JP2009098155A - Radiation sensitive composition - Google Patents

Abstract

Disclosed is a radiation-sensitive composition sensitive to radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, which has a small line edge roughness and a good pattern shape.
A radiation-sensitive composition comprising 1 to 49% by weight of a solid component and 51 to 99% by weight of a solvent, wherein the solid component is a monovalent to tetravalent aromatic ketone or aromatic having 5 to 45 carbon atoms. A polyphenol compound having a molecular weight of 300 to 3000, synthesized by a condensation reaction between an aldehyde and a compound having 6 to 15 carbon atoms and containing 1 to 3 phenolic hydroxyl groups.
A radiation-sensitive composition comprising:
[Selection figure] None

Description

  The present invention relates to a radiation-sensitive composition containing a specific compound. The composition of the present invention is used as a radiation-sensitive material sensitive to radiation such as ultraviolet rays, KrF excimer lasers, extreme ultraviolet rays, electron beams or X-rays, in LSIs in the field of electronics, masks used in the manufacture of VLSIs, and the like.

  In general, positive chemically amplified resists are widely used (for example, Patent Documents 1 to 3). Conventional positive chemically amplified resists are roughly classified into two types. One is a three-component system comprising an alkali-soluble resin, a compound that generates an acid upon radiation exposure, and a dissolution inhibiting compound for an alkali-soluble resin having an acid-dissociable group, and the other is decomposed by the action of an acid. , A two-component system comprising a resin having an alkali-soluble group and a photoacid generator.

  However, in lithography using any resist, since a high molecular weight material is used, there is a problem that roughness is generated on the pattern surface or the edge of the line when fine processing advances. In particular, the line edge roughness (LER) is a serious problem because it makes it difficult to control the pattern size and causes a decrease in yield of semiconductor devices and deterioration of transistor characteristics.

  In addition, resist materials having a low molecular weight and a narrow molecular weight distribution have been proposed in order to produce a pattern with reduced LER (for example, Patent Documents 4 to 6). However, although LER tends to improve, on the other hand, it is difficult to form a pattern having a good shape, and no practical resist material has been found.

U.S. Pat. No. 4,491,628 European Patent No. 249139 JP 2001-281847 A International Publication No. 2005/081062 Pamphlet JP 2005-309421 A International Publication No. 2005/029189 Pamphlet

  An object of the present invention is to provide a radiation-sensitive composition sensitive to radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. Another object of the present invention is to provide a positive radiation-sensitive composition and a negative radiation-sensitive composition that give a good pattern shape with a low LER.

As a result of intensive studies, the present inventors have found that a radiation-sensitive composition containing a specific compound is useful for solving the above problems.
That is, this invention relates to the radiation sensitive composition shown to following (1) to (3) containing a specific polyphenol compound or its derivative (s).
(1) A radiation-sensitive composition comprising 1 to 49% by weight of a solid component and 51 to 99% by weight of a solvent,
A molecular weight of 300 synthesized by a condensation reaction of a mono- to tetravalent aromatic ketone or aldehyde having 5 to 45 carbon atoms and a compound having 6 to 15 carbon atoms and containing 1 to 3 phenolic hydroxyl groups. To 3000 polyphenol compounds (A1)
It is related with the radiation sensitive composition characterized by including.
(2) Compound (B1) having a structure in which an acid-dissociable functional group is introduced into at least one phenolic hydroxyl group of the polyphenol compound (A1) and having a molecular weight of 400 to 3100
The present invention relates to a radiation-sensitive composition comprising 1 to 49% by weight of a solid component and 51 to 99% by weight of a solvent.
(3) A quinonediazide sulfonic acid ester compound (E1) synthesized from the above polyphenol compound (A1)
The present invention relates to a radiation-sensitive composition comprising 1 to 49% by weight of a solid component and 51 to 99% by weight of a solvent.

  The radiation-sensitive composition of the present invention comprising the polyphenol compound (A1) of (1), the compound (B1) of (2) or the quinonediazide sulfonic acid ester compound (E1) of (3) comprises a KrF excimer laser, extreme ultraviolet light, A good resist pattern can be formed with low LER by radiation such as electron beam or X-ray. Therefore, a highly integrated semiconductor device can be manufactured with high productivity.

Hereinafter, the present invention will be described in detail.
The radiation sensitive composition of (1) comprises 1 to 89% by weight of a solid component containing the polyphenol compound (A1) and 11 to 99% by weight of a solvent, preferably 1 to 49% by weight of a solid component and 51 to 99% by weight of a solvent. More preferably 1 to 39% by weight of the solid component and 61 to 99% by weight of the solvent, further preferably 1 to 29% by weight of the solid component and 71 to 99% by weight of the solvent, particularly preferably 1 to 19% by weight of the solid component and 81 to 81% of the solvent. Contains 99% by weight.
In this case, the radiation sensitive composition (1) is a positive radiation sensitive composition or a negative radiation sensitive composition.

  The total content of the polyphenol compound (A1) is 0.1 to 100% by weight of the total weight of the solid component, preferably 1 to 79.999% by weight, more preferably 1 to 59.999% by weight, still more preferably. It is 1 to 49.999% by weight, particularly preferably 1 to 39.999% by weight.

  The polyphenol compound (A1) is a condensation reaction of a monovalent to tetravalent aromatic ketone or aromatic aldehyde having 5 to 45 carbon atoms and a compound having 6 to 15 carbon atoms and containing 1 to 3 phenolic hydroxyl groups. Is a polyphenol compound having a molecular weight of 300 to 3000.

  Examples of the aromatic ketone or aromatic aldehyde include biphenyl structure, naphthalene structure, terphenyl structure, phenanthrene structure, anthracene structure, pyrene structure, fluorene structure, acenaphthene structure, benzophenone structure, xanthene structure, anthraquinone structure and thioxanthene structure. And monocarbonyl compounds, dicarbonyl compounds, tricarbonyl compounds, and tetracarbonyl compounds having a structure selected from the group consisting of.

  Examples of the monovalent aromatic ketone or aromatic aldehyde having 5 to 45 carbon atoms include acetophenone, benzophenone, acetonaphthone, fluorenone, acenaphthenone, benzoquinone, naphthoquinone, anthraquinone, acenaphthenequinone, benzoylbiphenyl, benzoylnaphthalene, acylbiphenyl, Acyl anthracene, acyl phenanthrene, acyl phenothiazane, acyl pyrene, acyl benzopyrene, acyl indacene, acyl phenacene, acyl acenaphthylene, acyl naphthacene, acyl pentacene, acyl triphenylene, acyl pyridine, acyl imidazole, acyl furan, acyl pyrrole acyl overene , Indanone, tetralone, acylthiazole, acridone, flavone, isoflavone, benzaldehyde Toluylaldehyde, anisaldehyde, naphthaldehyde, anthraldehyde, biphenylaldehyde, formylfluorene, formylbiphenyl, formylanthracene, formylphenanthrene, formylphenothiazan, formylpyrene, formylbenzopyrene, formylindacene, formylphenacene, formylacenaphthylene , Formylnaphthacene, formylpentacene, formyltriphenylene, formylpyridine, formylovalene and the like.

  Examples of the divalent aromatic ketone or aromatic aldehyde include diformylbenzene, diacetylbenzene, dibenzoylbenzene, diformyltoluene, diacetyltoluene, dibenzoyltoluene, diformylxylene, diacetylxylene, dibenzoylxylene, and diformyl. Naphthalene, diacetylnaphthalene, dibenzoylnaphthalene, diformylbiphenyl, diacetylbiphenyl, dibenzoylbiphenyl, diformylterphenyl, diacetylterphenyl, dibenzoylterphenyl, diformylanthracene, diacetylanthracene, dibenzoylanthracene, diformylphenanthrene, diacetyl Phenanthrene, dibenzoylphenanthrene, diformylpyrene, diacetylpyrene, dibenzoylpyrene, di Rumyl indacene, diacetyl indacene, dibenzoyl indacene, diformyl phenalene, diacetyl phenalene, dibenzoyl phenalene, diformyl acenaphthylene, diacetyl acenaphthylene, dibenzoyl acenaphthylene, diformyl phenalene, diacetyl phenalene, Dibenzoylphenalene, diformylnaphthacene, diacetylnaphthacene, dibenzoylnaphthacene, diformylpentacene, diacetylpentacene, dibenzoylpentacene, diformyltriphenylene, diacetyltriphenylene, dibenzoyltriphenylene, diformylpyridine, diacetylpyridine, dibenzoyl Pyridine, diformylimidazole, diacetylimidazole, dibenzoylimidazole, diformylfuran, diacetylfuran , Dibenzoyl furan, di-formylthiazole, diacetyl thiazole, dibenzo Lee thiazoles, di-formyl flavones, di-acetyl flavone, dibenzoyl flavones, di-formyl isoflavones, diacetyl isoflavones, such as dibenzoyl isoflavone can be mentioned.

  The divalent aromatic ketone or aromatic aldehyde preferably has a naphthalene structure having 10 to 20 carbon atoms, more preferably has a naphthalene structure having 10 to 17 carbon atoms, and has a naphthalene structure having 10 to 14 carbon atoms. More preferably, it has a C1-C12 naphthalene structure, and it is especially preferable.

  Specific examples of the divalent aromatic ketone or aromatic aldehyde having a naphthalene structure include, for example, naphthalene dicarbaldehyde, methyl naphthalene dicarbaldehyde, dimethyl naphthalene dicarbaldehyde, trimethyl naphthalene dicarbaldehyde, diacetylnaphthalene, diacetylmethyl Naphthalene, diacetyldimethylnaphthalene, diacetyltrimethylnaphthalene and the like can be mentioned.

  Among divalent aromatic ketones or aromatic aldehydes, naphthalene-2,5-dicarbaldehyde, naphthalene-2,6-dicarbaldehyde, naphthalene-2,7-dicarbaldehyde, 2,5-acetylnaphthalene, 2,6-acetylnaphthalene, 2,7-acetylnaphthalene, metaterphenyl-4,4 "-dicarbaldehyde, paraterphenyl-4,4" -dicarbaldehyde, orthoterphenyl-4,4 "-di Carbaldehyde is preferred, naphthalene-2,6-dicarbaldehyde, naphthalene-2,7-dicarbaldehyde, metaterphenyl-4,4 "-dicarbaldehyde, paraterphenyl-4,4" -dicarbaldehyde Are more preferable, and naphthalene-2,6-dicarbaldehyde is still more preferable.

  Examples of the trivalent aromatic ketone or aromatic aldehyde include triformylbenzene, triacetylbenzene, tribenzoylbenzene, triformyltoluene, triacetyltoluene, tribenzoyltoluene, triformylxylene, triacetylxylene, and tribenzoylxylene. , Triformylnaphthalene, triacetylnaphthalene, tribenzoylnaphthalene, triformylbiphenyl, triacetylbiphenyl, tribenzoylbiphenyl, triformylterphenyl, triacetylterphenyl, tribenzoylterphenyl, triformylanthracene, triacetylanthracene, tribenzoyl Anthracene, Triformylphenanthrene, Triacetylphenanthrene, Tribenzoylphenanthrene, Triformy Pyrene, triacetylpyrene, tribenzoylpyrene, triformylindacene, triacetylindacene, tribenzoylindacene, triformylphenalene, triacetylphenalene, tribenzoylphenalene, triformylacenaphthylene, triacetylacenaphthyl Len, tribenzoyl acenaphthylene, triformyl phenalene, triacetyl phenalene, tribenzoyl phenalene, triformyl naphthacene, triacetyl naphthacene, tribenzoyl naphthacene, triformyl pentacene, triacetyl pentacene, tribenzoyl pentacene, Triformyltriphenylene, triacetyltriphenylene, tribenzoyltriphenylene, triformylpyritrin, triacetylpyritrin, tribenzoylpyritrin Triformylimidazole, triacetylimidazole, tribenzoylimidazole, triformylfuran, triacetylfuran, tribenzoylfuran, triformylthiazole, triacetylthiazole, tribenzoylthiazole, triformylflavone, triacetylflavone, tribenzoylflavone, triformyl Examples include isoflavones, triacetylisoflavones, and tribenzoylisoflavones.

  Of these trivalent aromatic ketones or aromatic aldehydes, triformylbenzene, triacetylbenzene, triformylnaphthalene, triacetylnaphthalene, triformylbiphenyl, and triacetylbiphenyl are more preferable, and triformylbenzene and triformylnaphthalene are preferable. More preferred is triformylbenzene.

  Examples of tetravalent aromatic ketones or aromatic aldehydes include tetraformylbenzene, tetraacetylbenzene, tetrabenzoylbenzene, tetraformylnaphthalene, tetraacetylnaphthalene, tetrabenzoylnaphthalene, tetraformylbiphenyl, tetraacetylbiphenyl, and tetrabenzoylbiphenyl. , Tetraformylterphenyl, tetraacetylterphenyl, tetrabenzoylterphenyl, tetraformylanthracene, tetraacetylanthracene, tetrabenzoylanthracene, tetraformylphenanthrene, tetraacetylphenanthrene, tetrabenzoylphenanthrene, tetraformylpyrene, tetraacetylpyrene, tetrabenzoyl Pyrene, tetraformylindacene, tetraacetyl Dacene, tetrabenzoylindacene, tetraformylphenalene, tetraacetylphenalene, tetrabenzoylphenalene, tetraformylacenaphthylene, tetraacetylacenaphthylene, tetrabenzoylacenaphthylene, tetraformylphenalene, tetraacetylphenalene, Tetrabenzoylphenalene, tetraformylnaphthacene, tetraacetylnaphthacene, tetrabenzoylnaphthacene, tetraformylpentacene, tetraacetylpentacene, tetrabenzoylpentacene, tetraformyltetraphenylene, tetraacetyltetraphenylene, tetrabenzoyltetraphenylene, tetraformylpyri Tetran, tetraacetylpyritetrane, tetrabenzoylpyritetrane, tetraformylimidazole, teto Acetylimidazole, tetrabenzoylimidazole, tetraformylfuran, tetraacetylfuran, tetrabenzoylfuran, tetraformylthiazole, tetraacetylthiazole, tetrabenzoylthiazole, tetraformylflavone, tetraacetylflavone, tetrabenzoylflavone, tetraformylisoflavone, tetraacetylisoflavone And tetrabenzoylisoflavone.

  Among these tetravalent aromatic ketones or aromatic aldehydes, tetraformylbenzene, tetraacetylbenzene, tetraformylnaphthalene, tetraacetylnaphthalene, tetraformylbiphenyl, tetraacetylbiphenyl, tetraformylterphenyl, and tetraacetylterphenyl are more preferred. Tetraformylbenzene and tetraformylnaphthalene are more preferable.

  The mono- to tetravalent aromatic ketone or aromatic aldehyde having 5 to 45 carbon atoms is produced by any known method. For example, a method of reducing methyl naphthalenedicarboxylate or methyl benzenetricarboxylate using a reducing agent, a method of reducing naphthalenedinitrile or benzenetrinitrile using a reducing agent or hydrogen and a catalyst, an alkyl aromatic such as dimethylnaphthalene or trimesin A method of oxidizing a side chain methyl group of an aromatic compound by air, a method of oxidizing a chlorinated aromatic compound obtained by photochlorination of a side chain of an alkyl aromatic compound such as dimethylnaphthalene or trimesin, a naphthalene dicarboxylic acid chloride, and the like Examples include a method of oxidizing an aromatic carboxylic acid chloride such as trimesic acid chloride using an oxidizing agent, and a method of oxidizing dihydroxymethylnaphthalene or trihydroxymethylbenzene using an oxidizing agent.

  The polyphenol compound (A1) preferably includes a conjugated structure in which at least two benzene rings and / or non-bonded electron pairs of heteroatoms are involved. By having the above conjugated structure, it is possible to impart performance such as film forming property, high etching resistance, heat resistance, low outgassing property at the time of radiation exposure, and high sensitivity due to a sensitizing effect even though it is a low molecular compound. This sensitization effect is considered to absorb part of radiation such as an electron beam and then efficiently transmit the absorbed energy to the acid generator described later. When the aromatic ketone or aromatic aldehyde is trivalent or tetravalent, performance such as film-forming properties and heat resistance can be imparted without including the conjugated structure.

