JP4328951B2 - Resist material and pattern forming method - Google Patents

Description

  The present invention has a significantly high alkali dissolution rate contrast before and after exposure, high sensitivity and high resolution, excellent etching resistance and substrate adhesion, especially for ultra LSI manufacturing and photomask fine pattern formation The present invention relates to a chemically amplified positive resist material suitable as a material and a pattern forming method.

  In recent years, with the higher integration and higher speed of LSI, deep ultraviolet lithography has been put into practical use in response to the demand for finer pattern rules. Far-ultraviolet lithography can process 0.3 μm or less, and when a resist material with low light absorption is used, it is possible to form a pattern having sidewalls that are nearly perpendicular to the substrate.

  For example, a chemically amplified positive resist material using an acid as a catalyst (Patent Documents 1 and 2: JP-B-2-27660, JP-A-63-27829, etc.) is a high-brightness KrF excimer used as a light source for far ultraviolet rays. It is a resist material for deep ultraviolet lithography that uses a laser, has high sensitivity, resolution, dry etching resistance, and has excellent characteristics.

  As such a chemically amplified positive resist material, a two-component system comprising a base polymer and an acid generator, a three-component system comprising a base polymer, an acid generator and a dissolution inhibitor having an acid labile group are known. .

  For example, Japanese Patent Application Laid-Open No. 62-115440 (Patent Document 3) proposes a resist material comprising poly-p-tert-butoxystyrene and an acid generator. Japanese Patent Application Laid-Open No. 3-223858 is similar to this proposal. Gazette (Patent Document 4) discloses a two-component resist material composed of a resin having a tert-butoxy group in the molecule and an acid generator. Further, JP-A-4-21258 (Patent Document 5) discloses a methyl group and an isopropyl group. , A two-component resist material composed of polyhydroxystyrene containing a tert-butyl group, a tetrahydropyranyl group, or a trimethylsilyl group and an acid generator has been proposed.

  Further, JP-A-6-1000048 (Patent Document 6) discloses poly [3,4-bis (2-tetrahydropyranyloxy) styrene], poly [3,4-bis (tert-butoxycarbonyloxy) styrene]. Resist materials comprising polydihydroxystyrene derivatives such as poly [3,5-bis (2-tetrahydropyranyloxy) styrene] and acid generators have been proposed.

  However, the base resin of these resist materials has an acid labile group in the side chain, and the acid labile group is decomposed with a strong acid such as tert-butyl group and tert-butoxycarbonyl group. The pattern shape of the resist material tends to be a T-top shape. On the other hand, an alkoxyalkyl group such as an ethoxyethyl group is decomposed by a weak acid, so that the pattern shape changes with time from exposure to heat treatment. It has the disadvantages of being extremely thin and has a bulky group in the side chain, so there are problems such as low heat resistance and unsatisfactory sensitivity and resolution. Studies have been made such as using a substituent of

  Resist materials that use a copolymer of hydroxystyrene and (meth) acrylic acid tertiary ester to achieve higher transparency and adhesion to the substrate, improve tailing to the substrate, and improve etching resistance (Patent Documents 7 and 8: see JP-A-3-275149 and JP-A-6-289608). However, this type of resist material has poor heat resistance and a poor pattern shape after exposure. There was a problem and the etching resistance was not satisfactory.

  Here, a resist material characterized by adding a polymer whose end is controlled to JP-A-11-236416 (Patent Document 9) has been proposed. Here, the polymer terminal shows a group which is stable against acid.

  In Japanese Patent Application Laid-Open No. 2003-140350 (Patent Document 10), an attempt was made to improve dissolution contrast by attaching an acid labile group in which a hydrogen atom of a carboxylic acid was substituted to the polymer terminal. The influence of the polymer terminal is large on the dissolution contrast, and the dissolution contrast can be improved by block copolymerization in which a repeating unit substituted with an acid labile group is arranged at the polymer terminal.

  There are various methods for synthesizing the block copolymer, and examples of the polymerization method for the controlled block copolymer include a living polymerization method and a condensation polymerization method. In the living polymerization method, anionic polymerization is most often used, but cationic polymerization and radical polymerization are also used (Non-Patent Documents 1 to 3: “Block and graft polymers” JJ Gurke, V. Weiss Ed., Syracuse Univ.). Press (1973), “Block copolymers” D. J. Meier Ed., Harcade academic Press, New York (1979), “Multicomponent polymers, S. L. Co. E. M. E. A. Soc., Washington, DC (1979)).

SPIE Vol. 3678 p78-85 (1999) (Non-patent Document 4) The resolution is improved by adding a polymer obtained by block copolymerization of an acid labile group-containing monomer and an adhesive group-containing monomer to a random copolymerized polymer. It has been reported.
Japanese Patent Application Laid-Open No. 10-53621 (Patent Document 11) and Japanese Patent Application Laid-Open No. 2001-139626 (Patent Document 12) describe a block polymer of narrowly dispersed polyhydroxystyrene and (meth) acryl obtained by living anion polymerization. It is shown.

  A feature of block copolymerization is that a microphase separation structure is formed in a high-concentration solution. When a microphase separation structure is formed in the film after spin coating, the acid diffusion and alkali solubility of the separated domains are different, so a pattern completely different from the mask pattern is formed or the line edge roughness is large. It becomes. When a monomer having a different main chain structure is subjected to block copolymerization, such as copolymerization of hydroxystyrene and (meth) acryl, microphase separation is particularly easily formed. On the other hand, in the case of the block copolymer according to the present invention in which the main chain is the same hydroxystyrene and only the polymer terminal is substituted with an acid labile group, microphase separation hardly occurs. By having a repeating unit of polyhydroxystyrene substituted with an acid labile group in the vicinity of the polymer end, the alkali dissolution contrast before and after the elimination of the acid labile group is dramatically improved.

JP-B-2-27660 JP 63-27829 A JP 62-115440 A JP-A-3-223858 JP-A-4-21258 Japanese Patent Laid-Open No. 6-1000048 JP-A-3-275149 JP-A-6-289608 Japanese Patent Laid-Open No. 11-236416 JP 2003-140350 A Japanese Patent Laid-Open No. 10-53621 JP 2001-139626 A “Block and graph colors” J. Org. J. et al. Gurke, V.M. Weiss Ed. , J. et al. J. et al. Gurke, V.M. Weiss Ed. , Syracuse Univ. Press (1973) “Block copolymers” D.D. J. et al. Meier Ed. , D. J. et al. Meier Ed. , Harwood academic Press, New York (1979) “Multicomponent polymers” S.M. L. Cooper, G.C. M.M. Esters Ed. , Am. Chem. Soc. , Washington, D .; C. (1979) SPIE Vol. 3678 p78-85 (1999)

  The present invention has been made in view of the above circumstances, has higher sensitivity and higher resolution than conventional resist materials, exposure margin, process adaptability, good pattern shape after exposure, and excellent etching resistance. An object of the present invention is to provide a resist material exhibiting the above, in particular, a chemically amplified positive resist material and a pattern forming method.

  As a result of intensive investigations to achieve the above object, the present inventor has found that a repeating unit of hydroxystyrene, hydroxyvinylnaphthalene or hydroxyvinylanthracene in which a hydrogen atom of a hydroxy group is partially substituted with an acid labile group. By adding a polymer in which the hydrogen atom of the hydroxy group is selectively substituted with an acid labile group at one or both repeating units of the polymer, the resist dissolution contrast is increased. It was found that the resolution was improved dramatically and the resolution was improved.

  In particular, a high molecular compound having a repeating unit comprising a block copolymer represented by the following general formula (1), (2) or (3) and having a weight average molecular weight of 1,000 to 500,000 is a positive resist material. In particular, it is effective as a base resin for chemically amplified positive resist materials. This chemically amplified positive resist material containing a polymer compound, an acid generator and an organic solvent has a high dissolution contrast and resolution of the resist film. It has a margin, excellent process adaptability, good pattern shape after exposure, and better etching resistance, which makes it highly practical, resist material for VLSI or photomask pattern forming material As a result, the present invention has been found to be very effective.

（式中、Ｒ¹は炭素数１〜２０の直鎖状、分岐状もしくは環状のアルキル基であり、Ｒ²、Ｒ⁵は水素原子である。Ｒ³、Ｒ⁶は炭素数６〜２０の芳香環であり、Ｒ⁴は水素原子又は水素原子と酸不安定基との混在であり、繰り返し単位ａ及びｄ中の５０モル％以下のヒドロキシ基の水素原子が酸不安定基で置換されており、Ｒ⁷は酸不安定基である。Ｒ⁸はヒドロキシ基、カルボキシ基、炭素数１〜２０のヒドロキシ基、エステル基、エーテル基、ラクトン環、シアノ基を含んでいてもよい脂肪族もしくは芳香族１価炭化水素基、アルコキシ基、又は下記一般式（４）で示される基である。

ここで、上記一般式（４）中、Ｒ⁹は単結合、炭素数１〜１０の直鎖状、分岐状もしくは環状のアルキレン基、有橋環式のアルキレン基又は炭素数６〜１０のアリーレン基であり、Ｒ¹⁰は酸不安定基である。Ｚは単結合又はｐ＋１価の脂肪族もしくは芳香族炭化水素基で、カルボニル基、エステル基又はエーテル基を含んでいてもよい。ｐは１又は２である。ａ、ｂはそれぞれ正数であり、０．５≦ａ＜１．０、０＜ｂ≦０．５、０．５≦ｄ＜１．０、０＜ｃ≦０．２５、０＜ｅ≦０．２５の範囲であり、ｍ、ｎは１〜３の整数である。）
請求項２：
一般式（１）、（２）又は（３）において、Ｒ³、Ｒ⁶で示される芳香環が、ベンゼン環、ナフタレン環又はアントラセン環であることを特徴とする請求項１記載のレジスト材料。
請求項３：
一般式（１）、（２）又は（３）において、一般式（４）が、下記一般式（４−１）〜（４−３）から選ばれる基であることを特徴とする請求項１又は２記載のレジスト材料。

