8. The obtained poly (pt-butoxystyrene) was dissolved in 600 g of dioxane, diluted hydrochloric acid was added and a hydrolysis reaction was performed at 70 ° C. for 2 hours, and then the reaction product was coagulated in a large amount of water to give a white solution. A polymer was obtained. After repeating the operation of dissolving the obtained polymer in acetone and coagulating it in a large amount of water, the produced white powder is filtered and dried at 50 ° C. under reduced pressure overnight to obtain poly (p-hydroxystyrene). )

25 g of the obtained poly (p-hydroxystyrene) was dissolved in 100 g of n-butyl acetate, and after bubbling with nitrogen gas for 30 minutes, 3.4 g of ethyl vinyl ether was added. Furthermore, 1 g of p-toluenesulfonic acid pyridinium salt was added as a catalyst and reacted at room temperature for 12 hours. After the reaction, the obtained reaction solution was dropped into a 1% aqueous ammonia solution to solidify the polymer, filtered, and dried overnight at 50 ° C. under reduced pressure to obtain a polymer as a final product. When ¹ H-NMR analysis was performed on the obtained polymer, 20 mol% of the hydrogen atoms of the phenolic hydroxyl group in the poly (p-hydroxystyrene) was substituted with an ethoxyxyethyl group. It had a structure. This polymer was designated as “resin (B-5)”.

(Examples 1 to 3, Comparative Example 1)
The components shown in Table 1 were mixed in the amounts shown in Table 1 to obtain a uniform solution, and then filtered through a membrane filter having a pore size of 200 nm to prepare a composition solution. Next, each composition solution was spin-coated on a silicon wafer in a trade name “Clean Track ACT-8” manufactured by Tokyo Electron Co., Ltd., and then subjected to PB under the conditions shown in Table 2 to obtain a resist having a film thickness of 130 nm. A film was formed. Next, using a simple electron beam drawing apparatus (model “HL800D”, manufactured by Hitachi, Ltd., output: 50 KeV, current density: 5.0 amps / cm ² ), the formed resist film was irradiated with an electron beam. PEB was performed under the conditions shown in Table 2. Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was used and developed by the paddle method at 23 ° C. for 1 minute, followed by washing with pure water and drying to form a resist pattern. Table 2 shows the evaluation results of the formed resist patterns. Moreover, materials other than Resin (B-1), Resin (B-2), and Resin (B-5) used in the respective Examples and Comparative Examples are shown below.

(Acid generator (A))
(A-1): Triphenylsulfonium cyclo (1,3-perfluoropropanedisulfone) imidate (A-4): Compound represented by the following formula (14)

(Other acid generator (C))
(C-5): Diphenyliodonium trifluoromethanesulfonate

(Other solvents (D))
(D-1): Ethyl lactate (D-2): Ethyl 3-ethoxypropionate

(Acid diffusion control agent (E))
(E-1): Tri-n-octylamine

  Various evaluation methods are as shown in the following (1) to (5).

(1) Sensitivity (L / S):
The resist film formed on the silicon wafer was exposed to light, immediately subjected to PEB, then developed with alkali, washed with water, and dried to form a resist pattern. At this time, the exposure amount for forming a line-and-space pattern (1L1S) having a line width of 150 nm in a one-to-one line width was set as the optimum exposure amount, and the sensitivity was evaluated based on the optimum exposure amount.

(2) Resolution (L / S):
For the line-and-space pattern (1L1S), the minimum line width (nm) of the line pattern resolved with the optimum exposure dose was taken as the resolution.

(3) Sensitivity (1L / 5S, isolated line pattern):
The resist film formed on the silicon wafer was exposed to light, immediately subjected to PEB, then developed with alkali, washed with water, and dried to form a resist pattern. At this time, the exposure amount for forming a line-and-space pattern (1L5S) having a line width of 150 nm with a line width of 1: 5 was taken as the optimum exposure amount, and the sensitivity was evaluated based on this optimum exposure amount.