  The conjugated structure is biphenyl structure, naphthalene structure, fluorene structure, phenanthrene structure, anthracene structure, pyrene structure, benzopyrene structure, acenaphthene structure, acenaphthylene structure, 1-ketoacenaphthene structure, benzophenone structure, xanthene structure, thioxanthene structure, flavone structure, Isoflavone structure, indane structure, indene structure, indacene structure, phenalene structure, biphenylene structure, coronene structure, chrysene structure, trinaphthylene structure, hexaphen structure, hexacene structure, rubicene structure, fluoracene structure, acephenanthrylene structure, perylene structure, picene structure , Pentaphen structure, heptaphen structure, heptacene structure, pyranthrene structure, phenacene structure, naphthacene structure, pentacene structure, aceanthrene structure, Sefenantoren structure, azulene structure, triphenylene structure, terphenyl structure, triphenylbenzene structure, phenylnaphthalene structure, phenylnaphthalene structure, binaphthalene structure, ovalene structure, and the like. A relatively inexpensive raw material having at least one structure selected from a biphenyl structure, naphthalene structure, anthracene structure, phenanthrene structure, pyrene structure, fluorene structure, acenaphthene structure, ketoacenaphthene structure, benzophenone structure, xanthene structure, and thioxanthene structure It is preferable for reasons such as being able to be introduced. At least one structure selected from a naphthalene structure and a terphenyl structure is more preferable, and a naphthalene structure is particularly preferable.

  The aromatic ketone or aromatic aldehyde is more preferably an aromatic aldehyde. The reactivity of the aromatic aldehyde is higher than the reactivity of the aromatic ketone, and by-products are suppressed, and the polyphenol compound (A1) can be produced with a high yield.

Examples of the compound having 6 to 15 carbon atoms and containing 1 to 3 phenolic hydroxyl groups include phenol, (C _1-6 alkyl) phenol (for example, cresol such as o-cresol, m-cresol, p-cresol and the like). Dialkylphenol (for example, 2,3-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 2-ethyl-5-methylphenol, thymol), trialkylphenol (2,3,6). -Trimethylphenol), alkoxyphenol (for example, anisole such as 2-methoxyphenol), arylphenol (for example, phenylphenol such as 3-phenylphenol), cycloalkylphenol (for example, 3-cyclohexylphenol), halogenated phenol (Eg, chlorophenol, dichlorophenol, chlorocresol, bromophenol, dibromophenol), other phenols (eg, naphthol, 5,6,7,8-tetrahydronaphthol), polyhydric phenols (eg, catechol, alkyl) Catechol, chlorocatechol, resorcinol, alkylresorcinol, hydroquinone, alkylhydroquinone, chlororesorcinol, chlorohydroquinone, pyrogallol, alkylpyrogallol, phloroglicinol, 1,2,4-trihydroxyphenol) and the like. 2,5-xylenol, 2,6-xylenol, thymol and 2,3,6-trimethylphenol are preferred, 2,6-xylenol and 2,3,6-trimethylphenol are more preferred, and 2,3,6-trimethyl More preferred is phenol. You may use the said compound individually or in combination of 2 or more types. The purity is not particularly limited, but is usually 95% by weight or more, preferably 99% by weight or more.

  The molecular weight of the polyphenol compound (A1) is 300 to 3000, preferably 300 to 3000, more preferably 400 to 2000, still more preferably 500 to 1500, and particularly preferably 600 to 900. Within the above range, LER can be reduced and a good resist pattern can be provided while maintaining the film formability, heat resistance and etching resistance necessary for the resist.

  The polyphenol compound (A1) preferably has a low sublimation property under normal pressure at 100 ° C. or lower, preferably 120 ° C. or lower, more preferably 130 ° C., further preferably 140 ° C. or lower, particularly preferably 150 ° C. or lower. The low sublimation property means that, in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10%, preferably 5%, more preferably 3%, still more preferably 1%, particularly preferably 0.1. % Or less is preferable. Since the sublimation property is low, it is possible to prevent exposure apparatus from being contaminated by outgas during exposure. Moreover, a favorable pattern shape can be given with low LER.

  In one embodiment of the present invention, the polyphenol compound (A1) is preferably a compound represented by the following formula (1).

（式（１）中、
Ｒ^２Ａは、ハロゲン原子、アルキル基、アリール基、アラルキル基、アルコキシ基、アルケニル基、アシル基、アルコキシカルボニル基、アルキロイルオキシ基、アリーロイルオキシ基、シアノ基およびニトロ基からなる群から選ばれる置換基を表し、複数個のＲ^２Ａは同一でも異なっていてもよく；
Ｒ^３は、水素原子または炭素数１〜６のアルキル基であり、Ｒ^４は、ビフェニル構造、ターフェニル構造、ナフタレン構造、フェナントレン構造、アントラセン構造またはピレン構造を有する炭素数１０〜２８の一価の置換基；または、
Ｒ^３はＲ^４と共に、フルオレン構造、フェニルフルオレン構造、ジフェニルフルオレン構造、アセナフテン構造、１−ケトアセナフテン構造、９−ケト−９、１０−ジヒドロフェナントレン構造、またはベンゾフェノン構造を有する炭素数１０〜１８の二価の置換基であり、；
ｍ０、ｎ０は０〜３の整数であり；ｍ２、ｎ２は０〜４の整数であり；１≦ｍ０＋ｍ２≦５、１≦ｎ０＋ｎ２≦５、１≦ｍ０≦３、および１≦ｎ０≦３を満たす。）

(In the formula (1),
R ^2A is selected from the group consisting of halogen atoms, alkyl groups, aryl groups, aralkyl groups, alkoxy groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkyloyloxy groups, aryloyloxy groups, cyano groups, and nitro groups. Represents a substituent, and a plurality of R ^2A may be the same or different;
R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴ is a monovalent carbon atom having 10 to 28 carbon atoms having a biphenyl structure, a terphenyl structure, a naphthalene structure, a phenanthrene structure, an anthracene structure or a pyrene structure. A substituent of
R ^3, together with R ⁴ , has 10 to 18 carbon atoms having a fluorene structure, a phenylfluorene structure, a diphenylfluorene structure, an acenaphthene structure, a 1-ketoacenaphthene structure, a 9-keto-9, a 10-dihydrophenanthrene structure, or a benzophenone structure. A valent substituent;
m0 and n0 are integers of 0 to 3; m2 and n2 are integers of 0 to 4; 1 ≦ m0 + m2 ≦ 5, 1 ≦ n0 + n2 ≦ 5, 1 ≦ m0 ≦ 3, and 1 ≦ n0 ≦ 3 . )

In the substituent R ^2A , examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom; examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-propyl group, an n-butyl group, an isobutyl group, sec. -C1-C4 alkyl groups, such as a butyl group and a tert-butyl group; Examples of the cycloalkyl group include a cyclohexyl group, a norbornyl group, an adamantyl group, etc .; Examples of the aryl group include a phenyl group and a tolyl group. Aralkyl group includes benzyl group, hydroxybenzyl group, dihydroxybenzyl group and the like; alkoxy group includes methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, and the like. , Isopropoxy group, n-butoxy group, isobutoxy Groups, sec-butoxy groups, tert-butoxy groups and other alkoxy groups having 1 to 4 carbon atoms; aryloxy groups include phenoxy groups; alkenyl groups include vinyl groups, propenyl groups, and allyl groups. Alkenyl groups having 2 to 4 carbon atoms such as butenyl group; acyl groups having 1 to 6 carbon atoms such as formyl group, acetyl group, propionyl group, butyryl group, valeryl group, isovaleryl group, pivaloyl group, etc. And an aliphatic acyl group such as benzoyl group and toluoyl group; examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, Isobutoxycarbonyl group, sec-butoxycarbonyl group, an alkoxycarbonyl group having 2 to 5 carbon atoms such as an ert-butoxycarbonyl group; examples of the alkyloyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, and an isovaleryloxy group. A pivaloyloxy group; and the aryloyloxy group include a benzoyloxy group.

R ^2A may be a substituent composed of a repeating unit represented by the following formula (2-1) and a terminal group represented by the following formula (2-2).

In the formula (2-1) and / or (2-2), L is a single bond, a methylene group, an ethylene group or a carbonyl group. A plurality of L may be the same or different. n5 is an integer of 0 to 4, n6 is an integer of 1 to 3, and x is an integer of 0 to 3, which satisfies 1 ≦ n5 + n6 ≦ 5. A plurality of n5, n6, and x may be the same or different. R ⁹ is a halogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, alkenyl group, acyl group, alkoxycarbonyl group, alkyloyloxy group, aryloyloxy group, cyano group, And a substituent selected from the group consisting of nitro groups. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom; examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Cycloalkyl groups include cyclohexyl groups, norbornyl groups, adamantyl groups, etc .; aryl groups include phenyl groups, tolyl groups, xylyl groups, and naphthyl groups. Aralkyl groups include benzyl group, hydroxybenzyl group, dihydroxybenzyl group, etc .; alkoxy groups include methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, isopropoxy group, n -Butoxy group, isobutoxy group, sec-butoxy group Examples thereof include alkoxy groups having 1 to 4 carbon atoms such as tert-butoxy group; examples of aryloxy groups include phenoxy groups; examples of alkenyl groups include carbon atoms such as vinyl, propenyl, allyl, and butenyl groups. An acyl group having 1 to 6 carbon atoms such as formyl group, acetyl group, propionyl group, butyryl group, valeryl group, isovaleryl group, pivaloyl group, and the like. And aromatic acyl groups such as benzoyl group and toluoyl group; examples of alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec- Butoxycarbonyl group, tert-butoxycar An alkoxycarbonyl group having 2 to 5 carbon atoms such as an nyl group; the alkyloyloxy group includes an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, and a pivaloyloxy group. An aryloyloxy group includes a benzoyloxy group and the like. A plurality of R ⁹ may be the same or different.

R ^2A is a methyl group substituted at the 2,5-position, 2,6-position or 2,3,6-position of the phenolic hydroxyl group, or an isopropyl group substituted at the 2-position of the phenolic hydroxyl group and the 5-position. A substituted methyl group is preferred. By satisfying the above conditions, crystallinity is suppressed, film formability is improved, and a pattern having a good shape can be obtained.

R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, and cyclohexyl. Straight chain, branched or cyclic alkyl groups such as groups.

In the formula (1), R ⁴ represents the following formula:

で表される置換基であるのが好ましい。
上記式中、Ｒ^５Ａは、それぞれ独立に、炭素数１〜１０のアルキル基、炭素数３〜１０のシクロアルキル基、または炭素数６〜１０のアリール基である。炭素数１〜１０のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デカニル基などの直鎖又は分枝を有するアルキル基が挙げられ、メチル基が好ましい。炭素数３〜１０のシクロアルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロデシル基などが挙げられ、シクロヘキシル基が好ましい。炭素数６〜１０のアリール基としては、フェニル基、トリル基、キシリル基、ナフチル基などが挙げられ、フェニル基が好ましい。ｐ３は０〜３の整数である。ｒ３は０〜２の整数である。複数個のＲ^５Ａおよびｐ３、ｒ３は、各々同一でも異なっていても良い。

It is preferable that it is a substituent represented by these.
In the above formulae, each R ^5A is independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl And a straight chain or branched alkyl group such as a group, an octyl group, a nonyl group, and a decanyl group, and a methyl group is preferable. Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclodecyl group, and a cyclohexyl group is preferable. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group, and a phenyl group is preferable. p3 is an integer of 0-3. r3 is an integer of 0-2. A plurality of R ^5A and p3 and r3 may be the same or different.

R ⁴ having the above structure is obtained by using α-acetonaphthone, β-acetonaphthone, 1-naphthaldehyde, 2-naphthaldehyde, biphenylaldehyde, formylterphenyl, formylphenanthrene, formylpyrene, etc. as aromatic carbonyl compounds. Can be introduced.

In the formula (1), the divalent substituent represented by R ³ and R ⁴ bonded together has the following formula:

で表されるのが好ましい。
上記式中、Ｒ^５Ａ、ｐ３及びｒ３は前記と同様であり、Ｙは、単結合またはカルボニル基であり、Ｚは、メチレン基またはカルボニル基である。複数個のＲ^５Ａ、ｐ３、ｒ３は、各々同一でも異なっていても良い。

It is preferable to be represented by
In the above formula, R ^5A , p3 and r3 are the same as described above, Y is a single bond or a carbonyl group, and Z is a methylene group or a carbonyl group. A plurality of R ^5A , p3, and r3 may be the same or different.

By using 9-fluorenone, 3-phenyl-9-fluorenone, 1,3-diphenyl-9-fluorenone, acenaphthenone, acenaphthenequinone, phenanthrenequinone, etc. as the aromatic carbonyl compound. Can be introduced.

  The compound of the formula (1) is preferably represented by the following formulas (5-1) to (5-11).

上記式中、Ｒ^２Ａ、Ｒ^５Ａ、Ｙ、Ｚ、ｍ０、ｍ２、ｎ０、ｎ２、ｐ３及びｒ３は前記と同様である。

In the above formula, R ^2A , R ^5A , Y, Z, m0, m2, n0, n2, p3 and r3 are the same as described above.

上記式中、Ｒ^２Ａ、Ｒ^３は、前記と同様であり；
Ｒ^７は、水素原子または炭素数１〜６のアルキル基であり；
Ｒ^４Ａは、ビフェニル構造、ターフェニル構造、ナフタレン構造、フェナントレン構造、アントラセン構造、またはピレン構造を有する炭素数１０〜２８の二価の置換基であり、Ｒ^４Ａは、Ｒ^３およびＲ^７と共にフルオレン構造またはベンゾフェノン構造を有する炭素数１０〜２８の四価の置換基を形成してもよく；
ｋ０、ｊ０、ｍ０、ｎ０は０〜３の整数であり；ｋ２、ｊ２、ｍ２、ｎ２は０〜４の整数であり；１≦ｋ０＋ｋ２≦５、１≦ｊ０＋ｊ２≦５、１≦ｍ０＋ｍ２≦５、１≦ｎ０＋ｎ２≦５、１≦ｋ０≦３、１≦ｊ０≦３、１≦ｍ０≦３、および１≦ｎ０≦３を満たす。） In one embodiment of the present invention, the polyphenol compound (A1) is more preferably represented by the following formula (6).

In the above formula, R ^2A and R ³ are as defined above;
R ⁷ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
R ^4A is a divalent substituent having 10 to 28 carbon atoms having a biphenyl structure, a terphenyl structure, a naphthalene structure, a phenanthrene structure, an anthracene structure, or a pyrene structure, and R ^4A is fluorene together with R ³ and R ^7. A tetravalent substituent having 10 to 28 carbon atoms having a structure or a benzophenone structure may be formed;
k0, j0, m0 and n0 are integers from 0 to 3; k2, j2, m2 and n2 are integers from 0 to 4; 1 ≦ k0 + k2 ≦ 5, 1 ≦ j0 + j2 ≦ 5, 1 ≦ m0 + m2 ≦ 5, 1 ≦ n0 + n2 ≦ 5, 1 ≦ k0 ≦ 3, 1 ≦ j0 ≦ 3, 1 ≦ m0 ≦ 3, and 1 ≦ n0 ≦ 3 are satisfied. )

R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, and cyclohexyl. Straight chain, branched or cyclic alkyl groups such as groups.

R ^4A is a divalent substituent having 10 to 28 carbon atoms having a biphenyl structure, a terphenyl structure, a naphthalene structure, a phenanthrene structure, an anthracene structure, or a pyrene structure, and R ^4A together with R ³ and R ⁷ A tetravalent substituent having 10 to 28 carbon atoms and having a fluorene structure or a benzophenone structure is represented.

上記式中、Ｒ^５Ａ、ｐ３は、前記と同様である。 R ^4A is preferably a substituent represented by the following formulas (7-1) to (7-3).

In the above formula, R ^5A and p3 are the same as described above.