（式中、Ｒ⁹、Ｒ¹⁰は前記と同様である。Ｒ⁰は、単結合、又は炭素数１〜１０の直鎖状、分岐状、環状もしくは有橋環式のアルキレン基又は炭素数６〜１０のアリーレン基であり、カルボニル基、エステル基、又はエーテル基を含んでいてもよい。Ｒは、炭素数１〜６の直鎖状又は分岐状のアルキレン基より水素原子が１個脱離した３価の脂肪族炭化水素基を示す。又は、前記

を形成する基である。）
請求項４：
（Ａ）有機溶剤、
（Ｂ）ベース樹脂として請求項１乃至３のいずれか１項に記載の重合体、
（Ｃ）酸発生剤
を含有してなることを特徴とする化学増幅ポジ型レジスト材料。
請求項５：
（Ａ）有機溶剤、
（Ｂ）ベース樹脂として請求項１乃至３のいずれか１項に記載の重合体、
（Ｃ）酸発生剤、
（Ｄ）溶解阻止剤
を含有してなることを特徴とする化学増幅ポジ型レジスト材料。
請求項６：
更に、（Ｅ）添加剤として塩基性化合物を配合したことを特徴とする請求項４又は５記載の化学増幅ポジ型レジスト材料。
請求項７：
請求項１乃至６のいずれか１項に記載のレジスト材料を基板上に塗布する工程と、加熱処理後、フォトマスクを介して高エネルギー線もしくは電子線で露光する工程と、必要に応じて加熱処理した後、現像液を用いて現像する工程とを含むことを特徴とするパターン形成方法。 Accordingly, the present invention provides the following resist material and pattern forming method.
Claim 1:
A polymer having, as a repeating unit, hydroxystyrene, hydroxyvinylnaphthalene or hydroxyvinylanthracene in which a hydrogen atom of a hydroxy group is partially substituted with an acid labile group, wherein monomers are sequentially added using living anionic polymerization In the charging method, at the start and / or end of polymerization, hydroxystyrene, hydroxyvinylnaphthalene or hydroxyvinylanthracene substituted with an acid labile group is added, polymerized and charged, at one or both ends of the polymer, In the repeating unit at one or both ends, obtained by continuously arranging repeating units substituted with the acid labile group, the hydrogen atom of the hydroxy group is selectively substituted with an acid labile group. Add the block copolymer represented by the following general formula (1), (2) or (3) Resist material characterized by comprising Te.

(In the formula, R ¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ² and R ⁵ are hydrogen atoms. R ³ and R ⁶ have 6 to 20 carbon atoms. R ⁴ is an aromatic ring, R ⁴ is a hydrogen atom or a mixture of a hydrogen atom and an acid labile group, and the hydrogen atom of 50 mol% or less of the hydroxy group in the repeating units a and d is substituted with an acid labile group. R ⁷ is an acid labile group, R ⁸ is an aliphatic group which may contain a hydroxy group, a carboxy group, a hydroxy group having 1 to 20 carbon atoms, an ester group, an ether group, a lactone ring, a cyano group, or An aromatic monovalent hydrocarbon group, an alkoxy group, or a group represented by the following general formula (4).

Here, in the general formula (4), R ⁹ is a single bond, a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, a bridged cyclic alkylene group, or an arylene having 6 to 10 carbon atoms. R ¹⁰ is an acid labile group. Z is a single bond or a p + 1 valent aliphatic or aromatic hydrocarbon group which may contain a carbonyl group, an ester group or an ether group. p is 1 or 2. a and b are positive numbers, 0.5 ≦ a <1.0, 0 <b ≦ 0.5, 0.5 ≦ d <1.0, 0 <c ≦ 0.25, 0 <e ≦ The range is 0.25, and m and n are integers of 1 to 3. )
Claim 2:
The resist material according to claim 1, wherein the aromatic ring represented by R ³ or R ⁶ in the general formula (1), (2) or (3) is a benzene ring, a naphthalene ring or an anthracene ring.
Claim 3:
2. The general formula (1), (2) or (3), wherein the general formula (4) is a group selected from the following general formulas (4-1) to (4-3). Or the resist material of 2.

(Wherein R ⁹ and R ¹⁰ are the same as described above. R ⁰ is a single bond, a linear, branched, cyclic or bridged alkylene group having 1 to 10 carbon atoms, or 6 carbon atoms. Is an arylene group having from 10 to 10 and may contain a carbonyl group, an ester group, or an ether group, and R is one hydrogen atom removed from a linear or branched alkylene group having 1 to 6 carbon atoms. A trivalent aliphatic hydrocarbon group, or

Is a group that forms )
Claim 4 :
(A) an organic solvent,
(B) The polymer according to any one of claims 1 to 3 as a base resin,
(C) A chemically amplified positive resist material comprising an acid generator.
Claim 5 :
(A) an organic solvent,
(B) The polymer according to any one of claims 1 to 3 as a base resin,
(C) an acid generator,
(D) A chemically amplified positive resist material comprising a dissolution inhibitor.
Claim 6 :
Additionally, (E) a chemically amplified positive resist composition according to claim 4 or 5, wherein it has a basic compound as an additive.
Claim 7 :
A step of applying the resist material according to any one of claims 1 to 6 on a substrate, a step of exposing to a high energy beam or an electron beam through a photomask after the heat treatment, and heating if necessary And a step of developing using a developer after the treatment.

  The resist material of the present invention has a significantly high alkali dissolution rate contrast before and after exposure, high sensitivity and high resolution, and particularly excellent etching resistance. It is possible to provide a resist material such as a chemically amplified resist material suitable as a material.

The resist material of the present invention is a polymer having, as a repeating unit, hydroxystyrene, hydroxyvinylnaphthalene or hydroxyvinylanthracene in which a hydrogen atom of a hydroxy group is partially substituted with an acid labile group, Or the polymer in which the hydrogen atom of the hydroxy group is selectively substituted with an acid labile group in the repeating units at both ends is contained.
In this case, as this polymer, the hydrogen atom of the hydroxy group in the repeating unit at one end or both ends represented by the following general formula (1), (2) or (3) is selectively an acid labile group. Examples thereof include a polymer having a substituted hydroxystyrene, hydroxyvinylnaphthalene or hydroxyvinylanthracene as a repeating unit.

（式中、Ｒ¹は炭素数１〜２０の直鎖状、分岐状もしくは環状のアルキル基であり、Ｒ²、Ｒ⁵は水素原子である。Ｒ³、Ｒ⁶は炭素数６〜２０の芳香環であり、Ｒ⁴は水素原子又は酸不安定基であり、くり返し単位ａ及びｄ中の５０モル％以下のヒドロキシ基の水素原子が酸不安定基で置換されており、Ｒ⁷は酸不安定基である。Ｒ⁸はヒドロキシ基、カルボキシ基、炭素数１〜２０のヒドロキシ基、エステル基、エーテル基、ラクトン環、シアノ基を含んでいてもよい脂肪族もしくは芳香族１価炭化水素基、アルコキシ基、又は下記一般式（４）で示される基であってもよい。

ここで、上記一般式（４）中、Ｒ⁹は単結合、炭素数１〜１０の直鎖状、分岐状もしくは環状のアルキレン基、有橋環式のアルキレン基又は炭素数６〜１０のアリーレン基であり、Ｒ¹⁰は酸不安定基である。Ｚは単結合又はｐ＋１価の脂肪族もしくは芳香族炭化水素基で、カルボニル基、エステル基又はエーテル基を含んでいてもよい。ｐは１又は２である。ａ、ｂはそれぞれ正数であり、０．５≦ａ＜１．０、０＜ｂ≦０．５、０．５≦ｄ＜１．０、０＜ｃ≦０．２５、０＜ｅ≦０．２５の範囲であり、ｍ、ｎは１〜３の整数である。）

(In the formula, R ¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ² and R ⁵ are hydrogen atoms. R ³ and R ⁶ have 6 to 20 carbon atoms. R ⁴ is an aromatic ring, R ⁴ is a hydrogen atom or an acid labile group, hydrogen atoms of hydroxy groups of 50 mol% or less in the repeating units a and d are substituted with an acid labile group , and R ⁷ is an acid labile group R ⁸ is an aliphatic or aromatic monovalent hydrocarbon which may contain a hydroxy group, a carboxy group, a hydroxy group having 1 to 20 carbon atoms, an ester group, an ether group, a lactone ring or a cyano group. It may be a group, an alkoxy group, or a group represented by the following general formula (4).

Here, in the general formula (4), R ⁹ is a single bond, a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, a bridged cyclic alkylene group, or an arylene having 6 to 10 carbon atoms. R ¹⁰ is an acid labile group. Z is a single bond or a p + 1 valent aliphatic or aromatic hydrocarbon group which may contain a carbonyl group, an ester group or an ether group. p is 1 or 2. a and b are positive numbers, 0.5 ≦ a <1.0, 0 <b ≦ 0.5, 0.5 ≦ d <1.0, 0 <c ≦ 0.25, 0 <e ≦ The range is 0.25, and m and n are integers of 1 to 3. )

Here, in the general formula (4), R ⁹ is specifically methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, cyclohexylene group. And a bridged cyclic group such as a norbornylene group and an adamantylene group, and a methylene group, an ethylene group and an n-propylene group are particularly preferably used. Examples of the arylene group include a phenylene group.

Examples of Z include the following.

を形成する基を示す。 However, R ⁰ is a single bond, or a linear, branched, cyclic or bridged cyclic alkylene group or a C 6-10 arylene group similar to R ⁹ , It may contain a group, an ester group, or an ether group. R represents a trivalent aliphatic hydrocarbon group in which one hydrogen atom is eliminated from a linear or branched alkylene group having 1 to 6 carbon atoms. Or

The group which forms is shown.

Examples of the alkyl group for R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group and the like. The alkyl group of R ^{1 is} an alkyl group of an initiator used for anion living polymerization, and an n-butyl group, an isobutyl group, and a sec-butyl group are preferably used.