(4) Resolution (1L / 5S):
For the line-and-space pattern (1L5S), the minimum line width (nm) of the line pattern resolved with the optimum exposure amount was taken as the resolution.

(5) LWR:
A line-and-space pattern (1L1S) line pattern having a design line width of 150 nm was observed with a semiconductor scanning electron microscope (high resolution FEB length measuring device, trade name “S-9220”, manufactured by Hitachi, Ltd.). FIG. 1 is a schematic diagram showing a line pattern (however, the unevenness is exaggerated from the actual state). 1A is a plan view, and FIG. 1B is a sectional view of a line pattern 2 formed on the silicon wafer 1. The shape observed in each example was evaluated by measuring the difference “ΔCD” between the line width and the design line width of 150 nm at the most conspicuous unevenness generated along the lateral surface 2a of the line pattern.

  The positive-type radiation-sensitive resin composition of the present invention is excellent not only in the resolution of the line and space pattern at the time of pattern formation, but also in the resolution of the 1L5S pattern and in the nano edge roughness. This is useful for forming fine patterns by EUV and X-rays. Therefore, the positive-type radiation-sensitive resin composition of the present invention is extremely useful as a chemically amplified resist for manufacturing semiconductor devices, which is expected to be further refined in the future.

1: Silicon wafer, 2: Line pattern, 2a: Side surface of line pattern.

Claims (4)

(A) As a radiation sensitive acid generator, an onium salt represented by the following general formula (1) and / or (2);
(B) an acid-dissociable group, and an alkali-insoluble or hardly-soluble resin component that becomes alkali-soluble when the acid-dissociable group is dissociated,
The positive radiation sensitive resin composition in which the (B) resin component contains the following repeating unit (i) and the following repeating unit (iii).
(I): Repeating unit represented by the following general formula (3) (iii): At least one repeating unit selected from the group consisting of the following general formulas (5-1) to (5-4)

(In the general formulas (1) and (2), M ⁺ is a monovalent onium cation, and Y is a C 2-6 alkylene group substituted with one or more fluorine atoms. In 2), R is an alkyl group having 1 to 4 carbon atoms which may be fluorine-substituted, or a cycloalkyl group having 3 to 6 carbon atoms which may be fluorine-substituted, and the alkyl group and the cycloalkyl group The oxygen chain in the alkylene chain may be contained)

(In the general formula (3), R ¹ is a hydrogen atom or a methyl group, R ² is a monovalent organic group, p is an integer of 0 to 3, and q is an integer of 1 to 3. When a plurality of R ² are present, the plurality of R ² may be the same or different from each other)

(In the general formula (5-1), R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a monovalent organic group (excluding a group corresponding to —OR ⁵ , where R ⁵ is 1 - branched alkyl group or a triorganosilyl group, or a triorganogermyl group), t is an integer from 0 to 3, when R ⁷ there is a plurality, the plurality of R ⁷ are identical to each other Or it may be different)

(In the general formula (5-2), R ⁸ and R ¹⁰ are a hydrogen atom or a methyl group, and R ⁹ is a divalent acid-dissociable organic group. R ⁸ and R ¹⁰ are the same as each other. Or it may be different)

(In the general formula (5-3), R ¹¹ is a hydrogen atom or a methyl group, R ¹² is an alkyl group having 1 to 4 carbon atoms, and R ¹³ is a hydrogen atom, a methyl group, or an ethyl group. )

(In the general formula (5-4), R ¹⁴ is a hydrogen atom or a methyl group, and R ¹⁵ is a tertiary alkyl group)   R in said general formula (2) is a C1-C4 alkyl group which may be fluorine-substituted, or a C3-C6 cycloalkyl group which may be fluorine-substituted. The positive radiation sensitive resin composition described.   The positive radiation sensitive resin composition according to claim 1 or 2, wherein the (A) onium salt is a sulfonium salt or an iodonium salt.   The positive radiation sensitive resin composition according to any one of claims 1 to 3, which is patterned by an electron beam or extreme ultraviolet rays.

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