上記式中、Ｒ^５Ａは前記と同様であり、Ｙは単結合またはカルボニル基であり、ｑ３は０〜３の整数であり、ｒ３は０〜２の整数である。複数個のＲ^５Ａ、Ｙ、ｑ３およびｒ３は、各々同一でも異なっていても良い。 As the tetravalent substituent represented by the combination of R ^4A and R ³ and R ⁷ , substituents represented by the following formulas (8-1) and (8-2) are preferable.

In the above formula, R ^5A is the same as above, Y is a single bond or a carbonyl group, q 3 is an integer of 0 to 3, and r 3 is an integer of 0 to 2. A plurality of R ^5A , Y, q3 and r3 may be the same or different.

  In formula (3), k0, j0, m0, n0 are integers of 0-3, k2, j2, m2, n2 are integers of 0-4, 1 ≦ k0 + k2 ≦ 5, 1 ≦ j0 + j2 ≦ 5, 1 ≦ m0 + m2 ≦ 5, 1 ≦ n0 + n2 ≦ 5, 1 ≦ k0 ≦ 3, 1 ≦ j0 ≦ 3, 1 ≦ m0 ≦ 3, 1 ≦ n0 ≦ 3.

式（９）中、Ｒ^２Ａ、Ｒ^３、Ｒ^７、ｋ０、ｊ０、ｍ０、ｎ０、ｋ２、ｊ２、ｍ２、ｎ２は前記と同様であり；Ｒ^４Ｂは、ナフタレン構造を有する炭素数１０〜２０の二価の置換基またはターフェニル構造を有する炭素数１８〜２８の置換基を表す。
ナフタレン構造またはターフェニル構造は剛直な構造であるのでレジスト材料に耐熱性を付与することが出来る。更に、広がったπ共役構造の増感作用により、酸発生剤へのエネルギー伝達効率がよいため高感度が得られる。また、高炭素密度を有する構造であることからＥＵＶ光に対する光透過性がよく、高エネルギー線に対するアウトガス量が小さく、ドライエッチング耐性に優れる。 The compound of formula (6) is preferably represented by the following formula (9).

In Formula (9), R ^2A , R ³ , R ⁷ , k0, j0, m0, n0, k2, j2, m2, and n2 are the same as described above; R ^4B has 10 to 20 carbon atoms having a naphthalene structure. A divalent substituent or a substituent having 18 to 28 carbon atoms having a terphenyl structure.
Since the naphthalene structure or the terphenyl structure is a rigid structure, heat resistance can be imparted to the resist material. Furthermore, high sensitivity can be obtained because the energy transfer efficiency to the acid generator is good due to the sensitizing action of the spread π-conjugated structure. In addition, since it has a structure having a high carbon density, it has good light transmittance with respect to EUV light, a small amount of outgas with respect to high energy rays, and excellent dry etching resistance.

式（１０−１）または（１０−２）中、Ｒ^４Ｂは、前記と同様である。Ｒ^８は、それぞれ独立に、水素原子またはメチル基である。複数個のＲ^８は、同一でも異なっていてもよい。 The compound of the formula (9) is preferably represented by the following formula (10-1) or (10-2).

In formula (10-1) or (10-2), R ^4B is the same as described above. R ⁸ is each independently a hydrogen atom or a methyl group. A plurality of R ⁸ may be the same or different.

The compound of formula (9) is preferably represented by the following formula (11).

In formula (11), R ^2A , R ³ , R ⁷ , k0, j0, m0, n0, k2, j2, m2, and n2 are the same as described above. R ^5A is each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and p1 is an integer of 0 to 6. A plurality of R ¹ , R ^2A and R ^5A may be the same or different.
Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl And a straight chain or branched alkyl group such as a group, an octyl group, a nonyl group, and a decanyl group. Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclodecyl group. Examples of the aryl group having 6 to 10 carbon atoms include phenyl group, tolyl group, xylyl group, and naphthyl group.

式（１２）中、Ｒ^２Ａ、Ｒ^３、Ｒ^５Ａ、Ｒ^７、ｐ１、ｋ０、ｊ０、ｍ０、ｎ０、ｋ２、ｊ２、ｍ２、ｎ２は前記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of the formula (11) is preferably represented by the following formula (12).

In formula (12), R ^2A , R ³ , R ^5A , R ⁷ , p1, k0, j0, m0, n0, k2, j2, m2, and n2 are the same as described above. The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（１３）中、Ｒ^２Ａ、ｋ０、ｊ０、ｍ０、ｎ０、ｋ２、ｊ２、ｍ２、ｎ２は前記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of formula (12) is preferably represented by the following formula (13).

In Formula (13), R ^2A , k0, j0, m0, n0, k2, j2, m2, and n2 are the same as described above. The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（１４）中、Ｒ^８は上記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of the formula (13) is preferably represented by the following formula (14).

In formula (14), R ⁸ is the same as above. The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 Further, the compound of the formula (13) is preferably represented by the following formula (15).

The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（１６）中、Ｒ^２Ａ、Ｒ^３、Ｒ^５Ａ、Ｒ^７、ｐ１、ｋ０、ｊ０、ｍ０、ｎ０、ｋ２、ｊ２、ｍ２、ｎ２は前記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 Moreover, it is preferable that the compound of Formula (11) is represented by following formula (16).

In Formula (16), R ^2A , R ³ , R ^5A , R ⁷ , p1, k0, j0, m0, n0, k2, j2, m2, and n2 are the same as described above. The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（１７）中、Ｒ^１、Ｒ^２Ａ、ｋ０、ｊ０、ｍ０、ｎ０、ｋ２、ｊ２、ｍ２、ｎ２は前記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of the formula (16) is preferably represented by the following formula (17).

In Formula (17), R ¹ , R ^2A , k0, j0, m0, n0, k2, j2, m2, and n2 are the same as described above. The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（１８）中、Ｒ^８は前記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of the formula (17) is preferably represented by the following formula (18).

In formula (18), R ⁸ is the same as described above. The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（１９）中、Ｒ^２Ａ、Ｒ^３、Ｒ^５Ａ、Ｒ^７、ｋ０、ｊ０、ｍ０、ｎ０、ｋ２、ｊ２、ｍ２、ｎ２は前記と同様であり、ｐ２は０〜２の整数である。複数個のＲ^１、Ｒ^２ＡおよびＲ^５Ａは、同一でも異なっていても良い。 The compound of formula (9) is preferably represented by the following formula (19).

In formula (19), R ^2A , R ³ , R ^5A , R ⁷ , k0, j0, m0, n0, k2, j2, m2, and n2 are the same as described above, and p2 is an integer of 0 to 2. A plurality of R ¹ , R ^2A and R ^5A may be the same or different.

式（２０）中、Ｒ^２Ａ、Ｒ^３、Ｒ^５Ａ、Ｒ^７、ｐ２、ｋ０、ｊ０、ｍ０、ｎ０、ｋ２、ｊ２、ｍ２、ｎ２は前記と同様である。式（２０）で表される化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 Moreover, it is preferable that the compound of Formula (19) is represented by following formula (20).

In formula (20), R ^2A , R ³ , R ^5A , R ⁷ , p2, k0, j0, m0, n0, k2, j2, m2, and n2 are the same as described above. The compound represented by the formula (20) is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（２１）中、Ｒ^８は上記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of formula (20) is preferably represented by the following formula (21).

In formula (21), R ⁸ is the same as above. The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（２２）中、Ｒ^２Ａ、Ｒ^３、Ｒ^５Ａ、Ｒ^７、ｐ２、ｋ０、ｊ０、ｍ０、ｎ０、ｋ２、ｊ２、ｍ２、ｎ２は前記と同様である。式（２２）で表される化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of the formula (19) is preferably represented by the following formula (22).

In Formula (22), R ^2A , R ³ , R ^5A , R ⁷ , p2, k0, j0, m0, n0, k2, j2, m2, and n2 are the same as described above. The compound represented by the formula (22) is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（２３）中、Ｒ^８は前記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of formula (22) is preferably represented by the following formula (23).

In formula (23), R ⁸ is the same as described above. The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（２４）中、Ｒ^２Ａは前記と同様であり、
Ｒ^４Ｄはベンゼン構造、ナフタレン構造、ターフェニル構造、フェナントレン構造またはアントラセン構造を有する炭素数６〜２０の三価の置換基を表し、ｋ３、ｊ３、ｍ３、ｎ３、ｘ３、ｙ３は０〜３の整数であり、ｋ５、ｊ５、ｍ５、ｎ５、ｘ５、ｙ５は０〜４の整数であり、１≦ｋ３＋ｋ５≦５、１≦ｊ３＋ｊ５≦５、１≦ｍ３＋ｍ５≦５、１≦ｎ３＋ｎ５≦５、１≦ｘ３＋ｘ５≦５、１≦ｙ３＋ｙ５≦５、１≦ｋ３≦３、１≦ｊ３≦３、１≦ｍ３≦３、１≦ｎ３≦３、１≦ｘ３≦３、１≦ｙ３≦３を満たす。 In one embodiment of the present invention, the polyphenol compound (A1) is more preferably represented by the following formula (24).

In the formula (24), R ^2A is the same as described above,
R ^4D represents a trivalent substituent having 6 to 20 carbon atoms having a benzene structure, a naphthalene structure, a terphenyl structure, a phenanthrene structure or an anthracene structure, and k3, j3, m3, n3, x3, and y3 are 0 to 3 K5, j5, m5, n5, x5, y5 are integers from 0 to 4, 1 ≦ k3 + k5 ≦ 5, 1 ≦ j3 + j5 ≦ 5, 1 ≦ m3 + m5 ≦ 5, 1 ≦ n3 + n5 ≦ 5, 1 ≦ x3 + x5 ≦ 5, 1 ≦ y3 + y5 ≦ 5, 1 ≦ k3 ≦ 3, 1 ≦ j3 ≦ 3, 1 ≦ m3 ≦ 3, 1 ≦ n3 ≦ 3, 1 ≦ x3 ≦ 3, 1 ≦ y3 ≦ 3.

式（２５）中、Ｒ^１、Ｒ^２Ａ、ｋ３、ｊ３、ｍ３、ｎ３、ｘ３、ｙ３、ｋ５、ｊ５、ｍ５、ｎ５、ｘ５、ｙ５は前記と同様である。 The compound of the formula (24) is preferably represented by the following formula (25).

In the formula (25), R ¹ , R ^2A , k3, j3, m3, n3, x3, y3, k5, j5, m5, n5, x5, and y5 are the same as described above.

式（２６）中、Ｒ^８は上記と同様である。 The compound of formula (25) is preferably represented by the following formula (26).

In formula (26), R ⁸ is the same as above.

Hereinafter, the manufacturing method of a polyphenol compound (A1) is demonstrated.
1 mol to 1 mol of monovalent to tetravalent aromatic ketone or 1 mol of aromatic aldehyde, 1 mol to excess of compound containing phenolic hydroxyl group, acid catalyst (hydrochloric acid or sulfuric acid) and cocatalyst for suppressing by-products (thioacetic acid Or in the presence of β-mercaptopropionic acid) at 60 to 150 ° C. for about 0.5 to 20 hours. The remaining amount of aromatic ketone or aromatic aldehyde is traced by known methods such as liquid chromatography, gas chromatography, thin layer chromatography, IR analysis and ¹ H-NMR analysis, and the peak area indicating the remaining amount is not reduced. The end point of the reaction can be determined by the time point. After completion of the reaction, methanol or isopropyl alcohol is added to the reaction solution and heated to 60 to 80 ° C. and stirred for 0.5 to 2 hours, and then an appropriate amount of pure water is added to precipitate the reaction product. After cooling to room temperature, filtration is performed to separate the precipitate, and the polyphenol compound (A1) is obtained by drying. The polyphenol compound (A) is prepared by reacting the above aromatic ketone or aromatic aldehyde with a halogenated hydrogen or halogen gas and reacting with the isolated halide and a compound containing 1 to 3 phenolic hydroxyl groups. Can also be manufactured.

  In order to reduce the amount of residual metal in the polyphenol compound (A1), purification may be performed as necessary. Further, when the acid catalyst and the cocatalyst remain, generally, the storage stability of the radiation-sensitive composition is lowered. Therefore, purification for the purpose of the reduction may be performed. The purification can be performed by a known method as long as the polyphenol compound (A1) is not denatured, and is not particularly limited. For example, a method of washing with water, a method of washing with an acidic aqueous solution, a method of washing with a basic aqueous solution, an ion Examples include a method of treating with an exchange resin and a method of treating with silica gel column chromatography. These purification methods are more preferably performed in combination of two or more. Acidic aqueous solution, basic aqueous solution, ion exchange resin and silica gel column chromatography are optimal depending on the metal to be removed, the amount and type of acidic compound and / or basic compound, the type of polyphenol compound (A1) to be purified, etc. It is possible to select appropriately. For example, as acidic aqueous solution, hydrochloric acid, nitric acid, acetic acid aqueous solution having a concentration of 0.01 to 10 mol / L, aqueous ammonia solution having a concentration of 0.01 to 10 mol / L as basic aqueous solution, cation exchange resin as ion exchange resin, For example, Amberlyst 15J-HG Dry made by Organo can be mentioned. You may dry after refinement | purification. Drying can be performed by a known method, and is not particularly limited, and examples thereof include a vacuum drying method and a hot air drying method under conditions where the polyphenol compound (A1) is not denatured.

  The polyphenol compound (A1) is preferably 1 weight at 23 ° C. in at least one solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, butyl acetate, 3-methylmethoxypropionate or ethyl propionate. % Or more, more preferably 3% by weight or more, still more preferably 5% by weight or more. Use of a safe solvent that can be used in semiconductor factories because it has such solubility, can avoid problems such as precipitation and performance changes after the preparation of the radiation-sensitive composition containing the polyphenol compound (A1). Is possible.

  Since the solid component of the radiation-sensitive composition containing the polyphenol compound (A1) has a high extinction coefficient with respect to light having a wavelength of 248 nm used for KrF lithography, it can be used as a resist for a shade mask. The solid component can form an amorphous film by a spin coating method to form a resist pattern for a shade mask. The extinction coefficient of the resist for shade mask is preferably 5000 L / (cm · mol) or more, more preferably 10000 L / (cm · mol) or more, further preferably 20000 L / (cm · mol) or more, and 30000 L / (cm · mol). The above is particularly preferable.

  The polyphenol compound (A1) can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process.

  The dissolution rate of the polyphenol compound (A1) amorphous film in a 2.38 mass% TMAH aqueous solution at 23 ° C. is preferably 10 Å / sec or more, more preferably 10 to 10000 Å / sec, and further preferably 100 to 1000 Å / sec. It can melt | dissolve in an alkali developing solution as it is 10 tons / sec or more, and can be set as a resist. In addition, when the dissolution rate is 10000 kg / sec or less, the resolution may be improved. Further, there is an effect of reducing LER and reducing defects.

  The glass transition temperature of the polyphenol compound (A1) is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. When the glass transition temperature is within the above range, the semiconductor lithography process has heat resistance capable of maintaining the pattern shape and can provide performance such as high resolution.

  The calorific value of crystallization determined by differential scanning calorimetry of the glass transition temperature of the polyphenol compound (A1) is preferably less than 20 J / g. Further, (crystallization temperature) − (glass transition temperature) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, further preferably 100 ° C. or higher, and particularly preferably 130 ° C. or higher. When the crystallization heat generation amount is less than 20 J / g, or (crystallization temperature) − (glass transition temperature) is within the above range, an amorphous film can be easily formed by spin-coating the radiation-sensitive composition, and The film formability required for the resist can be maintained for a long time, and the resolution can be improved.

In the present invention, the crystallization calorific value, the crystallization temperature, and the glass transition temperature were measured and subjected to differential scanning calorimetry as follows using a DSC / TA-50WS manufactured by Shimadzu Corporation. About 10 mg of the sample was put in an aluminum non-sealed container and heated to a melting point or more at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (50 ml / min). After the rapid cooling, the temperature was again raised to the melting point or higher at a temperature elevation rate of 20 ° C./min in a nitrogen gas stream (30 ml / min). After further rapid cooling, the temperature was increased again to 400 ° C. at a rate of temperature increase of 20 ° C./min in a nitrogen gas stream (30 ml / min). The temperature at the midpoint of the region where the discontinuous portion appears in the baseline (where the specific heat changed to half) was the glass transition temperature (Tg), and the temperature of the exothermic peak that appeared thereafter was the crystallization temperature. The calorific value was determined from the area of the region surrounded by the exothermic peak and the baseline, and was defined as the crystallization calorific value.