R ³ and R ⁶ are preferably benzene rings for KrF excimer laser exposure, but naphthalene rings or anthracene rings can also be used for EB exposure. At the wavelength of 248 nm of the KrF excimer laser, the naphthalene ring and the anthracene ring have strong absorption, so that the pattern cannot be formed. However, since the EB has no absorption, a vertical pattern can be formed. Dry etching resistance is higher for naphthalene and anthracene rings than for benzene rings.

The acid labile groups R ⁴ and R ⁷ of the phenolic hydroxyl group in the base polymer and the acid labile group R ¹⁰ of the carboxyl group may be the same or different, and are selected variously. (AL10), (AL11) Or a tertiary alkyl group having 4 to 40 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the like represented by the following formula (AL12): Examples include structures.

In the above formulas (AL10) and (AL11), R ¹¹ and R ¹⁴ are linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms and may contain heteroatoms such as oxygen, sulfur, nitrogen and fluorine. Good.
R ¹² and R ¹³ are each a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain a heteroatom such as oxygen, sulfur, nitrogen and fluorine, and a is 0 to 10 Is an integer.
R ¹² and R ¹³ , R ¹² and R ¹⁴ , R ¹³ and R ¹⁴ may be bonded together to form a ring having 4 to 20 carbon atoms together with the carbon atom to which they are bonded.

  Specific examples of the compound represented by the formula (AL10) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl. Groups, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like, and substituents represented by the following general formulas (AL10) -1 to (AL10) -9.

In the above formulas (AL10) -1 to (AL10) -9, R ¹⁸ is the same or different linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, aryl group having 6 to 20 carbon atoms or aralkyl. Indicates a group. R ¹⁹ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ²⁰ represents an aryl group or aralkyl group having 6 to ²⁰ carbon atoms.

  Examples of the acetal compound represented by the above formula (AL11) are (AL11) -1 to (AL11) -30.

  Further, the base resin may be intermolecularly or intramolecularly crosslinked by an acid labile group represented by the following general formula (AL11-a) or (AL11-b).

In the above formula, R ³³ and R ³⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³³ and R ³⁴ may be bonded to form a ring, and when forming a ring, R ³³ and R ³⁴ represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ³⁵ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, b and d are 0 or 1 to 10, preferably 0 or an integer of 1 to 5, and c is an integer of 1 to 7. . A represents a (c + 1) -valent C1-C50 aliphatic or alicyclic saturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic group, and these groups represent heteroatoms such as O, S, and N. It may be interposed, or a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B represents —CO—O—, —NHCO—O— or —NHCONH—.

  In this case, preferably, A is a divalent to tetravalent C1-20 linear, branched or cyclic alkylene group, an alkyltriyl group, an alkyltetrayl group, or an arylene group having 6 to 30 carbon atoms. These groups may have intervening heteroatoms such as O, S and N, and a part of the hydrogen atoms bonded to the carbon atoms are substituted by a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. It may be. C is preferably an integer of 1 to 3.

  Specific examples of the crosslinked acetal groups represented by the general formulas (AL11-a) and (AL11-b) include those represented by the following formulas (AL11) -31 to (AL11) -38.

In the above formula (AL12), examples of R ¹⁵ , R ¹⁶ and R ¹⁷ include straight, branched or cyclic alkyl groups having 1 to 20 carbon atoms, particularly 1 to 16 carbon atoms. Alternatively, R ¹⁵ and R ¹⁶ , R ¹⁵ and R ¹⁷ or R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring having 3 to 20 carbon atoms, particularly 4 to 16 carbon atoms, together with the carbon atoms to which they are bonded. .

  The tertiary alkyl group represented by the above formula (AL12) includes a tert-butyl group, a triethylcarbyl group, a 1-ethylnorbornyl group, a 1-methylcyclohexyl group, a 1-ethylcyclopentyl group, and 2- (2-methyl). ) An adamantyl group, a 2- (2-ethyl) adamantyl group, a tert-amyl group or the like, or the following general formulas (AL12) -1 to (AL12) -18 can be exemplified.

In the above formula, R ²¹ represents the same or different linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, aryl group having 6 to 20 carbon atoms, and aralkyl group. R ²² and R ^{24 each} represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ²³ represents an aryl group or aralkyl group having 6 to 20 carbon atoms.

Furthermore, as shown in the following formulas (AL12) -19 and (AL12) -20, even if R ²⁵ which is a divalent or higher valent alkylene group or an arylene group is included, the polymer molecule or the molecule may be crosslinked. Good. In the following formula (AL12) -19, 20, R ²¹ is the same as described above, and R ²⁵ represents a linear, branched or cyclic alkylene group or arylene group having 1 to 20 carbon atoms, an oxygen atom, a sulfur atom, Hetero atoms such as nitrogen atoms may be included. b is an integer of 1 to 3.

R ²¹ , R ²² , R ²³ , and R ²⁴ may have heteroatoms such as oxygen, nitrogen, and sulfur, and are specifically shown in the following formulas (13) -1 to (13) -7. be able to.

  Examples of the trialkylsilyl group whose acid labile group is 1 to 6 carbon atoms include trimethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group and the like.

  The copolymerization of the repeating units ab and cde represented by the general formula (1), (2) or (3) is a block copolymer in which a unit and b unit, c unit, d unit and e unit are continuously connected. It is a coalescence. As a polymerization method of this block copolymer, a method of sequentially adding monomers using living polymerization can be mentioned. When anionic living polymerization using alkyllithium is used, hydroxystyrene substituted with an acid labile group is added to the end of the polymer by adding hydroxystyrene substituted with an acid labile group at the start or end of the polymerization. It is possible to arrange repeating units. The position of the acid labile group in the polymer molecule can be controlled by precisely controlling the type and amount of the monomer to be added. In living anionic polymerization, a narrow dispersion polymer having a molecular weight distribution of 1.5 or less can also be obtained. Narrowly dispersed molecular weight distribution polymers are characterized by high resolution and low line edge roughness.

  Here, in radical polymerization, random copolymerization is performed, the molecular weight distribution is 1.5 or more, and the polymer cannot be a narrow dispersion molecular weight distribution.

In the general formula (1), (2) or (3), when R ³ and R ⁶ are benzene rings, a hydroxystyrene derivative represented by the following general formula (5) -1 and R ³ and R ⁶ are naphthalene rings In the case, when the hydroxyvinylnaphthalene derivative represented by the following general formula (5) -2 and R ³ and R ⁶ are anthracene rings, the living anion polymerization is performed using the hydroxyvinylanthracene derivative represented by the following general formula (5) -3. I do.

（Ｒ^2,5はＲ²又はＲ⁵であることを示す。（ＯＲ⁴⁰）_m,nは（ＯＲ⁴⁰）_m又は（ＯＲ⁴⁰）_nであることを示す。）

(R ^2,5 represents R ² or R ^5. (OR ⁴⁰ ) _{m, n} represents (OR ⁴⁰ ) _m or (OR ⁴⁰ ) _n .)

Here, R ² , R ⁵ , m and n are as described above, and R ⁴⁰ is a linear, branched or cyclic primary or secondary alkyl group having 1 to 6 carbon atoms, the formula (AL11) An acetal group represented by formula (III), a tertiary alkyl group represented by the formula (AL12), a trialkylsilyl group, and the like.

The terminal of the polymerization in anionic polymerization is converted into a metal anion, which is not preferable as a polymer compound for semiconductor use because it is affected by metal contamination. It is necessary to perform a termination reaction to remove the anion and remove the metal. The termination reaction is carried out with water, alcohol, carbon dioxide, halide or the like. By the termination reaction, the terminal is represented by R ⁸ in the general formula (1), (2) or (3). When the termination reaction is carried out with water, R ⁸ becomes a hydroxy group, when it is carried out with carbon dioxide, it is a carboxy group, and when carried out with a halogenated hydrocarbon, it is a linear, branched or cyclic fatty acid having 1 to 20 carbon atoms. Or an aromatic hydrocarbon group when alcohol is used. In particular, since the termination reaction with a halide is performed instantaneously, a very narrow polymer having a molecular weight distribution of 1.1 or less can be obtained.

In this case, as the polymerization terminator, those represented by the following general formula (6) are preferable. The polymerization terminator represented by the following general formula (6) is represented by the following general formulas (6) -1 to (6) -3. Here, R, R ⁰ , R ⁹ , R ¹⁰ , Z, and p are as described above, and X includes a halogen atom, an aldehyde group, a hydroxyl group, a carboxyl group, and the like.

  Furthermore, the polymerization terminators represented by the general formulas (6) -1 to (6) -3 can be specifically exemplified as follows.

（上記式中、Ｒ¹⁰及びＸは上記の通りである。）

(In the above formula, R ¹⁰ and X are as described above.)

  Examples of living polymerization include living anion polymerization and living radical polymerization. Among them, living anionic polymerization is preferably used. When living anionic polymerization is performed, the reaction solvent is preferably a solvent such as toluene, benzene, tetrahydrofuran, dioxane, or ethyl ether, and particularly preferably a polar solvent such as tetrahydrofuran, dioxane, or ethyl ether. You can use it.

  As the initiator, alkyl lithium is used, and among them, sec-butyl lithium and n-butyl lithium are particularly preferable, and the amount used is proportional to the design molecular weight.

  The reaction temperature is −80 to 100 ° C., preferably −70 to 0 ° C., and the reaction time is 0.1 to 50 hours, preferably 0.5 to 5 hours. In the above method, a polymer having a weight average molecular weight of 1,000 to 1,000,000 and having a repeating unit represented by the general formula (1), (2) or (3) can be obtained.

  Examples of methods for synthesizing polyhydroxystyrene, polyhydroxyvinylnaphthalene, and polyhydroxyvinylanthracene substituted at the terminal with an acid labile group to be added to the resist compound of the present invention will be given. In the following schematic diagrams a-1 to a-6, OH is unprotected hydroxystyrene, hydroxyvinylnaphthalene, hydroxyvinylanthracene, A is an acid labile group, and OA is hydroxystyrene substituted with an acid labile group Represents a repeating unit of hydroxyvinylnaphthalene and hydroxyvinylanthracene.