  The polyphenol compound (A1) is useful as a negative resist material that becomes a compound that is hardly soluble in an alkali developer by irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. It is considered that the polyphenol compound (A1) is irradiated with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray to induce a condensation reaction between the compounds, resulting in a compound that is hardly soluble in an alkali developer. The resist pattern thus obtained has a very low LER.

  In addition, the solid component of the radiation-sensitive composition (1) includes a dissolution control agent (F), a sensitizer (G), a surfactant (H), an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof ( Various additives such as I) can be blended.

  When the solubility of the polyphenol compound (A1) in the alkaline developer is too high, the dissolution control agent (F) is a component having an action of reducing the solubility to moderate the dissolution rate during development.

  Examples of the dissolution control agent (F) include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. Examples include sulfones. These dissolution control agents can be used alone or in combination of two or more. Although the compounding quantity of a dissolution control agent is suitably adjusted according to the kind of compound (A1) to be used, 0-50 weight% of the solid component total weight is preferable, 0-40 weight% is more preferable, 0-30 More preferred is weight percent.

The sensitizer (G) is a component that absorbs the energy of the irradiated radiation and transmits the energy to the polyphenol compound (A) to improve the apparent sensitivity of the resist. Further, the sensitizer (G), when used in combination with the acid generator (C) described later, absorbs the energy of the irradiated radiation and transmits the energy to the acid generator (C). This has the effect of increasing the generation amount of the resist and improves the apparent sensitivity of the resist.
Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers (G) can be used alone or in combination of two or more. The blending amount of the sensitizer (G) is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, and further preferably 0 to 10% by weight based on the total weight of the solid component.

  The surfactant (H) is a component having an action of improving the coating property and striation of the radiation-sensitive composition of the present invention, the developability as a resist, and the like. As such a surfactant, any of anionic, cationic, nonionic or amphoteric can be used. Of these, nonionic surfactants are preferred. Nonionic surfactants have better affinity with the solvent used in the radiation-sensitive composition and are more effective. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyethylene glycol higher fatty acid diesters, and the following trade names: Ftop (manufactured by Gemco) , MegaFac (Dainippon Ink & Chemicals), Florard (Sumitomo 3M), Asahi Guard, Surflon (Asahi Glass), Pepol (Toho Chemical), KP (Shin-Etsu Chemical) The series products such as Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and the like can be mentioned, but are not particularly limited.

  The blending amount of the surfactant (H) is preferably 0 to 2% by weight, more preferably 0 to 1% by weight, and further preferably 0 to 0.1% by weight based on the total weight of the solid component. Further, by blending a dye or a pigment, the latent image in the exposed area can be visualized, and the influence of halation during exposure can be reduced. Furthermore, the adhesiveness with a board | substrate can be improved by mix | blending an adhesion aid.

  An organic carboxylic acid or an oxo acid of phosphorus or a derivative (I) thereof can be further contained as an optional component for the purpose of preventing sensitivity deterioration or improving the resist pattern shape, retention stability, and the like. In addition, it can also use together with the acid diffusion control agent (D) mentioned later, and may be used independently. As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable. Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid such as diphenyl ester phosphoric acid or derivatives thereof such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di- Derivatives such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester, etc., phosphonic acid or their esters, phosphinic acid, phosphinic acid such as phenylphosphinic acid, and derivatives thereof Of these, phosphonic acid is particularly preferred.

  The organic carboxylic acid or phosphorus oxo acid or its derivative (I) can be used alone or in combination of two or more. The amount of the organic carboxylic acid or phosphorus oxo acid or derivative thereof (I) is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, still more preferably 0 to 5% by weight, based on the total weight of the solid components. 0 to 1% by weight is particularly preferred.

  Examples of the solvent used in the radiation-sensitive composition of the present invention include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Ethylene glycol monoalkyl ethers such as; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; propylene such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether Glycol monoalkyl ethers; methyl lactate, ethyl lactate EL) lactate esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate (PE), etc .; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3 -Other esters such as methyl ethoxypropionate and ethyl 3-ethoxypropionate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; tetrahydrofuran, Although cyclic ethers, such as a dioxane, can be mentioned, It does not specifically limit. These solvents can be used alone or in combination of two or more.

  The polyphenol compound (A1) is a low molecular compound having a molecular weight of 300 to 3000, but has high amorphous properties, high heat resistance, high etching resistance, and high safety solvent solubility. In addition, it has characteristics such as no sublimation and a large absorption coefficient at 248 nm. From the above characteristics, the positive radiation-sensitive composition containing the polyphenol compound (A1) can give a good pattern shape with low LER. It is also useful as a material for KrF shade masks.

The radiation sensitive composition (1) has a solid component
Polyphenol compound (A1),
It is more preferable to include an acid generator (C) that generates an acid upon irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray.
In this case, the radiation sensitive composition (1) is usually a negative radiation sensitive composition.
The total content of the polyphenol compound (A1) and the acid generator (C) is 0.1 to 100% by weight, preferably 1 to 79.999% by weight, more preferably 1 to 59.% by weight based on the total weight of the solid components. It is 999 wt%, more preferably 1 to 49.999 wt%, particularly preferably 1 to 3.9999 wt%.

  The acid generator (C) is an acid generator that generates an acid upon irradiation with any radiation selected from a KrF excimer laser, extreme ultraviolet rays, an electron beam, and an X-ray.

  Since the acid generated from the acid generator (C) can effectively polymerize the polyphenol compound (A1), the sensitivity of the radiation-sensitive composition of the present invention is remarkably improved. The amount of the acid generator used is the total weight of the solid components (the total of solid components used arbitrarily such as the polyphenol compound (A1), the acid generator (C), and other acid diffusion control agents (D), and so on. 0.001 to 50% by weight, more preferably 1 to 40% by weight, and further preferably 3 to 30% by weight. By using it within the above range, a good pattern shape with high sensitivity and low LER can be obtained. In the present invention, if an acid is generated in the system, the method of generating the acid is not limited, but if a KrF excimer laser is used, fine processing is possible, and extreme ultraviolet rays, electron beams, X If a wire is used, further fine processing is possible.

  The amount of the acid generator used is particularly preferably 20 to 30% by weight based on the total weight of the solid components. In the conventional radiation-sensitive composition, it is difficult to use 20 to 30% by weight of the total weight of the solid component, and it is general to use 3 to 10% by weight. The radiation-sensitive composition of the present invention can be used in an amount of 20 to 30% by weight, and can achieve high sensitivity and high resolution that have been difficult in the past.

式（５６−１）中、Ｒ^１３は、同一でも異なっていても良く、それぞれ独立に、水素原子、直鎖状、分枝状もしくは環状アルキル基、直鎖状、分枝状もしくは環状アルコキシ基、ヒドロキシル基またはハロゲン原子であり；Ｘ^-は、アルキル基、アリール基、ハロゲン置換アルキル基もしくはハロゲン置換アリール基を有するスルホン酸イオンまたはハロゲン化物イオンである。
前記式（５６−１）で示される化合物は、トリフェニルスルホニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムノナフルオロ−ｎ−ブタンスルホネート、ジフェニルトリルスルホニウムノナフルオロ−ｎ−ブタンスルホネート、トリフェニルスルホニウムパーフルオロ−ｎ−オクタンスルホネート、ジフェニル−４−メチルフェニルスルホニウムトリフルオロメタンスルホネート、ジ−２，４，６−トリメチルフェニルスルホニウムトリフルオロメタンスルホネート、ジフェニル−４−t−ブトキシフェニルスルホニウムトリフルオロメタンスルホネート、ジフェニル−４−t−ブトキシフェニルスルホニウムノナフルオロ−ｎ−ブタンスルホネート、ジフェニル−４−ヒドロキシフェニルスルホニウムトリフルオロメタンスルホネート、ビス（４−フルオロフェニル）−４−ヒドロキシフェニルスルホニウムトリフルオロメタンスルホネート、ジフェニル−４−ヒドロキシフェニルスルホニウムノナフルオロ−ｎ−ブタンスルホネート、ビス（４−ヒドロキシフェニル）−フェニルスルホニウムトリフルオロメタンスルホネート、トリ（４−メトキシフェニル）スルホニウムトリフルオロメタンスルホネート、トリ（４−フルオロフェニル）スルホニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムｐ−トルエンスルホネート、トリフェニルスルホニウムベンゼンスルホネート、ジフェニル−２，４，６−トリメチルフェニル−ｐ−トルエンスルホネート、ジフェニル−２，４，６−トリメチルフェニルスルホニウム−２−トリフルオロメチルベンゼンスルホネート、ジフェニル−２，４，６−トリメチルフェニルスルホニウム−４−トリフルオロメチルベンゼンスルホネート、ジフェニル−２，４，６−トリメチルフェニルスルホニウム−２，４−ジフルオロベンゼンスルホネート、ジフェニル−２，４，６−トリメチルフェニルスルホニウムヘキサフルオロベンゼンスルホネート、ジフェニルナフチルスルホニウムトリフルオロメタンスルホネート、ジフェニル−４−ヒドロキシフェニルスルホニウム−ｐ−トルエンスルホネート、トリフェニルスルホニウム１０−カンファースルホネート、ジフェニル−４−ヒドロキシフェニルスルホニウム１０−カンファースルホネートおよびシクロ（１，３−パーフルオロプロパンジスルホン）イミデートからなる群から選択される少なくとも一種類であることが好ましい。
式（５６−２）中、Ｒ^１４は、同一でも異なっていても良く、それぞれ独立に、水素原子、直鎖状、分枝状もしくは環状アルキル基、直鎖状、分枝状もしくは環状アルコキシ基、ヒドロキシル基またはハロゲン原子を表す。Ｘ^-は前記と同様である。
前記式（５６−２）で示される化合物は、ビス（４−t−ブチルフェニル）ヨードニウムトリフルオロメタンスルホネート、ビス（４−t−ブチルフェニル）ヨードニウムノナフルオロ−ｎ−ブタンスルホネート、ビス（４−t−ブチルフェニル）ヨードニウムパーフルオロ−ｎ−オクタンスルホネート、ビス（４−t−ブチルフェニル）ヨードニウム ｐ−トルエンスルホネート、ビス（４−t−ブチルフェニル）ヨードニウムベンゼンスルホネート、ビス（４−t−ブチルフェニル）ヨードニウム−２−トリフルオロメチルベンゼンスルホネート、ビス（４−t−ブチルフェニル）ヨードニウム−４−トリフルオロメチルベンゼンスルホネート、ビス（４−t−ブチルフェニル）ヨードニウム−２，４−ジフルオロベンゼンスルホネート、ビス（４−t−ブチルフェニル）ヨードニウムヘキサフルオロベンゼンスルホネート、ビス（４−t−ブチルフェニル）ヨードニウム１０−カンファースルホネート、ジフェニルヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウムノナフルオロ−ｎ−ブタンスルホネート、ジフェニルヨードニウムパーフルオロ−ｎ−オクタンスルホネート、ジフェニルヨードニウム ｐ−トルエンスルホネート、ジフェニルヨードニウムベンゼンスルホネート、ジフェニルヨードニウム１０−カンファースルホネート、ジフェニルヨードニウム−２−トリフルオロメチルベンゼンスルホネート、ジフェニルヨードニウム−４−トリフルオロメチルベンゼンスルホネート、ジフェニルヨードニウム−２，４−ジフルオロベンゼンスルホネート、ジフェニルヨードニウムへキサフルオロベンゼンスルホネート、ジ（４−トリフルオロメチルフェニル）ヨードニウムトリフルオロメタンスルホネート、ジ（４−トリフルオロメチルフェニル）ヨードニウムノナフルオロ−ｎ−ブタンスルホネート、ジ（４−トリフルオロメチルフェニル）ヨードニウムパーフルオロ−ｎ−オクタンスルホネート、ジ（４−トリフルオロメチルフェニル）ヨードニウム ｐ−トルエンスルホネート、ジ（４−トリフルオロメチルフェニル）ヨードニウムベンゼンスルホネートおよびジ（４−トリフルオロメチルフェニル）ヨードニウム１０−カンファースルホネートからなる群から選択される少なくとも一種類であることが好ましい。 The acid generator (C) is not particularly limited, but is preferably at least one selected from the group consisting of compounds represented by the following formulas (56-1) to (62-2).

In formula (56-1), R ¹³ may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. A hydroxyl group or a halogen atom; X ⁻ is a sulfonate ion or a halide ion having an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.
The compound represented by the formula (56-1) is triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, diphenyltolylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-. Octanesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, di-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenyl Sulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethane Sulfonate, bis (4-fluorophenyl) -4-hydroxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, tri ( 4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (4-fluorophenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluene Sulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2-trifluoromethyl Benzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-4-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6 -Trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenylnaphthylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate and cyclo (1,3-perfluoropropanedisulfone) at least selected from the group consisting of imidates It is preferred that one kind.
In formula (56-2), R ¹⁴ may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. Represents a hydroxyl group or a halogen atom. X ⁻ is the same as described above.
The compound represented by the formula (56-2) includes bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t -Butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodoniumbenzenesulfonate, bis (4-t-butylphenyl) Iodonium-2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluorobenzenesulfonate, bis ( 4-t -Butylphenyl) iodonium hexafluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate Diphenyliodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyliodonium-2,4-difluoro Benzene sulfonate, dipheny Iodonium hexafluorobenzenesulfonate, di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, di (4-trifluoromethylphenyl) iodonium per From fluoro-n-octanesulfonate, di (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, di (4-trifluoromethylphenyl) iodoniumbenzenesulfonate and di (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate Preferably, at least one selected from the group consisting of:

式（５７）中、Ｑはアルキレン基、アリーレン基またはアルコキシレン基であり、Ｒ^１５はアルキル基、アリール基、ハロゲン置換アルキル基またはハロゲン置換アリール基である。
前記式（５７）で示される化合物は、Ｎ−（トリフルオロメチルスルホニルオキシ）スクシンイミド、Ｎ−（トリフルオロメチルスルホニルオキシ）フタルイミド、Ｎ−（トリフルオロメチルスルホニルオキシ）ジフェニルマレイミド、Ｎ−（トリフルオロメチルスルホニルオキシ）ビシクロ［２．２．１］へプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（トリフルオロメチルスルホニルオキシ）ナフチルイミド、Ｎ−（１０−カンファースルホニルオキシ）スクシンイミド、Ｎ−（１０−カンファースルホニルオキシ）フタルイミド、Ｎ−（１０−カンファースルホニルオキシ）ジフェニルマレイミド、Ｎ−（１０−カンファースルホニルオキシ）ビシクロ［２．２．１］へプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（１０−カンファースルホニルオキシ）ナフチルイミド、Ｎ−（ｎ−オクタンスルホニルオキシ）ビシクロ［２．２．１］へプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（ｎ−オクタンスルホニルオキシ）ナフチルイミド、Ｎ−（p−トルエンスルホニルオキシ）ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（p−トルエンスルホニルオキシ）ナフチルイミド、Ｎ−（２−トリフルオロメチルベンゼンスルホニルオキシ）ビシクロ［２．２．１］へプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（２−トリフルオロメチルベンゼンスルホニルオキシ）ナフチルイミド、Ｎ−（４−トリフルオロメチルベンゼンスルホニルオキシ）ビシクロ［２．２．１］へプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（４−トリフルオロメチルベンゼンスルホニルオキシ）ナフチルイミド、Ｎ−（パーフルオロベンゼンスルホニルオキシ）ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（パーフルオロベンゼンスルホニルオキシ）ナフチルイミド、Ｎ−（1−ナフタレンスルホニルオキシ）ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（1−ナフタレンスルホニルオキシ）ナフチルイミド、Ｎ−（ノナフルオロ−ｎ−ブタンスルホニルオキシ）ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（ノナフルオロ−ｎ−ブタンスルホニルオキシ）ナフチルイミド、Ｎ−（パーフルオロ−ｎ−オクタンスルホニルオキシ）ビシクロ［２．２．１］へプト−５−エンー２，３−ジカルボキシイミドおよびＮ−（パーフルオロ−ｎ−オクタンスルホニルオキシ）ナフチルイミドからなる群から選択される少なくとも一種類であることが好ましい。

In formula (57), Q is an alkylene group, an arylene group or an alkoxylene group, and R ¹⁵ is an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.
The compound represented by the formula (57) includes N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoro Methylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- ( 0-camphorsulfonyloxy) naphthylimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) Naphthylimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyl N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Perfluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) Naphthylimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept- - is preferably En 2,3-dicarboximide and N- at least one selected from the group consisting of (perfluoro--n- octane sulfonyloxy) naphthylimide.

式（５８）中、Ｒ^１６は、同一でも異なっていても良く、それぞれ独立に、任意に置換された直鎖、分枝もしくは環状アルキル基、任意に置換されたアリール基、任意に置換されたヘテロアリール基または任意に置換されたアラルキル基である。
前記式（５８）で示される化合物は、ジフェニルジスルフォン、ジ（４−メチルフェニル）ジスルフォン、ジナフチルジスルフォン、ジ（４−ｔｅｒｔ−ブチルフェニル）ジスルフォン、ジ（４−ヒドロキシフェニル）ジスルフォン、ジ（３−ヒドロキシナフチル）ジスルフォン、ジ（４−フルオロフェニル）ジスルフォン、ジ（２−フルオロフェニル）ジスルフォンおよびジ（４−トルフルオロメチルフェニル）ジスルフォンからなる群から選択される少なくとも一種類であることが好ましい。

In formula (58), R ¹⁶ may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, and optionally substituted. A heteroaryl group or an optionally substituted aralkyl group.
The compound represented by the formula (58) includes diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone, di It is at least one selected from the group consisting of (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone and di (4-toluromethylphenyl) disulfone. preferable.

式（５９）中、Ｒ^１７は、同一でも異なっていても良く、それぞれ独立に、任意に置換された直鎖、分枝もしくは環状アルキル基、任意に置換されたアリール基、任意に置換されたヘテロアリール基または任意に置換されたアラルキル基である。
前記式（５９）で示される化合物は、α−（メチルスルホニルオキシイミノ）−フェニルアセトニトリル、α−（メチルスルホニルオキシイミノ）−４−メトキシフェニルアセトニトリル、α−（トリフルオロメチルスルホニルオキシイミノ）−フェニルアセトニトリル、α−（トリフルオロメチルスルホニルオキシイミノ）−４−メトキシフェニルアセトニトリル、α−（エチルスルホニルオキシイミノ）−４−メトキシフェニルアセトニトリル、α−（プロピルスルホニルオキシイミノ）−４−メチルフェニルアセトニトリルおよびα−（メチルスルホニルオキシイミノ）−４−ブロモフェニルアセトニトリルからなる群から選択される少なくとも一種類であることが好ましい。

式（６０）中、Ｒ^１８は、同一でも異なっていても良く、それぞれ独立に、１以上の塩素原子および１以上の臭素原子を有するハロゲン化アルキル基である。ハロゲン化アルキル基の炭素原子数は１〜５が好ましい。

In formula (59), R ¹⁷ may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, and optionally substituted. A heteroaryl group or an optionally substituted aralkyl group.
The compound represented by the formula (59) includes α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -phenyl. Acetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile and α It is preferably at least one selected from the group consisting of-(methylsulfonyloxyimino) -4-bromophenylacetonitrile.

In formula (60), R ¹⁸ may be the same or different and each independently represents a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms. The halogenated alkyl group preferably has 1 to 5 carbon atoms.

式（６１‐１）および（６１‐２）中、Ｒ^１９およびＲ^２０はそれぞれ独立に、メチル基、エチル基、ｎ−プロピル基、イソプロピル基等の炭素原子数１〜３のアルキル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基、メトキシ基、エトキシ基、プロポキシ基等の炭素原子数１〜３のアルコキシル基、またはフェニル基、トルイル基、ナフチル基等アリール基、好ましくは、炭素原子数６〜１０のアリール基である。Ｌ^１９およびＬ^２０はそれぞれ独立に１，２−ナフトキノンジアジド基を有する有機基である。１，２−ナフトキノンジアジド基を有する有機基としては、具体的には、１，２−ナフトキノンジアジド−４−スルホニル基、１，２−ナフトキノンジアジド−５−スルホニル基、１，２−ナフトキノンジアジド−６−スルホニル基等の１，２−キノンジアジドスルホニル基を好ましいものとして挙げることができる。特に、１，２−ナフトキノンジアジド−４−スルホニル基および１，２−ナフトキノンジアジド−５−スルホニル基が好ましい。ｐは１〜３の整数、ｑは０〜４の整数、かつ１≦ｐ＋ｑ≦５である。Ｊ^１９は単結合、炭素原子数１〜４のポリメチレン基、シクロアルキレン基、フェニレン基、下記式（６２−１）で表わされる基、カルボニル基、エステル基、アミド基またはエーテル基であり、Ｙ^１９は水素原子、アルキル基またはアリール基であり、Ｘ^２０は、それぞれ独立に下記式（６２‐２）で示される基である。

In the formulas (61-1) and (61-2), R ¹⁹ and R ²⁰ are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or cyclopentyl. Group, cycloalkyl group such as cyclohexyl group, alkoxyl group having 1 to 3 carbon atoms such as methoxy group, ethoxy group and propoxy group, or aryl group such as phenyl group, toluyl group and naphthyl group, preferably 6 carbon atoms -10 aryl groups. L ¹⁹ and L ²⁰ are each independently an organic group having a 1,2-naphthoquinonediazide group. Specific examples of the organic group having a 1,2-naphthoquinonediazide group include a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, and a 1,2-naphthoquinonediazide- A 1,2-quinonediazidosulfonyl group such as a 6-sulfonyl group can be mentioned as a preferable one. In particular, 1,2-naphthoquinonediazido-4-sulfonyl group and 1,2-naphthoquinonediazide-5-sulfonyl group are preferable. p is an integer of 1 to 3, q is an integer of 0 to 4, and 1 ≦ p + q ≦ 5. J ¹⁹ is a single bond, a polymethylene group having 1 to 4 carbon atoms, a cycloalkylene group, a phenylene group, a group represented by the following formula (62-1), a carbonyl group, an ester group, an amide group or an ether group; ¹⁹ is a hydrogen atom, an alkyl group or an aryl group, and X ²⁰ is independently a group represented by the following formula (62-2).

式（６２‐２）中、Ｚ^２２はそれぞれ独立に、アルキル基、シクロアルキル基またはアリール基であり、Ｒ^２２はアルキル基、シクロアルキル基またはアルコキシル基であり、ｒは０〜３の整数である。

In formula (62-2), Z ²² each independently represents an alkyl group, a cycloalkyl group or an aryl group, R ²² represents an alkyl group, a cycloalkyl group or an alkoxyl group, and r represents an integer of 0 to 3. is there.

  Other acid generators include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) ) Diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, 1,3-bis (cyclohexylsulfonylazomethylsulfonyl) propane, 1, 4 -Bis (phenylsulfonylazomethylsulfonyl) butane, 1,6-bis (phenylsulfonylazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfonyla) Bissulfonyldiazomethanes such as methylsulfonyl) decane, 2- (4-methoxyphenyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6 Halogen-containing triazine derivatives such as-(bistrichloromethyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) isocyanurate Etc.

Among the acid generators, more preferred acid generator having an aromatic ring, represented by formula (56-1) X ^- is an acid generator having a sulfonic acid ion having an aryl group or a halogen-substituted aryl group is further Diphenyltrimethylphenylsulfonium p-toluenesulfonate and triphenylsulfonium p-toluenesulfonate are particularly preferable. LER can be reduced by using the acid generator.

The radiation sensitive composition (1) has a solid component
Polyphenol compound (A1),
Resin (B2) having an acid-dissociable functional group whose solubility in an alkaline developer is increased by the action of an acid and / or a dissolution inhibiting compound having an acid-dissociable functional group whose solubility in an alkaline developer is increased by the action of an acid (B3),
An acid generator (C) that generates acid upon irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray;
It is more preferable to contain.
In this case, the radiation sensitive composition (1) is usually a positive radiation sensitive composition.

  The total content of the polyphenol compound (A1), the resin (B2) having an acid dissociable functional group and / or the dissolution inhibiting compound (B3) having an acid dissociable functional group, and the acid generator (C) is the total weight of the solid component. 0.1 to 100% by weight, preferably 1 to 79.999% by weight, more preferably 1 to 59.999% by weight, still more preferably 1 to 49.999% by weight, particularly preferably 1 to 39.3%. 999% by weight.

  The resin (B2) having an acid-dissociable functional group is a resin whose solubility in an alkaline developer is increased by the action of an acid, and is acid dissociated in the main chain or side chain of the resin, or in both the main chain and side chain. It is resin which has a functional functional group. Among these, a resin having an acid dissociable functional group in the side chain is more preferable. The acid dissociable functional group will be described later.

  The resin for introducing the acid dissociable functional group is a resin that is hardly soluble in water and soluble in an alkaline developer. For example, a resin having a phenolic hydroxyl group or carboxyl group in the side chain, o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated polyhydroxystyrene, halogen or alkyl-substituted poly (hydroxy). Styrene), partially o-alkylated or o-acylated product of poly (hydroxystyrene), styrene-hydroxystyrene copolymer, copolymer of styrene and a monomer having a phenolic hydroxyl group, α-methylstyrene -Hydroxystyrene copolymer, resin obtained by copolymerization of two or more monomers having a phenolic hydroxyl group, hydrogenated novolac resin, copolymer of hydroxystyrene and (meth) acrylic acid derivative, poly (meth) Examples thereof include, but are not limited to acrylic acid derivatives.

  Resin (B2) having an acid-dissociable functional group is hardly soluble in water and reacts with a compound for introducing an acid-dissociable functional group into an alkali-soluble resin, or a monomer is introduced in advance with an acid-dissociable functional group And an alkali-soluble resin monomer having an acid-dissociable functional group can be obtained by copolymerization with various monomers.

  It is preferable that the weight average molecular weight (Mw) of resin (B2) which has an acid dissociable functional group is 5000-200000. If it is less than 5000, the film thickness of the unexposed portion is large, and if it exceeds 200000, the sensitivity is lowered. More preferably, it is 7000-100,000, More preferably, it is the range of 10,000-50000.

  The dissolution inhibiting compound (B3) having an acid dissociable functional group is a dissolution inhibiting compound having an acid dissociable functional group whose solubility in an alkaline developer is increased by the action of an acid. The acid dissociable functional group will be described later.

  When these acid dissociable functional groups are bonded, the base compound is a compound that is hardly soluble in water and soluble in an alkaline developer. It is a compound having a phenolic hydroxyl group or a carboxyl group, and examples thereof include low molecular weight phenolic compounds such as bisphenols, tris (hydroxyphenyl) methane, polyphenol compound (A1), and the following formula (55-1) to The compound etc. which are shown by (55-18) can be mentioned.

  The dissolution inhibiting compound (B3) having an acid-dissociable functional group can be obtained by reacting a compound for introducing an acid-dissociable functional group into an alkali-soluble compound that is hardly soluble in water. This is the same as the synthesis method.

  The molecular weight of the dissolution inhibiting compound (B3) having an acid dissociable functional group is 150 to 3000, preferably 150 to 3000, more preferably 150 to 2000, still more preferably 150 to 1500, and particularly preferably 150 to 900. is there.

  The acid generator (C) is an acid generator that generates an acid upon irradiation with any radiation selected from a KrF excimer laser, extreme ultraviolet rays, an electron beam, and an X-ray.

  The acid generated from the acid generator (C) effectively cleaves the acid dissociable reactive group of the resin (B2) having an acid dissociable functional group and / or the dissolution inhibiting compound (B3) having an acid dissociable functional group. Therefore, the sensitivity of the radiation sensitive composition of the present invention is remarkably improved. The amount of the acid generator used is the total weight of the solid component (polyphenol compound (A1), resin (B2) having an acid dissociable functional group and / or dissolution inhibiting compound (B3) having an acid dissociable functional group), acid generator 0.001 to 50% by weight of (C) and the total of solid components optionally used such as other acid diffusion control agents (D), the same applies hereinafter), preferably 1 to 40% by weight, more preferably 3 More preferred is ˜30% by weight. By using it within the above range, a good pattern shape with high sensitivity and low LER can be obtained. In the present invention, if an acid is generated in the system, the method of generating the acid is not limited, but if a KrF excimer laser is used, fine processing is possible, and extreme ultraviolet rays, electron beams, X If a wire is used, further fine processing is possible.

  The amount of the acid generator used is particularly preferably 20 to 30% by weight based on the total weight of the solid components. In the conventional radiation-sensitive composition, it is difficult to use 20 to 30% by weight of the total weight of the solid component, and it is general to use 3 to 10% by weight. The radiation-sensitive composition of the present invention can be used in an amount of 20 to 30% by weight, and can achieve high sensitivity and high resolution that have been difficult in the past.

  In the radiation-sensitive composition (1), it is preferable that the solid component further contains an acid diffusion controller (D).

  The acid diffusion controller (D) has a function of controlling an undesired chemical reaction in an unexposed region by controlling diffusion of an acid generated from the acid generator by irradiation in the resist film. By using such an acid diffusion controller, the storage stability of the radiation-sensitive composition is improved. Further, the resolution is improved, and a change in the line width of the resist pattern due to fluctuations in the holding time before electron beam irradiation and the holding time after electron beam irradiation can be suppressed, and the process stability is extremely excellent. Examples of such an acid diffusion controller include electron beam radiation-decomposable basic compounds such as a nitrogen atom-containing basic compound, a basic sulfonium compound, and a basic iodonium compound. The acid diffusion controller can be used alone or in combination of two or more.

  The blending amount of the acid diffusion controller (D) is preferably 0 to 10% by weight, more preferably 0.001 to 5% by weight, and still more preferably 0.001 to 3% by weight based on the total weight of the solid component. Within the above range, it is possible to prevent degradation in resolution, pattern shape, dimensional fidelity, and the like. Furthermore, even if the holding time from radiation irradiation to heating after radiation irradiation becomes longer, the shape of the pattern upper layer portion does not deteriorate. Further, when the blending amount is 10% by weight or less, it is possible to prevent a decrease in sensitivity, developability of an unexposed portion, and the like.

  The solid component of the radiation sensitive composition (1) includes a resin (A2) that is hardly soluble in water and soluble in an alkali developer and / or a dissolution accelerator that is hardly soluble in water and soluble in an alkali developer. (A3) can be blended.

Resin (A2) is a resin that is hardly soluble in water and soluble in an alkali developer, and is hardly soluble in water and used for alkali development, which was used when synthesizing the resin (B2) having an acid-dissociable functional group. Resins that are soluble in the liquid can be used.

The dissolution accelerator (A3) is a compound that is hardly soluble in water and soluble in an alkaline developer, and is difficult to dissolve in water used when synthesizing the dissolution inhibiting compound (B3) having an acid-dissociable functional group. A compound which is soluble and soluble in an alkaline developer can be used.

The radiation sensitive composition (1) has a solid component
Polyphenol compound (A1),
More preferably, quinonediazide sulfonic acid ester (E2) synthesized from a polyphenol compound other than the polyphenol compound (A1) is included.
In this case, the radiation sensitive composition (1) is usually a positive radiation sensitive composition.

  The total content of the polyphenol compound (A1) and the quinonediazide sulfonic acid ester (E2) is 0.1 to 100% by weight, preferably 1 to 79.999% by weight, more preferably 1 to 59% by weight based on the total weight of the solid component. .999% by weight, more preferably 1 to 49.999% by weight, and particularly preferably 1 to 39.999% by weight.