  Here, in the a-1, the whole polymer is randomly substituted with acid labile groups. Both ends of a-2 are substituted with acid labile at both ends, and the central part is randomly substituted with acid labile groups. In a-3, one end is substituted with an acid labile group, and the central portion and the other one end are randomly substituted with an acid labile group. In a-4, only both ends are substituted with acid labile groups, and the central part is all hydroxy groups. The central part of a-5 is substituted with an acid labile group, and both ends are all hydroxy groups. The center of a-6 is substituted with an acid labile group, and both ends are randomly substituted with an acid labile group.

a-1 is a conventional polymer in which the position of the acid labile group in the polymer chain is not controlled.
a-2 and a-3 are polymers used in the photoresist of the present invention. The photoresist to which the block copolymer shown in a-4 and a-5 is added causes microphase separation. Although the position of the acid labile group of a-6 is opposite to that of a-2, the dissolution contrast of the resist is different, and the resist added with the a-2 polymer has a higher contrast.

  Examples of the polymerization method of the polymers represented by the above (a-2) and (a-3) used in the photoresist of the present invention include a method of sequentially charging monomers. For example, as shown in the figure below, t-butoxystyrene and a polymerization initiator are charged and polymerization is started (Step 1), and then ethoxyethoxystyrene is added to perform polymerization (Step 2). Is added (Step 3), and finally a polymerization terminator is added (Step 4). If a weak acid such as vinegar, acid, formic acid, oxalic acid, hydrochloric acid and water are added and heated and stirred, only ethoxyethoxy is deprotected and the polymer shown in a-4 can be obtained (Step 5). By partially protecting the polymer of a-4 with an acid labile group (Step 6), the polymer represented by a-2 can be obtained.

  As another method, as shown in the figure below, t-butoxystyrene and a polymerization initiator are charged to start polymerization (Step 1), and then a mixture of ethoxyethoxystyrene and t-butoxystyrene is added to perform polymerization. (Step 2), t-butoxystyrene is then added (Step 3), and finally a polymerization terminator is added (Step 4). If an acid and water are added and heated and stirred, only ethoxyethoxy is deprotected (Step 5), and the polymer shown in a-2 can be obtained.

  In this case, sec-butyllithium can be used as a polymerization initiator, and tbutyl 3-bromopropionate can be used as a polymerization terminator.

  Here, in order to perform deprotection selectively in the above Step 5, deprotection using an acid as a catalyst is performed. By combining acid labile groups having different acid elimination rates, only acid labile groups having a high acid elimination rate can be deprotected. Accordingly, the terminal acid labile group is limited to an acid labile group having a slow acid elimination rate. Examples of acid labile groups with slow acid elimination include tertiary ethers, and examples of acid labile groups with fast acid elimination include various acetals, ketals, and trialkylsilyl ethers.

  When all the acid labile groups other than the terminal are deprotected and the polymer shown in the above (a-4) is synthesized, it is necessary to partially protect the intermediate phenol residue. As a method for introducing the acid labile group represented by the general formula (AL11) into the phenolic hydroxyl group after isolating the polymer compound, for example, the phenolic hydroxyl group of the polymer compound is converted to an alkenyl ether compound and an acid catalyst. A method of obtaining a polymer compound in which a phenolic hydroxyl group is partially protected with an alkoxyalkyl group by a lower reaction is exemplified.

  At this time, the reaction solvent is preferably an aprotic polar solvent such as dimethylformamide, dimethylacetamide, tetrahydrofuran or ethyl acetate, and may be used alone or in combination. As the acid of the catalyst, hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid pyridinium salt and the like are preferable, and the amount used thereof is the phenolic hydroxyl group of the polymer compound to be reacted. It is preferable that a hydrogen atom is 0.1-10 mol% with respect to 1 mol of the whole hydroxyl group. The reaction temperature is −20 to 100 ° C., preferably 0 to 60 ° C., and the reaction time is 0.2 to 100 hours, preferably 0.5 to 20 hours.

  It is also possible to obtain a polymer compound in which a phenolic hydroxyl group is partially protected with an alkoxyalkyl group by reacting with a polymer compound in the presence of a base using a halogenated alkyl ether compound.

  At this time, the reaction solvent is preferably an aprotic polar solvent such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran, or dimethylsulfoxide, and may be used alone or in combination. As the base, triethylamine, pyridine, diisopropylamine, potassium carbonate and the like are preferable, and the amount used is 10 mol% or more of the hydrogen atom of the phenolic hydroxyl group of the polymer compound to be reacted with respect to 1 mol of the total hydroxyl group. Is preferred. The reaction temperature is −50 to 100 ° C., preferably 0 to 60 ° C., and the reaction time is 0.5 to 100 hours, preferably 1 to 20 hours.

  Further, the acid labile group of the above formula (AL10) can be introduced by reacting a dialkyl dicarbonate compound or an alkoxycarbonylalkyl halide with a polymer compound in a solvent in the presence of a base. The reaction solvent is preferably an aprotic polar solvent such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran, or dimethyl sulfoxide, and may be used alone or in admixture of two or more.

As the base, triethylamine, pyridine, imidazole, diisopropylamine, potassium carbonate and the like are preferable, and the amount used is 10 mol% or more of the hydrogen atom of the phenolic hydroxyl group of the original polymer compound with respect to 1 mol of the total hydroxyl group. Preferably there is.
The reaction temperature is 0 to 100 ° C, preferably 0 to 60 ° C. The reaction time is 0.2 to 100 hours, preferably 1 to 10 hours.

Examples of the dialkyl dicarbonate compound include di-tert-butyl dicarbonate and di-tert-amyl dicarbonate. Examples of the alkoxycarbonylalkyl halide include tert-butoxycarbonylmethyl chloride, tert-amyloxycarbonylmethyl chloride, and tert-butoxy. Examples thereof include carbonylmethyl bromide and tert-butoxycarbonylethyl chloride.
However, it is not limited to these synthesis methods.

  The ratio of the repeating units a, b, c, d, e shown in the general formula (1), (2) or (3) is 0.5 ≦ a <1.0, 0 <b ≦ 0.5, 0. 5 ≦ d <1.0, 0 <c ≦ 0.25, 0 <e ≦ 0.25, preferably 0.6 ≦ a <1.0, 0 <b ≦ 0.4, 0. The ranges are 6 ≦ d <1.0, 0 <c ≦ 0.2, and 0 <e ≦ 0.2.

  The polymer represented by the general formula (1), (2) or (3) has a polymerization average molecular weight (Mw) of 1,000 to 1,000,000, particularly 2,000 to 500,000. preferable. The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) is preferably 1.0 to 2.0, particularly preferably 1.0 to 1.5.

  The resist material of the present invention is characterized in that a polymer having a polymer terminal substituted with an acid labile group is added, but a conventional polymer material can be added, that is, a polymer blend can be used. Conventional polymer materials include substituted or unsubstituted novolaks, polyhydroxystyrenes, polyhydroxystyrene- (meth) acrylic acid derivatives, (meth) acrylic derivatives, norbornene derivatives, maleic anhydride, maleimide derivatives, acenaphthene derivatives, Polymers such as vinyl naphthalene derivatives, vinyl anthracene derivatives, vinyl ether derivatives, allyl ether derivatives, vinyl acetate, (meth) acrylonitrile, vinyl pyrrolidone, tetrafluoroethylene, or indene derivatives, indole derivatives, benzofuran derivatives, benzothiophene derivatives, or these It is a copolymer with polyhydroxystyrene. The polymer polymerization method may be anionic polymerization, radical polymerization, or cationic polymerization. Furthermore, in the resist material of the present invention, two or more polymer blends having different molecular weights and dispersities, or two or more polymer blends having different acid labile groups and different terminal structures are possible.

  In addition, the content of the polymer represented by the general formula (1), (2) or (3) in which the polymer terminal according to the present invention in the polymer blend is substituted with an acid labile group is 30 to 100% by mass. In particular, it is 40 to 100% by mass.

  Hydroxystyrene in which the polymer terminal used in the present invention is substituted with an acid labile group can be hydrogenated on the benzene ring for the purpose of improving transparency. The ratio of hydrogenation is 1% to 90%, preferably 5% to 80% of the repeating unit.

The resist material of the present invention is particularly useful as a positive type, and is a polymer compound represented by the general formula (1), (2) or (3) in which the above-described polymer terminal is substituted with an acid labile group In this case, the resist material of the present invention is
(A) an organic solvent,
(B) the polymer compound as a base resin,
(C) an acid generator,
If necessary, (D) a dissolution inhibitor,
Preferably, it is used as a chemically amplified positive resist material containing (E) a basic compound.

  The organic solvent used in the positive resist material of the present invention, particularly the chemically amplified positive resist material, may be any organic solvent that can dissolve the base resin, acid generator, other additives, and the like. Examples of such organic solvents include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy- Alcohols such as 2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and other ethers, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxy Ethyl propionate, acetate tert- butyl, tert- butyl propionate, and propylene glycol monobutyl tert- butyl ether acetate, although lactones such as γ- butyl lactone, not being limited thereto.

These organic solvents can be used individually by 1 type or in mixture of 2 or more types. In the present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate, and mixed solvents thereof, which are most excellent in solubility of the acid generator in the resist component, are preferably used. .
The amount of the organic solvent used is preferably 200 to 1,000 parts, particularly 400 to 800 parts, with respect to 100 parts (parts by mass) of the base resin.

As an acid generator blended in the positive resist material of the present invention,
(I) Onium salt of the following general formula (P1a-1), (P1a-2) or (P1b),
(Ii) a diazomethane derivative of the following general formula (P2):
(Iii) a glyoxime derivative of the following general formula (P3),
(Iv) a bissulfone derivative of the following general formula (P4),
(V) a sulfonic acid ester of an N-hydroxyimide compound of the following general formula (P5),
(Vi) β-ketosulfonic acid derivative,
(Vii) a disulfone derivative,
(Viii) a nitrobenzyl sulfonate derivative,
(Ix) sulfonic acid ester derivatives and the like.