  The quinonediazide sulfonate ester (E2) is hardly soluble in an alkali developer, but the diazo group is decomposed by irradiation with any radiation selected from KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, and ketene is decomposed. After formation, it becomes a carboxylic acid by hydrolysis. Since this carboxylic acid is soluble in an alkaline developer, the solubility of the exposed area is remarkably increased.

  Examples of the quinonediazide sulfonate ester (E2) include 1,2-naphthoquinonediazide-5-sulfonate ester, 1,2-naphthoquinonediazide-4-sulfonate ester, 1,2-naphthoquinonediazide-6-sulfonate ester, 1 2,2-benzoquinonediazide-5-sulfonic acid ester, 1,2-benzoquinonediazide-4-sulfonic acid ester, etc., preferably 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,2-naphthoic acid ester Examples include quinonediazide-4-sulfonic acid ester, and 1,2-naphthoquinonediazide-4-sulfonic acid ester is more preferable.

The method for producing these quinonediazide sulfonic acid esters (E2) is not particularly limited, but quinonediazidesulfonic acid halide, preferably quinonediazidesulfonic acid chloride, in a solvent such as acetone, dioxane, tetrahydrofuran, etc. according to a conventional method, sodium carbonate, In the presence of inorganic bases such as sodium bicarbonate, sodium hydroxide, potassium hydroxide, or organic bases such as trimethylamine, triethylamine, tripropylamine, diisopropylamine, tributylamine, pyrrolidine, piperidine, piperazine, morpholine, pyridine, dicyclohexylamine It can be obtained by reacting with a polyphenol other than the polyphenol compound (A1).
The polyphenols used here are polyhydroxy compounds having 2 or more, preferably 3 or more, more preferably 4 or more phenolic hydroxyl groups in the molecule.
Examples of polyphenols include compounds represented by the above formulas (55-1) to (55-18).

  The solid component of the radiation-sensitive composition (1) includes (B2) a resin having an acid-dissociable functional group whose solubility in an alkali developer is increased by the action of an acid and / or (B3) an alkali development by the action of an acid. A dissolution inhibiting compound having an acid dissociable functional group that increases solubility in a liquid can be blended.

The radiation-sensitive composition (2) includes a compound (B1) having a molecular weight of 400 to 3100 having a structure in which an acid-dissociable functional group is introduced into at least one phenolic hydroxyl group of the polyphenol compound (A1). 1-89 wt% solid component and 11-99 wt% solvent, preferably 1-49 wt% solid component and 51-99 wt% solvent, more preferably 1-39 wt% solid component and 61-99 wt% solvent, More preferably, it contains 1 to 29% by weight of the solid component and 71 to 99% by weight of the solvent, particularly preferably 1 to 19% by weight of the solid component and 81 to 99% by weight of the solvent.
In this case, the radiation sensitive composition (2) is usually a positive radiation sensitive composition.

  The total content of the compound (B1) is 0.1 to 100% by weight, preferably 1 to 79.999% by weight, more preferably 1 to 59.999% by weight, and further preferably 1 to the total weight of the solid component. It is -49.999 weight%, Most preferably, it is 1-39-1999 weight%.

  The acid-dissociable functional group may be appropriately selected from those proposed for hydroxystyrene-based resins and (meth) acrylic acid-based resins used in chemically amplified resist compositions for KrF and ArF. it can. For example, a substituted methyl group, 1-substituted ethyl group, 1-substituted-n-propyl group, 1-branched alkyl group, silyl group, acyl group, 1-substituted alkoxymethyl group, cyclic ether group, alkoxycarbonyl group, etc. Can be mentioned. The acid dissociable functional group preferably has no crosslinkable functional group.

  The molecular weight of the compound (B1) is 400 to 3100, preferably 400 to 2000, more preferably 500 to 1500, and particularly preferably 600 to 900. Within the above range, LER can be reduced and a good resist pattern can be provided while maintaining the film formability, heat resistance and etching resistance necessary for the resist.

  The compound (B1) preferably has a low sublimation property under normal pressure at 100 ° C. or lower, preferably 120 ° C. or lower, more preferably 130 ° C., further preferably 140 ° C. or lower, particularly preferably 150 ° C. or lower. The low sublimation property means that, in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10%, preferably 5%, more preferably 3%, still more preferably 1%, particularly preferably 0.1. % Or less is preferable. Since the sublimation property is low, it is possible to prevent exposure apparatus from being contaminated by outgas during exposure. Moreover, a favorable pattern shape can be given with low LER.

  In one embodiment of the present invention, the compound (B1) is preferably a compound represented by the following formula (27).

式（２７）中、
Ｒ^２Ａ、Ｒ^３、Ｒ^４は前記と同様であり；
Ｒ^１は、置換メチル基、１−置換エチル基、１−置換−ｎ−プロピル基、１−分岐アルキル基、シリル基、アシル基、１−置換アルコキシメチル基、環状エーテル基およびアルコキシカルボニル基からなる群から選択される酸解離性官能基であり；
ｍ０、ｎ０は０〜３の整数であり；ｍ１、ｎ１は０〜３の整数であり；ｍ２、ｎ２は０〜４の整数であり；１≦ｍ０＋ｍ１＋ｍ２≦５、１≦ｎ０＋ｎ１＋ｎ２≦５、１≦ｍ１≦３、および１≦ｎ１≦３を満たす。

In formula (27),
R ^2A , R ³ and R ⁴ are as defined above;
R ¹ is a substituted methyl group, 1-substituted ethyl group, 1-substituted n-propyl group, 1-branched alkyl group, silyl group, acyl group, 1-substituted alkoxymethyl group, cyclic ether group and alkoxycarbonyl group. An acid dissociable functional group selected from the group consisting of;
m0 and n0 are integers of 0 to 3; m1 and n1 are integers of 0 to 3; m2 and n2 are integers of 0 to 4; 1 ≦ m0 + m1 + m2 ≦ 5, 1 ≦ n0 + n1 + n2 ≦ 5, 1 ≦ It satisfies m1 ≦ 3 and 1 ≦ n1 ≦ 3.

Examples of the substituted methyl group include methoxymethyl group, methylthiomethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, t-butoxymethyl group, 2-methylpropoxymethyl group, Ethylthiomethyl group, methoxyethoxymethyl group, phenyloxymethyl group, 1-cyclopentyloxymethyl group, 1-cyclohexyloxymethyl group, benzylthiomethyl group, phenacyl group, 4-bromophenacyl group, 4-methoxyphenacyl group, piperonyl Group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, isopropoxycarbonylmethyl group, n-butoxycarbonylmethyl group, tert-butoxycarbonylmethyl group, and the following formula (28-1) to It can be exemplified a substituent group represented by 28-13).

Examples of the 1-substituted ethyl group include 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl. Group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, t-butoxyethyl group, 2-methylpropoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-di Phenoxyethyl group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, and substitutions represented by the following formulas (29-1) to (29-13) Groups and the like.

  Examples of the 1-substituted-n-propyl group include a 1-methoxy-n-propyl group and a 1-ethoxy-n-propyl group.

  Examples of the 1-branched alkyl group include isopropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, 2-methyladamantyl group, And 2-ethyladamantyl group.

  Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiethylsilyl group, tert-butyldiphenylsilyl group, and tri-tert-butylsilyl. Group and triphenylsilyl group.

  Examples of the acyl group include acetyl group, phenoxyacetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, laurylyl group, adamantyl group, benzoyl group and naphthoyl group. Can do.

  Examples of the 1-substituted alkoxymethyl group include 1-cyclopentylmethoxymethyl group, 1-cyclopentylethoxymethyl group, 1-cyclohexylmethoxymethyl group, 1-cyclohexylethoxymethyl group, 1-cyclooctylmethoxymethyl group and 1-adamantyl group. A methoxymethyl group etc. can be mentioned.

  Examples of the cyclic ether group include a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group, a 4-methoxytetrahydropyranyl group, and a 4-methoxytetrahydrothiopyranyl group. it can.

  Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, and a tert-butoxycarbonyl group.

  Of these acid dissociable functional groups, a substituted methyl group, a substituted ethyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, and an alkoxycarbonyl group are preferable, and the substituted methyl group and the substituted ethyl group are more sensitive. 1-ethoxyethyl group and cyclohexyloxyethyl group are more preferable, and cyclohexyloxyethyl group is particularly preferable because of high resolution.

In addition, the acid dissociable functional group R ¹ in the formula (27) may be a substituent composed of a repeating unit represented by the following formula (30-1) and a terminal group represented by the following formula (30-2). .

In the formula (30-1) and / or (30-2), R ¹ , R ⁹ , L, n5, and n6 are the same as described above.

The hydroxy group contained in R ^2A may be substituted with an acid dissociable functional group represented by R ¹ as long as the effects of the present invention are not impaired.

In the formula (27), R ⁴ represents the following formula:

で表される置換基であるのが好ましい。
上記式中、Ｒ^５Ａ、ｐ３、ｒ３は前記と同様である。

It is preferable that it is a substituent represented by these.
In the above formula, R ^5A , p3 and r3 are the same as described above.

R ⁴ having the above structure is obtained by using α-acetonaphthone, β-acetonaphthone, 1-naphthaldehyde, 2-naphthaldehyde, biphenylaldehyde, formylterphenyl, formylphenanthrene, formylpyrene, etc. as aromatic carbonyl compounds. Can be introduced.

In the above formula (27), the divalent substituent represented by the combination of R ³ and R ⁴ is represented by the following formula:

で表されるのが好ましい。
上記式中、Ｒ^５Ａ、Ｙ、Ｚ、ｐ３およびｒ３は前記と同様である。

It is preferable to be represented by
In the above formula, R ^5A , Y, Z, p3 and r3 are the same as described above.

By using 9-fluorenone, 3-phenyl-9-fluorenone, 1,3-diphenyl-9-fluorenone, acenaphthenone, acenaphthenequinone, phenanthrenequinone, etc. as the aromatic carbonyl compound. Can be introduced.

  The compound of the formula (27) is preferably represented by the following formulas (33-1) to (33-11).

上記式中、Ｒ^１、Ｒ^２Ａ、Ｒ^５Ａ、Ｙ、Ｚ、ｍ０、ｍ２、ｎ０、ｎ２、ｐ３及びｒ３は前記と同様である。

In the above formula, R ¹ , R ^2A , R ^5A , Y, Z, m0, m2, n0, n2, p3 and r3 are the same as described above.

上記式中、Ｒ^１、Ｒ^２Ａ、Ｒ^３、Ｒ^４Ａ、Ｒ^７は、前記と同様であり；
ｋ０、ｊ０、ｍ０、ｎ０は０〜３の整数であり；ｋ１、ｊ１、ｍ１、ｎ１は０〜３の整数であり；ｋ２、ｊ２、ｍ２、ｎ２は０〜４の整数であり；１≦ｋ０＋ｋ１＋ｋ２≦５、１≦ｊ０＋ｊ１＋ｊ２≦５、１≦ｍ０＋ｍ１＋ｍ２≦５、１≦ｎ０＋ｎ１＋ｎ２≦５、１≦ｋ１≦３、１≦ｊ１≦３、１≦ｍ１≦３、および１≦ｎ１≦３を満たす。） In one embodiment of the present invention, the compound (B1) is more preferably represented by the following formula (34).

In the above formula, R ¹ , R ^2A , R ³ , R ^4A and R ⁷ are the same as described above;
k0, j0, m0, n0 are integers of 0-3; k1, j1, m1, n1 are integers of 0-3; k2, j2, m2, n2 are integers of 0-4; 1 ≦ k0 + k1 + k2 ≦ 5, 1 ≦ j0 + j1 + j2 ≦ 5, 1 ≦ m0 + m1 + m2 ≦ 5, 1 ≦ n0 + n1 + n2 ≦ 5, 1 ≦ k1 ≦ 3, 1 ≦ j1 ≦ 3, 1 ≦ m1 ≦ 3, and 1 ≦ n1 ≦ 3. )

上記式中、Ｒ^５Ａ、ｐ３は、前記と同様である。 R ^4A is preferably a substituent represented by the following formulas (35-1) to (35-3).

In the above formula, R ^5A and p3 are the same as described above.

上記式中、Ｒ^５Ａ、Ｙ、ｑ３、ｒ３は前記と同様である。 As the tetravalent substituent represented by the combination of R ^4A and R ³ and R ⁷ , substituents represented by the following formulas (36-1) and (36-2) are preferable.

In the above formula, R ^5A , Y, q3, and r3 are the same as described above.

式（３７）中、Ｒ^１、Ｒ^２Ａ、Ｒ^３、Ｒ^４Ｂ、Ｒ^７、ｋ０、ｊ０、ｍ０、ｎ０、ｋ２、ｊ２、ｍ２、ｎ２は前記と同様である。
ナフタレン構造またはターフェニル構造は剛直な構造であるのでレジスト材料に耐熱性を付与することが出来る。更に、広がったπ共役構造の増感作用により、酸発生剤へのエネルギー伝達効率がよいため高感度が得られる。また、高炭素密度を有する構造であることからＥＵＶ光に対する光透過性がよく、高エネルギー線に対するアウトガス量が小さく、ドライエッチング耐性に優れる。 The compound of formula (34) is preferably represented by the following formula (37).

In formula (37), R ¹ , R ^2A , R ³ , R ^4B , R ⁷ , k0, j0, m0, n0, k2, j2, m2, and n2 are the same as described above.
Since the naphthalene structure or the terphenyl structure is a rigid structure, heat resistance can be imparted to the resist material. Furthermore, high sensitivity can be obtained because the energy transfer efficiency to the acid generator is good due to the sensitizing action of the spread π-conjugated structure. In addition, since it has a structure having a high carbon density, it has good light transmittance with respect to EUV light, a small amount of outgas with respect to high energy rays, and excellent dry etching resistance.

式（３８−１）または（３８−２）中、Ｒ^４Ｂ、Ｒ^８は、前記と同様であり；
Ｒ^１Ｂは、水素または置換メチル基、１−置換エチル基、１−置換−ｎ−プロピル基、１−分岐アルキル基、シリル基、アシル基、１−置換アルコキシメチル基、環状エーテル基およびアルコキシカルボニル基からなる群から選択される酸解離性官能基であり；
複数個のＲ^１Ｂ、Ｒ^８、Ｙ、ｑ３およびｒ３は、各々同一でも異なっていても良い。 The compound of formula (37) is preferably represented by the following formula (38-1) or (38-2).

In formula (38-1) or (38-2), R ^4B and R ⁸ are the same as defined above;
R ^1B is hydrogen or a substituted methyl group, 1-substituted ethyl group, 1-substituted n-propyl group, 1-branched alkyl group, silyl group, acyl group, 1-substituted alkoxymethyl group, cyclic ether group and alkoxycarbonyl. An acid dissociable functional group selected from the group consisting of groups;
A plurality of R ^1B , R ⁸ , Y, q3 and r3 may be the same or different.

The compound of formula (37) is preferably represented by the following formula (39).

In formula (39), R ¹ , R ^2A , R ³ , R ^5A , R ⁷ , k0, j0, m0, n0, k1, j1, m1, n1, k2, j2, m2, and n2 are the same as described above. .

式（４０）中、Ｒ^１、Ｒ^２Ａ、Ｒ^３、Ｒ^５Ａ、Ｒ^７、ｐ１、ｋ０、ｊ０、ｍ０、ｎ０、ｋ１、ｊ１、ｍ１、ｎ１、ｋ２、ｊ２、ｍ２、ｎ２は前記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of formula (39) is preferably represented by the following formula (40).

In formula (40), R ¹ , R ^2A , R ³ , R ^5A , R ⁷ , p1, k0, j0, m0, n0, k1, j1, m1, n1, k2, j2, m2, and n2 are the same as above. It is. The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（４１）中、Ｒ^１、Ｒ^２Ａ、ｋ０、ｊ０、ｍ０、ｎ０、ｋ１、ｊ１、ｍ１、ｎ１、ｋ２、ｊ２、ｍ２、ｎ２は前記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of formula (40) is preferably represented by the following formula (41).

In formula (41), R ¹ , R ^2A , k0, j0, m0, n0, k1, j1, m1, n1, k2, j2, m2, and n2 are the same as described above. The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（１４）中、Ｒ^１Ｂ、Ｒ^８は上記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of formula (41) is preferably represented by the following formula (42).

In formula (14), R ^1B and R ⁸ are the same as described above. The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 Further, the compound of the formula (41) is preferably represented by the following formula (43).

The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（４４）中、Ｒ^１、Ｒ^２Ａ、Ｒ^３、Ｒ^５Ａ、Ｒ^７、ｋ０、ｊ０、ｍ０、ｎ０、ｋ１、ｊ１、ｍ１、ｎ１、ｋ２、ｊ２、ｍ２、ｎ２は前記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of formula (39) is preferably represented by the following formula (44).

In formula (44), R ¹ , R ^2A , R ³ , R ^5A , R ⁷ , k0, j0, m0, n0, k1, j1, m1, n1, k2, j2, m2, and n2 are the same as described above. . The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（４５）中、Ｒ^１、Ｒ^２Ａ、ｋ０、ｊ０、ｍ０、ｎ０、ｋ１、ｊ１、ｍ１、ｎ１、ｋ２、ｊ２、ｍ２、ｎ２は前記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of formula (44) is preferably represented by the following formula (45).

In Formula (45), R ¹ , R ^2A , k0, j0, m0, n0, k1, j1, m1, n1, k2, j2, m2, and n2 are the same as described above. The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（４６）中、Ｒ^１Ｂ、Ｒ^８は前記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of formula (45) is preferably represented by the following formula (46).

In formula (46), R ^1B and R ⁸ are the same as described above. The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（４７）中、Ｒ^１、Ｒ^２Ａ、Ｒ^３、Ｒ^５Ａ、Ｒ^７、ｋ０、ｊ０、ｍ０、ｎ０、ｋ１、ｊ１、ｍ１、ｎ１、ｋ２、ｊ２、ｍ２、ｎ２、ｐ２は前記と同様である。 The compound of formula (37) is preferably represented by the following formula (47).

In formula (47), R ¹ , R ^2A , R ³ , R ^5A , R ⁷ , k0, j0, m0, n0, k1, j1, m1, n1, k2, j2, m2, n2, and p2 are the same as above. It is.

式（４８）中、Ｒ^１、Ｒ^２Ａ、Ｒ^３、Ｒ^５Ａ、Ｒ^７、ｐ２、ｋ０、ｊ０、ｍ０、ｎ０、ｋ１、ｊ１、ｍ１、ｎ１、ｋ２、ｊ２、ｍ２、ｎ２は前記と同様である。式（４８）で表される化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 Moreover, it is preferable that the compound of Formula (47) is represented by following formula (48).

In formula (48), R ¹ , R ^2A , R ³ , R ^5A , R ⁷ , p2, k0, j0, m0, n0, k1, j1, m1, n1, k2, j2, m2, and n2 are the same as above. It is. The compound represented by the formula (48) is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（４９）中、Ｒ^１Ｂ、Ｒ^８は上記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of formula (48) is preferably represented by the following formula (49).

In formula (49), R ^1B and R ⁸ are the same as above. The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（５０）中、Ｒ^１、Ｒ^２Ａ、Ｒ^３、Ｒ^５Ａ、Ｒ^７、ｐ２、ｋ０、ｊ０、ｍ０、ｎ０、ｋ１、ｊ１、ｍ１、ｎ１、ｋ２、ｊ２、ｍ２、ｎ２は前記と同様である。式（５０）で表される化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of the formula (47) is preferably represented by the following formula (50).

In formula (50), R ¹ , R ^2A , R ³ , R ^5A , R ⁷ , p2, k0, j0, m0, n0, k1, j1, m1, n1, k2, j2, m2, and n2 are the same as above. It is. The compound represented by the formula (50) is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（５１）中、Ｒ^１Ｂ、Ｒ^８は前記と同様である。上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易である。 The compound of formula (50) is preferably represented by the following formula (51).

In formula (51), R ^1B and R ⁸ are the same as described above. The above compound is excellent in sensitivity, heat resistance, and resolution. Moreover, it can be produced from relatively inexpensive phenols, and is easily isolated and purified.

式（５２）中、Ｒ^１、Ｒ^２Ａ、Ｒ^４Ｄは前記と同様であり；
ｋ３、ｊ３、ｍ３、ｎ３、ｘ３、ｙ３は０〜３の整数であり、ｋ４、ｊ４、ｍ４、ｎ４、ｘ４、ｙ４は０〜３の整数であり、ｋ５、ｊ５、ｍ５、ｎ５、ｘ５、ｙ５は０〜４の整数であり、１≦ｋ３＋ｋ４＋ｋ５≦５、１≦ｊ３＋ｊ４＋ｊ５≦５、１≦ｍ３＋ｍ４＋ｍ５≦５、１≦ｎ３＋ｎ４＋ｎ５≦５、１≦ｘ３＋ｘ４＋ｘ５≦５、１≦ｙ３＋ｙ４＋ｙ５≦５、１≦ｋ４≦３、１≦ｊ４≦３、１≦ｍ４≦３、１≦ｎ４≦３、１≦ｘ４≦３、１≦ｙ４≦３を満たす。 In one embodiment of the present invention, the compound (B1) is more preferably represented by the following formula (52).

In formula (52), R ¹ , R ^2A and R ^4D are the same as described above;
k3, j3, m3, n3, x3, y3 are integers of 0-3, k4, j4, m4, n4, x4, y4 are integers of 0-3, k5, j5, m5, n5, x5, y5 is an integer of 0 to 4, 1 ≦ k3 + k4 + k5 ≦ 5, 1 ≦ j3 + j4 + j5 ≦ 5, 1 ≦ m3 + m4 + m5 ≦ 5, 1 ≦ n3 + n4 + n5 ≦ 5, 1 ≦ x3 + x4 + x5 ≦ 5, 1 ≦ y3 + y4 + y5 ≦ 5, 1 ≦ k4 ≦ 3, 1 ≦ j4 ≦ 3, 1 ≦ m4 ≦ 3, 1 ≦ n4 ≦ 3, 1 ≦ x4 ≦ 3, 1 ≦ y4 ≦ 3.

式（５３）中、Ｒ^１、Ｒ^２Ａ、ｋ３、ｊ３、ｍ３、ｎ３、ｘ３、ｙ３、ｋ４、ｊ４、ｍ４、ｎ４、ｘ４、ｙ４、ｋ５、ｊ５、ｍ５、ｎ５、ｘ５、ｙ５は前記と同様である。 The compound of the formula (52) is preferably represented by the following formula (53).

In the formula (53), R ¹ , R ^2A , k3, j3, m3, n3, x3, y3, k4, j4, m4, n4, x4, y4, k5, j5, m5, n5, x5, y5 are as described above. It is the same.

式（５４）中、Ｒ^１Ｂ、Ｒ^８は上記と同様である。 The compound of the formula (53) is preferably represented by the following formula (54).

In formula (54), R ^1B and R ⁸ are the same as described above.

Hereinafter, the manufacturing method of a compound (B1) is demonstrated. For example, an acid dissociable functional group can be introduced into at least one phenolic hydroxyl group of the polyphenol compound (A1) as follows.

  Examples of the compound for introducing an acid dissociable functional group include compounds having an acid dissociable functional group or a compound that reacts with a phenolic hydroxyl group of the polyphenol compound (A1) to form an acid dissociable functional group. Active carboxylic acid derivative compounds such as acid, acid chloride, acid anhydride, dicarbonate, alkyl halide, chloromethyl ether, bromomethyl ether, butyl bromoacetate, adamantyl bromoacetate, vinyl alkyl ether, dihydropyran, etc. There is no particular limitation. A compound for introducing an acid-dissociable functional group can be synthesized by a known method or easily available.

  The polyphenol compound (A1) is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran or 1,3-dioxolane. A compound for introducing an acid dissociable functional group such as vinyl alkyl ether or tetrahydropyran is added, and the reaction is carried out at 20 to 60 ° C. for 6 to 72 hours at atmospheric pressure in the presence of an acid catalyst such as pyridinium tosylate. The reaction solution is neutralized with an alkali compound and added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain compound (B1). As the aprotic solvent, 1,3-dioxolane having high solubility in the polyphenol compound (A1) and the acid catalyst is most preferable because of high productivity.

  The polyphenol compound (A1) is dissolved or suspended in an aprotic solvent such as propylene glycol monomethyl ether acetate. Add a compound for introducing an acid dissociable functional group such as chloromethyl ether, bromomethyl ether, butyl bromoacetate, adamantyl bromoacetate, and 20 to 110 ° C. at atmospheric pressure in the presence of an alkali catalyst such as potassium carbonate. React for 6-72 hours. The reaction solution is neutralized with an acid such as hydrochloric acid and added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain compound (B1).

  The polyphenol compound (A1) is dissolved or suspended in an aprotic solvent such as dioxane. A compound for introducing an acid dissociable functional group such as acid chloride, acid anhydride or dicarbonate is added, and in the presence of a base catalyst such as triethylamine or dimethylaminopyridine, 0 to 60 ° C. and 1 to 36 at normal pressure. Let react for hours. The reaction solution is neutralized with an acid such as hydrochloric acid and added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain compound (B1).

  The polyphenol compound (A1) is dissolved or suspended in an aprotic solvent such as dichloromethane. In the presence of an esterifying agent such as 2-bromo-1-ethylpyridinium tetrafluoroborate and a base catalyst such as triethylamine or dimethylaminopyridine, a compound for introducing an acid dissociable functional group such as carboxylic acid is added. The reaction is carried out at 10 to 120 ° C. for 1 to 36 hours. The reaction solution is neutralized with an acid such as hydrochloric acid and added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain compound (B1).

  In the present invention, the acid dissociable functional group means a characteristic group that is cleaved in the presence of an acid to generate an alkali-soluble group. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group. A phenolic hydroxyl group and a carboxyl group are preferable, and a phenolic hydroxyl group is particularly preferable. The acid-dissociable functional group preferably has a property of causing a chain-breaking reaction in the presence of an acid in order to enable pattern formation with higher sensitivity and higher resolution.

  In order to further reduce the amount of residual metal of the compound (B1), purification may be performed as necessary. The purification method is the same as the purification method of the polyphenol compound (A1).

  Compound (B1) is preferably 1% by weight at 23 ° C. in at least one solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, butyl acetate, 3-methylmethoxypropionate or ethyl propionate. Above, more preferably 3% by weight or more, still more preferably 5% by weight or more. Since it has such solubility, troubles such as precipitation after preparation of the radiation-sensitive composition containing the compound (B1) or performance change can be avoided, and the use of a safe solvent that can be used in a semiconductor factory can be avoided. It becomes possible.

  Since the solid component of the radiation-sensitive composition containing the compound (B1) has a high extinction coefficient with respect to light having a wavelength of 248 nm used for KrF lithography, it can be used as a resist for a shade mask. The solid component can form an amorphous film by a spin coating method to form a resist pattern for a shade mask. The extinction coefficient of the resist for shade mask is preferably 5000 L / (cm · mol) or more, more preferably 10000 L / (cm · mol) or more, further preferably 20000 L / (cm · mol) or more, and 30000 L / (cm · mol). The above is particularly preferable.

  Compound (B1) can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process.

  The dissolution rate of the amorphous film of the compound (B1) in the 2.38 mass% TMAH aqueous solution at 23 ° C. is preferably 10 Å / sec or more, more preferably 10 to 10000 Å / sec, further preferably 100 to 1000 Å / sec. It can melt | dissolve in an alkali developing solution as it is 10 tons / sec or more, and can be set as a resist. In addition, when the dissolution rate is 10000 kg / sec or less, the resolution may be improved. This is because the change in solubility due to the dissociation of the acid-dissociable functional group of compound (B1) results in a large contrast at the interface between the exposed portion dissolved in the alkali developer and the unexposed portion not dissolved in the alkali developer. Presumed to be. Further, there is an effect of reducing LER and reducing defects.

  The glass transition temperature of the compound (B1) is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. When the glass transition temperature is within the above range, the semiconductor lithography process has heat resistance capable of maintaining the pattern shape and can provide performance such as high resolution.

  The crystallization calorific value obtained by differential scanning calorimetry of the glass transition temperature of the compound (B1) is preferably less than 20 J / g. Further, (crystallization temperature) − (glass transition temperature) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, further preferably 100 ° C. or higher, and particularly preferably 130 ° C. or higher. When the crystallization heat generation amount is less than 20 J / g, or (crystallization temperature) − (glass transition temperature) is within the above range, an amorphous film can be easily formed by spin-coating the radiation-sensitive composition, and The film formability required for the resist can be maintained for a long time, and the resolution can be improved.

  The compound (B1) is useful as a positive resist material that becomes a compound soluble in an alkaline developer by irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. It is considered that the compound (B1) is irradiated with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, whereby the acid dissociable functional group is dissociated and becomes a compound soluble in an alkali developer.

  The solvent used for the radiation sensitive composition of (1) can be used for the radiation sensitive composition of (2).

  The dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition with respect to the 2.38 mass% TMAH aqueous solution at 23 ° C. is preferably 5 Å / sec or less. The amorphous film is exposed to a desired pattern by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, and heated at 20 to 250 ° C., if necessary, against 2.38 mass% TMAH aqueous solution at 23 ° C. The dissolution rate is preferably 10 Å / sec or more. By satisfying the above conditions, it is possible to provide a pattern shape with excellent yield and excellent shape.

  Although the compound (B1) is a low molecular weight compound having a molecular weight of 400 to 3100, it has high amorphous properties, high heat resistance, high etching resistance, and high safety solvent solubility. In addition, it has characteristics such as no sublimation and a large absorption coefficient at 248 nm. From the above characteristics, the positive radiation-sensitive composition containing the compound (B1) can give a good pattern shape with low LER. It is also useful as a material for KrF shade masks.

The radiation sensitive composition (2) has a solid component
Compound (B1)
It preferably contains an acid generator (C) that generates acid upon irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray.
In this case, the radiation sensitive composition (2) is usually a positive radiation sensitive composition.

  The total content of the compound (B1) and the acid generator (C) is 0.1 to 100% by weight, preferably 1 to 79.999% by weight, more preferably 1 to 59.999%, based on the total weight of the solid components. % By weight, more preferably 1-49.999% by weight, particularly preferably 1-39.999% by weight.

  The solid component of the radiation-sensitive composition (2) includes a polyphenol compound (A1), a resin (A2) that is hardly soluble in water and soluble in an alkaline developer, hardly soluble in water and soluble in an alkaline developer. A certain dissolution accelerator (A3), a resin (B2) having an acid dissociable functional group whose solubility in an alkaline developer is increased by the action of an acid, and an acid dissociative function whose solubility in an alkaline developer is increased by the action of an acid A dissolution inhibiting compound (B3) having a group, an acid diffusion controller (D), and a quinonediazide sulfonic acid ester compound (E2) can be blended.

  In addition, the radiation-sensitive composition (2) includes a dissolution control agent (F), a sensitizer (G), a surfactant (H), an organic carboxylic acid, an oxo acid of phosphorus, or a derivative (I) thereof. Various additives can be blended.

The radiation sensitive composition (3) comprises 1 to 89% by weight of a solid component containing a quinonediazide sulfonic acid ester compound (E1) synthesized from a polyphenol compound (A1) and 11 to 99% by weight of a solvent, preferably 1 to 1% of a solid component. 49% by weight and 51 to 99% by weight of solvent, more preferably 1 to 39% by weight of solid component and 61 to 99% by weight of solvent, further preferably 1 to 29% by weight of solid component and 71 to 99% by weight of solvent, particularly preferably Contains 1 to 19 weight percent solids and 81 to 99 weight percent solvent.
In this case, the radiation sensitive composition (3) is a positive radiation sensitive composition.

  The total content of the quinonediazide sulfonic acid ester compound (E1) is 0.1 to 100% by weight, preferably 1 to 79.999% by weight, more preferably 1 to 59.999% by weight, based on the total weight of the solid components. More preferably, it is 1-49999 weight%, Most preferably, it is 1-39-1999 weight%.