（式中、Ｒ^101a、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基、アルケニル基、オキソアルキル基又はオキソアルケニル基、炭素数６〜２０のアリール基、又は炭素数７〜１２のアラルキル基又はアリールオキソアルキル基を示し、これらの基の水素原子の一部又は全部がアルコキシ基等によって置換されていてもよい。また、Ｒ^101bとＲ^101cとは環を形成してもよく、環を形成する場合には、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜６のアルキレン基を示す。Ｋ^-は非求核性対向イオンを表す。）

Wherein R ^101a , R ^101b and R ^101c are each a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, and an aryl having 6 to 20 carbon atoms. Group, an aralkyl group having 7 to 12 carbon atoms or an aryloxoalkyl group, part or all of hydrogen atoms of these groups may be substituted by an alkoxy group, etc. R ^101b and R ^{101c May} form a ring, and in the case of forming a ring, R ^101b and R ^101c each represent an alkylene group having 1 to 6 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.)

R ^101a , R ^101b and R ^101c may be the same as or different from each other. Specifically, as an alkyl group, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl Group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group, etc. Is mentioned. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like. Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ion and bromide ion, fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethane sulfonate, and nonafluorobutane sulfonate, tosylate, and benzene sulfonate. And aryl sulfonates such as 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

（式中、Ｒ^102a、Ｒ^102bはそれぞれ炭素数１〜８の直鎖状、分岐状又は環状のアルキル基を示す。Ｒ¹⁰³は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基を示す。Ｒ^104a、Ｒ^104bはそれぞれ炭素数３〜７の２−オキソアルキル基を示す。Ｋ^-は非求核性対向イオンを表す。）

(In the formula, R ^102a and R ^102b each represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ¹⁰³ is a linear, branched or cyclic alkylene having 1 to 10 carbon atoms. R ^104a and R ^104b each represent a 2-oxoalkyl group having 3 to 7 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.)

Specific examples of R ^102a and R ^102b include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. , Cyclopentyl group, cyclohexyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group and the like. R ¹⁰³ is methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene. Group, 1,3-cyclopentylene group, 1,4-cyclooctylene group, 1,4-cyclohexanedimethylene group and the like. ^{Examples of} R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. K ^- is can be exemplified the same ones as described in the formulas (P1a-1) and (P1a-2).

（式中、Ｒ¹⁰⁵、Ｒ¹⁰⁶は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。）

(In the formula, R ¹⁰⁵ and R ¹⁰⁶ are linear, branched or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, aryl groups or halogenated aryl groups having 6 to 20 carbon atoms, or carbon atoms. 7 to 12 aralkyl groups are shown.)

^Examples of the alkyl group of R ¹⁰⁵ and R ¹⁰⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, amyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

（式中、Ｒ¹⁰⁷、Ｒ¹⁰⁸、Ｒ¹⁰⁹は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。Ｒ¹⁰⁸、Ｒ¹⁰⁹は互いに結合して環状構造を形成してもよく、環状構造を形成する場合、Ｒ¹⁰⁸、Ｒ¹⁰⁹はそれぞれ炭素数１〜６の直鎖状、分岐状のアルキレン基を示す。）

(Wherein R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are each a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 20 carbon atoms, Or an aralkyl group having 7 to 12 carbon atoms, R ¹⁰⁸ and R ¹⁰⁹ may be bonded to each other to form a cyclic structure, and in the case of forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ each have 1 to 6 carbon atoms. A linear or branched alkylene group.)

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group of R ¹⁰⁷ , R ¹⁰⁸ , and R ¹⁰⁹ include the same groups as those described for R ¹⁰⁵ and R ¹⁰⁶ . ^Examples of the alkylene group for R ¹⁰⁸ and R ¹⁰⁹ include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

（式中、Ｒ^101a、Ｒ^101bは上記と同様である。）

(In the formula, R ^101a and R ^101b are the same as above.)

（式中、Ｒ¹¹⁰は炭素数６〜１０のアリーレン基、炭素数１〜６のアルキレン基又は炭素数２〜６のアルケニレン基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４の直鎖状又は分岐状のアルキル基又はアルコキシ基、ニトロ基、アセチル基、又はフェニル基で置換されていてもよい。Ｒ¹¹¹は炭素数１〜８の直鎖状、分岐状又は置換のアルキル基、アルケニル基又はアルコキシアルキル基、フェニル基、又はナフチル基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４のアルキル基又はアルコキシ基；炭素数１〜４のアルキル基、アルコキシ基、ニトロ基又はアセチル基で置換されていてもよいフェニル基；炭素数３〜５のヘテロ芳香族基；又は塩素原子、フッ素原子で置換されていてもよい。）

(In the formula, R ¹¹⁰ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, and some or all of the hydrogen atoms of these groups are further carbon atoms. It may be substituted with a linear or branched alkyl group or alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetyl group, or a phenyl group, and R ¹¹¹ is a linear or branched chain having 1 to 8 carbon atoms. Or a substituted alkyl group, an alkenyl group or an alkoxyalkyl group, a phenyl group, or a naphthyl group, and part or all of the hydrogen atoms of these groups are further an alkyl group or alkoxy group having 1 to 4 carbon atoms; A phenyl group which may be substituted with an alkyl group of 4 to 4, an alkoxy group, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or a phenyl group which may be substituted with a chlorine atom or a fluorine atom.

Here, as the arylene group of R ¹¹⁰ , 1,2-phenylene group, 1,8-naphthylene group, etc., and as the alkylene group, methylene group, ethylene group, trimethylene group, tetramethylene group, phenylethylene group, norbornane Examples of the alkenylene group such as -2,3-diyl group include 1,2-vinylene group, 1-phenyl-1,2-vinylene group, 5-norbornene-2,3-diyl group and the like. The alkyl group for R ¹¹¹ is the same as R ^{101a to} R ^101c, and the alkenyl group is a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1- Pentenyl group, 3-pentenyl group, 4-pentenyl group, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl Groups such as alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, methoxyethyl, ethoxyethyl, Propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, methoxypro Group, ethoxypropyl group, propoxypropyl group, butoxy propyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, a methoxy pentyl group, an ethoxy pentyl group, a methoxy hexyl group, a methoxy heptyl group.

    In addition, examples of the optionally substituted alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. As the alkoxy group of ˜4, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like are an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a nitro group. As the phenyl group which may be substituted with an acetyl group, a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group, a p-nitrophenyl group, etc. are heterocycles having 3 to 5 carbon atoms. Examples of the aromatic group include a pyridyl group and a furyl group.

  Examples of onium salts include diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyl. Iodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert) trifluoromethanesulfonate -Butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenyl nonafluorobutanesulfonate Sulfonium, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) ) Sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, di-p-toluenesulfonic acid Tylphenylsulfonium, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, ethylenebis [ And onium salts such as methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate] and 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate.

  Diazomethane derivatives include bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane Bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane Bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfur) Nyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane And the like.

  Examples of glyoxime derivatives include bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl)- α-dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, bis-O- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, Bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -α-dicyclohexylglyoxime Bis-O- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-O- ( -Butanesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis -O- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-O- (perfluorooctanesulfonyl)- α-dimethylglyoxime, bis-O- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α- Dimethylglyoxime, bis-O- (p-tert-butylbenzenesulfonyl) α- dimethylglyoxime, bis -O- (xylene sulfonyl)-.alpha.-dimethylglyoxime, and bis -O- (camphorsulfonyl)-.alpha.-glyoxime derivatives such as dimethylglyoxime.

  Examples of bissulfone derivatives include bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane. Bissulfone derivatives can be mentioned.

  Examples of β-ketosulfone derivatives include β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.

  Examples of the disulfone derivative include disulfone derivatives such as diphenyl disulfone derivatives and dicyclohexyl disulfone derivatives.

  Examples of the nitrobenzyl sulfonate derivative include nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

  Examples of sulfonic acid ester derivatives include 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy). Mention may be made of sulfonic acid ester derivatives such as benzene.

  Further, N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide ethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid Ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxysuccinimide p-methoxybenzenesulfonic acid ester, N-hydroxy Succinimide 2-chloroethane sulfonate, N-hydroxysuccinimide benzene sulfonate N-hydroxysuccinimide-2,4,6-trimethylbenzenesulfonic acid ester, N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N-hydroxy-2-phenylsuccinimide methanesulfonic acid Ester, N-hydroxymaleimide methanesulfonate, N-hydroxymaleimide ethanesulfonate, N-hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate, N-hydroxyglutarimide benzenesulfone Acid ester, N-hydroxyphthalimidomethanesulfonic acid ester, N-hydroxyphthalimidobenzenesulfonic acid ester, N-hydroxyl Phthalimide trifluoromethanesulfonate, N-hydroxyphthalimide p-toluenesulfonate, N-hydroxynaphthalimide methanesulfonate, N-hydroxynaphthalimidebenzenesulfonate, N-hydroxy-5-norbornene-2,3- Dicarboximide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide p-toluenesulfonate Examples thereof include sulfonic acid ester derivatives of N-hydroxyimide compounds.

  In particular, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p -Toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) ) Sulfonium, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonyl trifluoromethanesulfonate Onium salts such as 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) Diazomethane derivatives such as diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis-O Glyoxime derivatives such as-(p-toluenesulfonyl) -α-dimethylglyoxime and bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bisnaphthy Bissulfone derivatives such as sulfonylmethane, N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N- Hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, etc. Derivatives are preferably used.

  In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. Since onium salts are excellent in rectangularity improving effect and diazomethane derivatives and glyoxime derivatives are excellent in standing wave reducing effect, it is possible to finely adjust the profile by combining both.

  The addition amount of the acid generator is preferably 0.1 to 50 parts, more preferably 0.5 to 40 parts with respect to 100 parts of the base resin. If the amount is less than 0.1 part, the amount of acid generated during exposure is small and the sensitivity and resolution may be inferior. If the amount exceeds 50 parts, the transmittance of the resist may be lowered and the resolution may be inferior.

  Next, as a dissolution inhibitor to be blended in the positive resist material of the present invention, particularly a chemically amplified positive resist material, the weight average molecular weight is 100 to 1,000, preferably 150 to 800, and in the molecule. The compound having two or more phenolic hydroxyl groups, the hydrogen atom of the phenolic hydroxyl group substituted with an acid labile group in an average of 0 to 100 mol% as a whole, or the carboxy group of a compound having a carboxy group in the molecule A compound in which the hydrogen atoms are substituted with an acid labile group as a whole at an average ratio of 50 to 100 mol% is preferred.

  The substitution rate of the hydrogen atom of the phenolic hydroxyl group by an acid labile group is on average 0 mol% or more, preferably 30 mol% or more of the entire phenolic hydroxyl group, and the upper limit is 100 mol%, more preferably 80 mol. %. The substitution rate of the hydrogen atom of the carboxy group with an acid labile group is 50 mol% or more, preferably 70 mol% or more of the entire carboxy group on average, and the upper limit is 100 mol%.

  In this case, as the compound having two or more phenolic hydroxyl groups or the compound having a carboxy group, those represented by the following formulas (D1) to (D14) are preferable.

(In the above formulae, R ²⁰¹ and R ²⁰² each represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms. R ²⁰³ represents a hydrogen atom or 1 to 8 carbon atoms. Represents a linear or branched alkyl group or alkenyl group, or — (R ²⁰⁷ ) _h COOH, wherein R ²⁰⁴ is — (CH ₂ ) _i — (i = 2 to 10), arylene having 6 to 10 carbon atoms. A group, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ²⁰⁵ represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R ²⁰⁶ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a phenyl group or naphthyl group each substituted with a hydroxyl group, and R ²⁰⁷ represents a straight chain having 1 to 10 carbon atoms. Chain or branched alkyl R ²⁰⁸ represents a hydrogen atom or a hydroxyl group, j is an integer of 0 to 5. u and h are 0 or 1. s, t, s ′, t ′, s ″, t ″ Is a number satisfying s + t = 8, s ′ + t ′ = 5, s ″ + t ″ = 4, respectively, and having at least one hydroxyl group in each phenyl skeleton. Α is a formula (D8 ), (D9) is a number that makes the molecular weight of the compound of 100 to 1,000.)

  The compounding quantity of a dissolution inhibitor is 0-50 parts with respect to 100 parts of base resins, Preferably it is 5-50 parts, More preferably, it is 10-30 parts, It can use individually or in mixture of 2 or more types. If the blending amount is small, the resolution may not be improved. If the blending amount is too large, the pattern film is reduced and the resolution tends to decrease.

Furthermore, a basic compound can be mix | blended with the resist material of this invention.
As the basic compound, a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By adding a basic compound, the acid diffusion rate in the resist film is suppressed and resolution is improved, sensitivity change after exposure is suppressed, and substrate and environment dependency is reduced, and exposure margin and pattern profile are reduced. Etc. can be improved.
Examples of such basic compounds include primary, secondary, and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, and sulfonyl groups. A nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like.

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

  Examples of hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine.

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

  Furthermore, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine , Phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like, and examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and the like. Nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, and 3-indolemethanol. Drate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) Ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propane Diol, 8-hydroxyuroli , 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. Illustrated. Examples of amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Examples of imide derivatives include phthalimide, succinimide, maleimide and the like.

Furthermore, 1 type, or 2 or more types chosen from the basic compound shown by the following general formula (B) -1 can also be mix | blended.
N (X) _n (Y) _3-n (B) -1
(In the formula, n is 1, 2 or 3. The side chain X may be the same or different and can be represented by the following general formulas (X) -1 to (X) -3. The side chain Y is It represents the same or different hydrogen atom or linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain an ether group or a hydroxyl group, and Xs may combine to form a ring. May be.)

Here, R ³⁰⁰ , R ³⁰² and R ³⁰⁵ are linear or branched alkylene groups having 1 to 4 carbon atoms, and R ³⁰¹ and R ³⁰⁴ are hydrogen atoms, linear and branched chains having 1 to 20 carbon atoms. Or a cyclic alkyl group, which may contain one or a plurality of hydroxy groups, ether groups, ester groups and lactone rings. R ³⁰³ is a single bond, a linear or branched alkylene group having 1 to 4 carbon atoms, R ³⁰⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a hydroxy group, One or a plurality of ether groups, ester groups and lactone rings may be contained.

Specific examples of the compound represented by the general formula (B) -1 are given below.
Tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl } Amine, Tris {2- (1-ethoxyethoxy) ethyl} amine, Tris {2- (1-ethoxypropoxy) ethyl} amine, Tris [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] Eicosane, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris (2-acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, tris (2-pivaloyloxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-tert-butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] Amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amine Tris [2- (tert-butoxycarbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N , N-bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxy) Ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryl Oxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl ) Oxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (4 -Hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (2-formyloxy) Ethoxycarbonyl) ethylamine, N, N-bis (2- Toxiethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1-propyl) ) Bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxy Carbonyl) ethyl] amine, N-butylbis [2- (methoxycarbonyl) ethyl] amine, N-butyl Rubis [2- (2-methoxyethoxycarbonyl) ethyl] amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine, N-methylbis (2-pivaloyloxyethyl) amine N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N -Butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, and β- (diethylamino) -δ-valerolactone can be exemplified, but are not limited thereto.

  Furthermore, 1 type, or 2 or more types of the basic compound which has a cyclic structure shown by the following general formula (B) -2 can also be added.

（式中、Ｘは前述の通り、Ｒ³⁰⁷は炭素数２〜２０の直鎖状又は分岐状のアルキレン基であり、カルボニル基、エーテル基、エステル基又はスルフィドを１個あるいは複数個含んでいてもよい。）

(In the formula, as described above, R ³⁰⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms, and includes one or more carbonyl groups, ether groups, ester groups or sulfides. May be.)

  Specific examples of the formula (B) -2 include 1- [2- (methoxymethoxy) ethyl] pyrrolidine, 1- [2- (methoxymethoxy) ethyl] piperidine, 4- [2- (methoxymethoxy) ethyl. ] Morpholine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxyethoxy) ) Methoxy] ethyl] morpholine, 2- (1-pyrrolidinyl) ethyl acetate, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate, 2-morpholinoethyl acetoxyacetate , 2- (1-pyrrolidinyl) ethyl methoxyacetate, 4- [2- (methoxycarbonyloxy) ethyl Morpholine, 1- [2- (t-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, 3-piperidi Methyl nopropionate, methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, methyl 2-methyl-3- (1-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, 3-piperidinopropion Methoxycarbonylmethyl acid, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate, 3-morpholino Propionic acid tetrahydrofur Ryl, glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2- (2-methoxyethoxy) ethyl 3- (1-pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-pi Cyclohexyl peridinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate, Mention may be made of methyl thiomorpholinoacetate, ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate.

  Furthermore, a basic compound containing a cyano group represented by the following general formulas (B) -3 to (B) -6 can be added.

（式中、Ｘ、Ｒ³⁰⁷、ｎは前述の通り、Ｒ³⁰⁸、Ｒ³⁰⁹は同一又は異種の炭素数１〜４の直鎖状又は分岐状のアルキレン基である。）

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

  Specific examples of the base containing a cyano group include 3- (diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, and N, N-bis (2-acetoxyethyl). -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl) -3-aminopropiononitrile, N, N -Bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, methyl N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionate, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionic acid methyl, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopro Methyl onate, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropiononitrile, N- ( 2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-aminopropiononitrile, N- (2 -Cyanoethyl) -N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- ( 2-cyanoethyl) -N- (3-hydroxy-1-propyl) -3-aminopropiononitrile, N- (3-acetoxy-1-propyl) -N- (2 Cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-formyloxy-1-propyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N-tetrahydrofur Furyl-3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis ( 2-acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2- (methoxymethoxy) ethyl Aminoacetonitrile, N-cyanomethyl-N- (2-methoxyethyl) ) Methyl 3-aminopropionate, methyl N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionate, methyl N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate, N -Cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile, N-cyanomethyl -N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile, N- (3-acetoxy-1-propyl) -N (Cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, cyanomethyl N, N-bis (2-hydroxyethyl) -3-aminopropionate, N, Cyanomethyl N-bis (2-acetoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-formyloxyethyl) -3-aminopropionate, N, N-bis (2-methoxyethyl) Cyanomethyl 3-aminopropionate, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionate cyanomethyl, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2-hydroxyethyl) ) -3-Aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-formyloxyethyl) -3 Aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2- (methoxymethoxy) ethyl] -3- Aminopropionic acid (2-cyanoethyl), 1-pyrrolidinepropionate cyanomethyl, 1-piperidinepropionate cyano Examples include methyl, cyanomethyl 4-morpholine propionate, 1-pyrrolidinepropionic acid (2-cyanoethyl), 1-piperidinepropionic acid (2-cyanoethyl), 4-morpholine propionic acid (2-cyanoethyl).

  In addition, the compounding quantity of the base compound of this invention is 0.001-2 parts with respect to 100 parts of base resins, Especially 0.01-1 part is suitable. If the blending amount is less than 0.001 part, there is no blending effect, and if it exceeds 2 parts, the sensitivity may be too low.

  As the compound having a group represented by ≡C—COOH in the molecule that can be added to the positive resist material of the present invention, for example, one or more compounds selected from the following groups I and II are used. However, it is not limited to these. By blending this component, the PED stability of the resist is improved, and the edge roughness on the nitride film substrate is improved.

[Group I]
A part or all of the hydrogen atoms of the phenolic hydroxyl groups of the compounds represented by the following general formulas (A1) to (A10) are converted to —R ⁴⁰¹ —COOH (where R ⁴⁰¹ is a linear or branched alkylene having 1 to 10 carbon atoms). The molar ratio of the phenolic hydroxyl group (C) in the molecule to the group (D) represented by ≡C—COOH is C / (C + D) = 0.1 to 1.0. Compound.

(In the formula, R ⁴⁰⁸ represents a hydrogen atom or a methyl group. R ⁴⁰² and R ⁴⁰³ each represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms. R ⁴⁰⁴ represents It represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or a — (R ⁴⁰⁹ ) _h —COOR ′ group (R ′ represents a hydrogen atom or —R ⁴⁰⁹ —COOH). ⁴⁰⁵ represents — (CH ₂ ) _i — (i = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ⁴⁰⁶ represents an alkylene having 1 to 10 carbon atoms. Group, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, R ⁴⁰⁷ is a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, Phenyls each substituted with a hydroxyl group Or .R ⁴⁰⁹ showing a naphthyl group is a straight or branched alkyl or alkenyl group or -R showing a ⁴¹¹ -COOH groups .R ⁴¹⁰ is hydrogen atom or a straight-1 to 8 carbon atoms A chain or branched alkyl group, an alkenyl group, or —R ⁴¹¹ —COOH group, R ⁴¹¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms, j is 0 to 3, s1 s4 and t1 to t4 satisfy s1 + t1 = 8, s2 + t2 = 5, s3 + t3 = 4, and s4 + t4 = 6, respectively, and each phenyl skeleton has at least one hydroxyl group, and κ is a formula (A6). Is a number with a weight average molecular weight of 1,000 to 5,000. Λ is a number with a weight average molecular weight of 1,000 to 10,000 for the compound of formula (A7).)

[Group II]
Compounds represented by the following general formulas (A11) to (A15).

（Ｒ⁴⁰²、Ｒ⁴⁰³、Ｒ⁴¹¹は上記と同様の意味を示す。Ｒ⁴¹²は水素原子又は水酸基を示す。ｓ５、ｔ５は、ｓ５≧０、ｔ５≧０で、ｓ５＋ｔ５＝５を満足する数である。ｈ’は０又は１である。）

(R ⁴⁰² , R ⁴⁰³ , and R ⁴¹¹ have the same meanings as described above. R ⁴¹² represents a hydrogen atom or a hydroxyl group. S5 and t5 are numbers satisfying s5 + t5 = 5 when s5 ≧ 0 and t5 ≧ 0. H 'is 0 or 1.)

  Specific examples of this component include, but are not limited to, compounds represented by the following general formulas (AI-1) to (AI-14) and (AII-1) to (AII-10). It is not a thing.

（式中、Ｒ’’は水素原子又はＣＨ₂ＣＯＯＨ基を示し、各化合物においてＲ’’の１０〜１００モル％はＣＨ₂ＣＯＯＨ基である。α、κは上記と同様の意味を示す。）

(In the formula, R ″ represents a hydrogen atom or a CH ₂ COOH group, and in each compound, 10 to 100 mol% of R ″ is a CH ₂ COOH group. Α and κ have the same meanings as described above. )

In addition, the compound which has group shown by (≡C-COOH) in the said molecule | numerator can be used individually by 1 type or in combination of 2 or more types.
The amount of the compound having a group represented by ≡C—COOH in the molecule is 0 to 5 parts, preferably 0.1 to 5 parts, more preferably 0.1 to 3 parts, relative to 100 parts of the base resin. More preferably, it is 0.1 to 2 parts. If it exceeds 5 parts, the resolution of the resist material may be lowered.

  Examples of the surfactant include, but are not limited to, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, and polyoxyethylene Polyoxyethylene alkyl allyl ethers such as octylphenol ether and polyoxyethylene nonylphenol, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monovalmitate, sorbitan monostearate, poly Oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monovalmitate, polyoxyethylene sorbitan monostearate Nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (manufactured by Tochemmptodacts), MegaFuck F171 , F172, F173 (Dainippon Ink Chemical Co., Ltd.), Florard FC430, FC431FC-4430 (Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103, Fluorosurfactants such as SC104, SC105, SC106, Surfinol E1004, KH-10, KH-20, KH-30, KH-40 (Asahi Glass Co., Ltd.), organosiloxane polymer KP-341 X-70-092, (manufactured by Shin-Etsu Chemical (Co.)) X-70-093, acrylic acid or methacrylic acid Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), among which FC430, FC-4430, Surflon S-381, Surfynol E1004, KH-20, and KH-30 are preferred. These can be used alone or in combination of two or more.

  The addition amount of the surfactant in the positive resist material of the present invention, particularly the chemically amplified positive resist material, is 2 parts or less, preferably 1 part or less with respect to 100 parts of the base resin in the resist material.

  Various chemically amplified positive resist materials containing (A) an organic solvent of the present invention, (B) a polymer compound represented by the above general formula (1) and (2), and (C) an acid generator. In the case of use in the manufacture of integrated circuits, a known lithography technique can be used, although not particularly limited.

Spin coating, roll coating, flow coating, dip on a substrate for manufacturing an integrated circuit (Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflection film, Cr, CrO, CrON, MoSi, etc.) It is applied so as to have a coating film thickness of 0.1 to 2.0 μm by an appropriate coating method such as coating, spray coating, doctor coating, and the like, and is performed on a hot plate at 60 to 150 ° C. for 1 to 10 minutes, preferably 80 to Pre-bake at 120 ° C. for 1-5 minutes. Next, a target pattern is exposed through a predetermined mask at a light source selected from ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays, synchrotron radiation, and the like, preferably at an exposure wavelength of 300 nm or less. The exposure is preferably performed so that the exposure amount is about 1 to 200 mJ / cm ² , preferably about 10 to 100 mJ / cm ² . Post exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 120 ° C. for 1 to 3 minutes.

  Furthermore, 0.1-5%, preferably 2-3% tetramethylammonium hydroxide (TMAH) or other alkaline aqueous developer is used for 0.1-3 minutes, preferably 0.5-2 minutes. A target pattern is formed on the substrate by developing by a conventional method such as a (dip) method, a paddle method, or a spray method. The resist material of the present invention is a fine patterning by far ultraviolet rays of 254 to 193 nm, vacuum ultraviolet rays of 157 nm, electron beams, soft X-rays, X-rays, excimer lasers, γ rays and synchrotron radiation, especially among high energy rays. Ideal for. In addition, when the above range deviates from the upper limit and the lower limit, the target pattern may not be obtained.

  EXAMPLES Hereinafter, although a synthesis example, a comparative synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the measurement methods (measurement conditions) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) are as follows. Gel permeation chromatography (GPC) was used to determine polystyrene-equivalent Mw, Mn, and dispersity (Mw / Mn).

[Synthesis Example 1] Monodispersion Synthesis of both ends pt-butoxystyrene-partial pt-butoxypolyhydroxystyrene 1 L flask was charged with 1,000 mL of tetrahydrofuran as a solvent and 0.01 mol of sec-butyllithium as an initiator. It is. To this mixed solution, 17 g of pt-butoxystyrene was added at −78 ° C., polymerized while stirring for 30 minutes, and the completion of the reaction was confirmed by gas chromatography (GC). Next, a mixture of 17 g of pt-butoxystyrene and 134 g of p-trimethylsiloxystyrene was added and stirred for 30 minutes, and the completion of the reaction was confirmed by GC. Next, 17 g of pt-butoxystyrene was added, and 30 minutes Stir. The reaction solution turned red. Subsequently, 0.1 mol of benzyl bromide was added to carry out a polymerization termination reaction.
Next, in order to purify the polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated, then separated and dried. As a result, 173 g of a white polymer was obtained.
Further, 173 g of the above polymer was dissolved in 1,000 ml of acetone, a small amount of concentrated hydrochloric acid was added at 20 ° C. and stirred for 7 hours, then poured into water, the polymer was precipitated, washed and dried, and 133 g of polymer was obtained. It was. Further, analysis by gel permeation chromatography (GPC), the absence of a peak derived from a trimethylsilyl group by ¹ H-NMR, weight-average molecular weight in terms of polystyrene Mw 12,000, pt-butoxy having Mw / Mn 1.03 It was confirmed that the copolymer was styrene: p-hydroxystyrene: 31: 69. This was designated as Polymer 1.

[Synthesis Example 2] Monodispersion Synthesis of one-terminal pt-butoxystyrene-partial pt-butoxypolyhydroxystyrene A 1 L flask was charged with 1,000 mL of tetrahydrofuran as a solvent and 0.01 mol of sec-butyllithium as an initiator. It is. To this mixed solution, a mixture of 17 g of pt-butoxystyrene and 134 g of p-trimethylsiloxystyrene was added at −78 ° C. and stirred for 30 minutes. The completion of the reaction was confirmed by GC, and then 34 g of pt-butoxystyrene was obtained. Was added and stirred for 30 minutes. The reaction solution turned red. Subsequently, 0.1 mol of t-butyl 3-bromopropionate was added to carry out a polymerization termination reaction.
Next, in order to purify the polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated, then separated and dried to obtain 175 g of a white polymer.
Further, 175 g of the above polymer was dissolved in 1,000 ml of acetone, a small amount of concentrated hydrochloric acid was added at 20 ° C., stirred for 7 hours, poured into water, precipitated into a polymer, washed and dried to obtain 136 g of polymer. It was. Moreover, the peak derived from a trimethylsilyl group is not observed by the analysis by GPC and ¹ H-NMR, and the weight of pt-butoxystyrene: p-hydroxystyrene: 32: 68 of Mw12,000 and Mw / Mn1.03. It was confirmed to be a coalescence. This was designated as Polymer 2.

[Synthesis Example 3] Monodispersion Synthesis of one-end pt-amyloxystyrene-partial pt-amyloxypolyhydroxystyrene 1,000 mL of tetrahydrofuran as a solvent in a 1 L flask and 0.01 mol of sec-butyllithium as an initiator Was charged. To this mixed solution, a mixture of 17 g of pt-amyloxystyrene and 134 g of p-trimethylsiloxystyrene was added at −78 ° C. and stirred for 30 minutes. The completion of the reaction was confirmed by GC, and then pt-amyloxy was obtained. 34 g of styrene was added and stirred for 30 minutes. The reaction solution turned red. Subsequently, 0.1 mol of t-butyl 3-bromopropionate was added to carry out a polymerization termination reaction.
Next, in order to purify the polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated, then separated and dried to obtain 175 g of a white polymer.
Further, 175 g of the above polymer was dissolved in 1,000 ml of acetone, a small amount of concentrated hydrochloric acid was added at 20 ° C., stirred for 7 hours, poured into water, precipitated into a polymer, washed and dried to obtain 136 g of polymer. It was. In addition, the peak derived from the trimethylsilyl group is not observed in the analysis by GPC and ¹ H-NMR, and both pt-amyloxystyrene: p-hydroxystyrene: 27: 73 of Mw 12,000 and Mw / Mn 1.03 are observed. It was confirmed to be a polymer. This was designated as Polymer 3.

[Synthesis Example 4] Monodispersion Synthesis of one-end pt-amyloxystyrene-partial pt-butoxycarbonyloxypolyhydroxystyrene 1,000 mL of tetrahydrofuran as a solvent in a 1 L flask and sec-butyllithium as an initiator .01 mol was charged. To this mixed solution, 182 g of p-ethoxyethoxystyrene was added at −78 ° C. and stirred for 30 minutes. After completion of the reaction was confirmed by GC, 34 g of pt-amyloxystyrene was added and stirred for 30 minutes. The reaction solution turned red. Subsequently, 0.1 mol of t-butyl 3-bromopropionate was added to carry out a polymerization termination reaction.
Next, in order to purify the polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated, then separated and dried to obtain 175 g of a white polymer.
Further, 175 g of the above polymer was dissolved in 1,000 ml of acetone, a small amount of concentrated hydrochloric acid was added at 20 ° C. and stirred for 7 hours, then poured into water, the polymer was precipitated, washed and dried, and 142 g of polymer was obtained. It was. The obtained polymer was dissolved in 400 ml of pyridine, and 22.6 g of di-tert-butyl dicarbonate was added with stirring at 45 ° C. After making it react for 1 hour, when the reaction liquid was dripped at 3 L of water, white solid was obtained.
This was filtered, dissolved in 100 ml of acetone, dropped into 5 L of water, filtered, and vacuum dried to obtain a polymer.
In addition, no peak derived from a trimethylsilyl group is observed by GPC analysis or ¹ H-NMR, pt-amyloxystyrene of Mw 10,500, Mw / Mn 1.05: pt-butoxycarbonyloxystyrene: p -It was confirmed to be a copolymer of hydroxystyrene: 19: 8: 73. This was designated as Polymer 4.

[Comparative Synthesis Example 1] Monodispersion Synthesis of Partially pt-Butoxypolyhydroxystyrene A 1 L flask was charged with 1,000 mL of tetrahydrofuran as a solvent and 0.01 mol of sec-butyllithium as an initiator. A mixture of 52 g of pt-butoxystyrene and 134 g of p-trimethylsiloxystyrene was added to this mixed solution at −78 ° C. and stirred for 30 minutes, and the completion of the reaction was confirmed by GC. The reaction solution turned red. Subsequently, 0.1 mol of benzyl bromide was added to carry out a polymerization termination reaction.
Next, in order to purify the polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated, then separated and dried. As a result, 173 g of a white polymer was obtained.
Further, 173 g of the above polymer was dissolved in 1,000 ml of acetone, a small amount of concentrated hydrochloric acid was added at 20 ° C. and stirred for 7 hours, then poured into water, the polymer was precipitated, washed and dried, and 131 g of polymer was obtained. It was. Moreover, the peak derived from a trimethylsilyl group is not observed by the analysis by GPC and ¹ H-NMR, Mw 12,000, Mw / Mn 1.03 pt-butoxystyrene: p-hydroxystyrene: 30: 70 It was confirmed to be a coalescence. This was designated as Comparative Polymer 1.

[Comparative Synthesis Example 2] Synthesis of polydisperse partial pt-butoxypolyhydroxystyrene 52 g of pt-butoxystyrene, 134 g of p-trimethylsiloxystyrene, and 200 g of toluene as a solvent were added to a 1 L flask. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 7.5 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. The reaction solution was concentrated to 1/2 and precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water. The resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 132 g of a white polymer. It was.
Further, 132 g of the above polymer was dissolved in 1,000 ml of acetone, a small amount of concentrated hydrochloric acid was added at 20 ° C., stirred for 7 hours, poured into water, the polymer was precipitated, washed and dried, and 106 g of polymer was obtained. It was. Moreover, the peak derived from a trimethylsilyl group is not observed by the analysis by GPC and ¹ H-NMR, Mw14,600, Mw / Mn1.773 pt-butoxystyrene: p-hydroxystyrene: 28: 72 It was confirmed to be a coalescence. This was designated as Comparative Polymer 2.

Evaluation of exposure patterning Using the polymers obtained in the above synthesis examples and comparative synthesis examples, resist materials were prepared with the compositions shown in Table 1, and exposure patterning was evaluated by the following methods. The results are shown in Table 1.
A solution dissolved with the composition shown in Table 1 was filtered through a 0.2 μm high density polyethylene filter to prepare a resist solution. A resist solution is spin-coated on a substrate in which DUV-30 (manufactured by Nissan Chemical Industries, Ltd.) having a film thickness of 55 nm is formed on a silicon wafer, and the resist thickness is baked at 110 ° C. for 90 seconds using a hot plate. Was set to 300 nm.
This was exposed using an excimer laser stepper (Nikon Corporation, NSR-S203A, NA-0.68, σ0.75, 2/3 annular illumination), and immediately after exposure, baked at 120 ° C. for 90 seconds, Development was carried out with an aqueous solution of 2.38% tetramethylammonium hydroxide for 60 seconds to obtain a positive pattern.

The obtained resist pattern was evaluated as follows.
Evaluation methods:
In a mask pattern having a line-to-space width ratio of 1: 1.5, the exposure amount at which a 0.15 μm line is resolved according to dimensions is defined as the resist sensitivity. The line width was defined as the resolution of the evaluation resist.
PGMEA: Propylene glycol monomethyl ether acetate From the results shown below, the resist material to which the polymer having an acid labile group is added at the terminal of the present invention has high sensitivity and resolution, and is a promising material for achieving further fine processing. It turned out to be.

Claims (7)

A polymer having, as a repeating unit, hydroxystyrene, hydroxyvinylnaphthalene or hydroxyvinylanthracene in which a hydrogen atom of a hydroxy group is partially substituted with an acid labile group, wherein monomers are sequentially added using living anionic polymerization In the charging method, at the start and / or end of polymerization, hydroxystyrene, hydroxyvinylnaphthalene or hydroxyvinylanthracene substituted with an acid labile group is added, polymerized and charged, at one or both ends of the polymer, In the repeating unit at one or both ends, obtained by continuously arranging repeating units substituted with the acid labile group, the hydrogen atom of the hydroxy group is selectively substituted with an acid labile group. Add the block copolymer represented by the following general formula (1), (2) or (3) Resist material characterized by comprising Te.

(In the formula, R ¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ² and R ⁵ are hydrogen atoms. R ³ and R ⁶ have 6 to 20 carbon atoms. R ⁴ is an aromatic ring, R ⁴ is a hydrogen atom or a mixture of a hydrogen atom and an acid labile group, and the hydrogen atom of 50 mol% or less of the hydroxy group in the repeating units a and d is substituted with an acid labile group R ⁷ is an acid labile group, R ⁸ is an aliphatic group which may contain a hydroxy group, a carboxy group, a hydroxy group having 1 to 20 carbon atoms, an ester group, an ether group, a lactone ring, a cyano group, or An aromatic monovalent hydrocarbon group, an alkoxy group, or a group represented by the following general formula (4).

Here, in the general formula (4), R ⁹ is a single bond, a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, a bridged cyclic alkylene group, or an arylene having 6 to 10 carbon atoms. R ¹⁰ is an acid labile group. Z is a single bond or a p + 1 valent aliphatic or aromatic hydrocarbon group which may contain a carbonyl group, an ester group or an ether group. p is 1 or 2. a and b are positive numbers, 0.5 ≦ a <1.0, 0 <b ≦ 0.5, 0.5 ≦ d <1.0, 0 <c ≦ 0.25, 0 <e ≦ The range is 0.25, and m and n are integers of 1 to 3. ) The resist material according to claim 1, wherein the aromatic ring represented by R ³ or R ⁶ in the general formula (1), (2) or (3) is a benzene ring, a naphthalene ring or an anthracene ring. 2. The general formula (1), (2) or (3), wherein the general formula (4) is a group selected from the following general formulas (4-1) to (4-3). Or the resist material of 2.

(Wherein R ⁹ and R ¹⁰ are the same as described above. R ⁰ is a single bond, a linear, branched, cyclic or bridged alkylene group having 1 to 10 carbon atoms, or 6 carbon atoms. Is an arylene group having from 10 to 10 and may contain a carbonyl group, an ester group, or an ether group, and R is one hydrogen atom removed from a linear or branched alkylene group having 1 to 6 carbon atoms. A trivalent aliphatic hydrocarbon group, or

Is a group that forms ) (A) an organic solvent,
(B) The polymer according to any one of claims 1 to 3 as a base resin,
(C) A chemically amplified positive resist material comprising an acid generator. (A) an organic solvent,
(B) The polymer according to any one of claims 1 to 3 as a base resin,
(C) an acid generator,
(D) A chemically amplified positive resist material comprising a dissolution inhibitor. Additionally, (E) a chemically amplified positive resist composition according to claim 4 or 5, wherein it has a basic compound as an additive. A step of applying the resist material according to any one of claims 1 to 6 on a substrate, a step of exposing to a high energy beam or an electron beam through a photomask after the heat treatment, and heating if necessary And a step of developing using a developer after the treatment.