  The production method of the quinonediazide sulfonic acid ester compound (E1) is not particularly limited, but quinonediazidesulfonic acid halide, preferably quinonediazidesulfonic acid chloride, in a solvent such as acetone, dioxane, tetrahydrofuran, etc. according to a conventional method, sodium carbonate, carbonic acid In the presence of an inorganic base such as sodium hydride, sodium hydroxide, potassium hydroxide, or an organic base such as trimethylamine, triethylamine, tripropylamine, diisopropylamine, tributylamine, pyrrolidine, piperidine, piperazine, morpholine, pyridine, dicyclohexylamine, It can be obtained by reacting with the polyphenol compound (A1).

  In order to further reduce the residual metal amount of the quinonediazide sulfonic acid ester compound (E1), purification may be performed as necessary. The purification method is the same as the purification method of the polyphenol compound (A1).

  The molecular weight of the quinonediazide sulfonic acid ester compound (E1) is 400 to 3100, preferably 400 to 2000, more preferably 400 to 1500, still more preferably 500 to 1500, and particularly preferably 600 to 900. Within the above range, LER can be reduced and a good resist pattern can be provided while maintaining the film formability, heat resistance and etching resistance necessary for the resist.

  The quinonediazide sulfonic acid ester compound (E1) has a low sublimation property under normal pressure at 100 ° C. or lower, preferably 120 ° C. or lower, more preferably 130 ° C., further preferably 140 ° C. or lower, particularly preferably 150 ° C. or lower. preferable. The low sublimation property means that, in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10%, preferably 5%, more preferably 3%, still more preferably 1%, particularly preferably 0.1. % Or less is preferable. Since the sublimation property is low, it is possible to prevent exposure apparatus from being contaminated by outgas during exposure. Moreover, a favorable pattern shape can be given with low LER.

  The quinonediazide sulfonic acid ester compound (E1) is preferably at 23 ° C. in at least one solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, butyl acetate, 3-methylmethoxypropionate or ethyl propionate. Dissolves 1% by weight or more, more preferably 3% by weight or more, and still more preferably 5% by weight or more. Because of this solubility, it is possible to avoid troubles such as precipitation and performance changes after the preparation of the radiation-sensitive composition containing quinonediazide sulfonate (E1), and a safe solvent that can be used in semiconductor factories. Can be used.

  Since the solid component of the radiation-sensitive composition containing the quinonediazide sulfonic acid ester compound (E1) has a high extinction coefficient with respect to light having a wavelength of 248 nm used for KrF lithography, it can be used as a resist for a shade mask. The solid component can form an amorphous film by a spin coating method to form a resist pattern for a shade mask. The extinction coefficient of the resist for shade mask is preferably 5000 L / (cm · mol) or more, more preferably 10000 L / (cm · mol) or more, further preferably 20000 L / (cm · mol) or more, and 30000 L / (cm · mol). The above is particularly preferable.

  The quinonediazide sulfonic acid ester compound (E1) can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process.

  The glass transition temperature of the quinonediazide sulfonic acid ester compound (E1) is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. When the glass transition temperature is within the above range, the semiconductor lithography process has heat resistance capable of maintaining the pattern shape and can provide performance such as high resolution.

  The calorific value of crystallization determined by differential scanning calorimetric analysis of the glass transition temperature of the quinonediazide sulfonic acid ester compound (E1) is preferably less than 20 J / g. Further, (crystallization temperature) − (glass transition temperature) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, further preferably 100 ° C. or higher, and particularly preferably 130 ° C. or higher. When the crystallization heat generation amount is less than 20 J / g, or (crystallization temperature) − (glass transition temperature) is within the above range, an amorphous film can be easily formed by spin-coating the radiation-sensitive composition, and The film formability required for the resist can be maintained for a long time, and the resolution can be improved.

    The quinonediazide sulfonic acid ester compound (E1) is useful as a positive resist material that becomes a compound soluble in an alkaline developer by irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. The quinonediazide sulfonic acid ester compound (E1) is hardly soluble in an alkali developer, but the diazo group is decomposed by irradiation with any one of radiation selected from KrF excimer laser, extreme ultraviolet light, electron beam or X-ray irradiation. This is thought to be because, after producing ketene, it becomes a carboxylic acid by hydrolysis and becomes a compound soluble in an alkaline developer.

  The solid component of the radiation-sensitive composition (3) includes a polyphenol compound (A1), a resin (A2) that is hardly soluble in water and soluble in an alkaline developer, and hardly soluble in water and soluble in an alkaline developer. A certain solubility accelerator (A3), compound (B1), a resin (B2) having an acid-dissociable functional group whose solubility in an alkaline developer is increased by the action of an acid, and an increase in solubility in an alkaline developer by the action of an acid A dissolution inhibiting compound (B3) having an acid dissociable functional group, an acid generator (C), an acid diffusion controller (D), and a quinonediazide sulfonic acid ester compound (E2) can be blended.

  Other solid components of the radiation sensitive composition (3) include a dissolution control agent (F), a sensitizer (G), a surfactant (H), an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof (I ) And other additives can be blended.

  As the solid component of the radiation sensitive composition (3), a solvent used in the radiation sensitive composition (1) can be used.

  The dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition (3) in the 2.38 mass% TMAH aqueous solution at 23 ° C. is preferably 5 Å / sec or less. The amorphous film is exposed to a desired pattern by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, and heated at 20 to 250 ° C., if necessary, against 2.38 mass% TMAH aqueous solution at 23 ° C. The dissolution rate is preferably 10 Å / sec or more. By satisfying the above conditions, it is possible to provide a pattern shape with excellent yield and excellent shape.

  The quinonediazide sulfonic acid ester compound (E1) is a low molecular compound having a molecular weight of 400 to 3100, but has high amorphous properties, high heat resistance, high etching resistance, and high safety solvent solubility. In addition, it has characteristics such as no sublimation and a large absorption coefficient at 248 nm. From the above characteristics, the positive radiation sensitive composition containing the quinonediazide sulfonic acid ester compound (E1) can give a good pattern shape with low LER. It is also useful as a material for KrF shade masks.

  To form a resist pattern, first, the radiation-sensitive composition of the present invention is applied to a substrate such as a silicon wafer, a gallium arsenide wafer, or an aluminum-coated wafer by spin coating, casting coating, roll coating, etc. A resist film is formed by coating by a coating means. The thickness of the resist film is not particularly limited, and is preferably 0.01 to 10 μm, more preferably 0.05 to 1 μm, and still more preferably 0.08 to 0.5 μm.

  If necessary, a surface treatment agent may be applied in advance on the substrate. Examples of the surface treatment agent include silane coupling agents such as hexamethylene disilazane (hydrolyzable polymerizable silane coupling agent having a polymerizable group), anchor coating agents or base agents (polyvinyl acetal, acrylic resins, vinyl acetate). Based resins, epoxy resins, urethane resins, etc.), and coating agents in which these base materials and inorganic fine particles are mixed.

  If necessary, a protective film may be formed on the resist film in order to prevent an amine or the like floating in the atmosphere from entering. By forming a protective film, the acid generated in the resist film due to radiation reacts with a compound that reacts with an acid such as amine floating as an impurity in the atmosphere and deactivates, and the resist image deteriorates and sensitivity. Can be prevented from decreasing. As the material for the protective film, a water-soluble and acidic polymer is preferable. Examples thereof include polyacrylic acid and polyvinyl sulfonic acid.

  In order to obtain a high-precision fine pattern and to reduce outgas during exposure, it is preferable to heat before irradiation (before exposure). The heating temperature varies depending on the composition of the radiation sensitive composition, but is preferably 20 to 250 ° C, more preferably 40 to 150 ° C.

  Next, the resist film is exposed to a desired pattern by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. The exposure conditions and the like are appropriately selected according to the composition of the radiation sensitive composition. In the present invention, in order to stably form a high-precision fine pattern, it is preferable to heat after irradiation (after exposure). The post-exposure heating temperature (PEB) varies depending on the composition of the radiation-sensitive composition, but is preferably 20 to 250 ° C, more preferably 40 to 150 ° C.

  Next, the exposed resist film is developed with an alkaline developer to form a predetermined resist pattern. Examples of the alkaline developer include alkaline such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), choline and the like. An alkaline aqueous solution of preferably 1 to 10% by weight, more preferably 1 to 5% by weight, in which one or more compounds are dissolved, is used. An appropriate amount of alcohols such as methanol, ethanol, isopropyl alcohol and the above surfactants can be added to the alkaline developer. Of these, it is particularly preferable to add 10 to 30% by weight of isopropyl alcohol. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  After forming the resist pattern, the pattern wiring board is obtained by etching. Etching can be performed by a known method such as dry etching using plasma gas, wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like. After the resist pattern is formed, a plating process such as copper plating, solder plating, nickel plating, or gold plating can be performed.

  The residual resist pattern after etching can be peeled off with an aqueous solution that is stronger than an organic solvent or an alkaline developer. Examples of the organic solvent include PGMEA, PGME, EL, acetone, tetrahydrofuran, and the like. Examples of the strong alkaline aqueous solution include 1 to 20% by weight sodium hydroxide aqueous solution and 1 to 20% by weight potassium hydroxide aqueous solution. Is mentioned. Examples of the peeling method include a dipping method and a spray method. In addition, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.

  After forming a resist pattern using the radiation-sensitive composition of the present invention, a wiring substrate can also be formed by a method in which a metal is vacuum-deposited and then the resist pattern is eluted with a solution, that is, a lift-off method.

Synthesis Examples 1-30
The polyphenol compound (A1), which is a compound represented by the following formulas (101) to (130), was synthesized with reference to JP-A-2005-326838. The raw materials used are shown in Table 1.

Synthesis Examples 31-63
The compound (B1) represented by the following formulas (201) to (233) was synthesized with reference to JP-A-2005-346024. The raw materials used are shown in Table 2.

Synthesis Example 64
Synthesis of Compound (701) (Quinone Diazide Sulfonate Compound (E1)) 69.2 g of Compound (126) and 24.4 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride were dissolved in 200 ml of acetone. A solution of N-methylpiperidine (9.46 g) in acetone (10 ml) was added dropwise at room temperature and room temperature over 30 minutes, and the mixture was stirred for 3 hours, and then acetic acid (5.7 g) was added. Thereafter, in addition to a large amount of water, a solid was precipitated. After washing with distilled water three times, suction filtration was performed, and the resulting yellow powder was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/1) to obtain the target compound (701).

Synthesis Example 65
Synthesis of Resin (501) (Resin Having Acid-Dissociable Functional Group (B2)) To a solution obtained by adding 5 ml of acetone and 1.2 mg of dimethylaminopyridine to 0.74 g of polyhydroxystyrene weight average molecular weight 8000 (aldrich reagent), Di-tert-butyl dicarbonate 0.37 g (1.5 mmol) was added dropwise over 10 minutes, and the mixture was stirred at 40 ° C. for 24 hours. The reaction solution was added to a large amount of water to precipitate a solid to obtain a white powder. After washing with distilled water three times, suction filtration was performed, and finally, drying under reduced pressure was performed to obtain a target resin (501). The introduction rate of the acid-dissociable protecting group was 30 mol%.

Synthesis Example 66
Synthesis of Compound (601) (Dissolution-inhibiting Compound (B3) Having Acid-Dissociable Functional Group) Tris (4-hydroxyphenyl) benzene (aldrich reagent) 1.77 g (5 mmol) in acetone 5 ml, dimethylaminopyridine 1. To a solution to which 2 mg was added, 3.93 g (16 mmol) of di-tert-butyl dicarbonate was added dropwise over 10 minutes, and the mixture was stirred at 40 ° C. for 24 hours. The reaction solution was added to a large amount of water to precipitate a solid to obtain a white powder. After washing with distilled water three times, suction filtration was performed, and finally drying under reduced pressure was performed to obtain the target compound (601).

Evaluation of resist pattern The products obtained in Synthesis Examples 1 to 64 and Comparative Synthesis Examples 1 and 2 and the components shown in Table 3 were blended, and filtered through a 0.1 μm Teflon (registered trademark) filter for radiation sensitivity. A sex composition was prepared. Each radiation-sensitive composition was applied onto a silicon wafer using a spin coater and dried on a hot plate at 110 ° C. for 90 seconds to obtain a resist film having a thickness of about 0.1 μm.
The resist film was irradiated with an electron beam using an electron beam lithography apparatus (ELS-7500, manufactured by Elionix Co., Ltd., acceleration voltage 50 KeV). After irradiation, each was heated at a predetermined temperature for 90 seconds, immersed in a 2.38 wt% TMAH aqueous solution for 60 seconds, rinsed with distilled water for 30 seconds, and dried. The obtained line and space was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technology Corporation).
The evaluation was performed on a 1: 1 line and space with an interval of 80 nm. The results are shown in Table 4.
(1) Evaluation of pattern shape The cross-sectional photograph of the obtained line and space was observed and evaluated with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technology Corporation).
A: Rectangular pattern (good pattern)
B: Almost rectangular pattern (almost good pattern)
C: Non-rectangular pattern (unfavorable pattern)
(2) Evaluation of line edge roughness (LER) SEM terminal PC V5 offline measurement software for Hitachi Semiconductor (Hitachi Science Systems Co., Ltd.) at an arbitrary 300 points in the length direction (0.75 μm) of line patterns at intervals of 80 nm. Was used to measure the distance between the edge and the reference line. The standard deviation (3σ) was calculated from the measurement result.
A: LER (3σ) ≦ 4.5 nm (good LER)
B: 4.5 nm <LER (3σ) ≦ 5.5 nm (almost good LER)
C: 5.5 nm <LER (3σ) (not good LER)

In Tables 1 to 3, the abbreviations are as follows.
R-1: polyhydroxystyrene weight average molecular weight 8000 (aldrich reagent)
R-2: Polyhydroxystyrene weight average molecular weight 20000 (Aldrich reagent)
P-1: triphenylsulfonium p-toluenesulfonate P-2: diphenyltrimethylphenylsulfonium p-toluenesulfonate P-3: triphenylsulfonium trifluoromethanesulfonate P-4: triphenylsulfonium nonafluoromethanesulfonate Q-1: 2, 4,6-triphenylimidazole Q-2: trioctylamine Q-3: triethanolamine S-1: PGME
S-2: EP
S-3: PGMEA
S-4: EL
D-1: Megafuck R-08 (Dainippon Ink Chemical Co., Ltd.)
D-2: BYK-302 (manufactured by Big Chemie Japan Co., Ltd.)

Claims (9)

A radiation-sensitive composition comprising 1 to 49% by weight of a solid component and 51 to 99% by weight of a solvent, wherein the solid component is
A molecular weight of 300 synthesized by a condensation reaction of a mono- to tetravalent aromatic ketone or aldehyde having 5 to 45 carbon atoms and a compound having 6 to 15 carbon atoms and containing 1 to 3 phenolic hydroxyl groups. To 3000 polyphenol compounds (A1)
A radiation-sensitive composition comprising: The solid component is
Acid generator (C) that generates acid upon irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray
The radiation sensitive composition of Claim 1 characterized by the above-mentioned. The solid component is
Resin (B2) having an acid-dissociable functional group whose solubility in an alkaline developer is increased by the action of an acid and / or a dissolution inhibiting compound having an acid-dissociable functional group whose solubility in an alkaline developer is increased by the action of an acid (B3),
An acid generator (C) that generates acid upon irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray;
The radiation sensitive composition of Claim 1 characterized by the above-mentioned. The solid component is
A quinonediazide sulfonic acid ester compound (E2) synthesized from a polyphenol other than the polyphenol compound (A1),
The radiation sensitive composition of Claim 1 characterized by the above-mentioned. The solid component
The compound (B1) having a molecular weight of 400 to 3100 having a structure in which an acid-dissociable functional group is introduced into at least one phenolic hydroxyl group of the polyphenol compound (A1) according to claim 1.
A radiation-sensitive composition comprising 1 to 49% by weight of a solid component and 51 to 99% by weight of a solvent. The solid component is
Acid generator (C) that generates acid upon irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray
The radiation sensitive composition of Claim 5 characterized by the above-mentioned. The solid component
The quinonediazide sulfonic acid ester compound (E1) synthesized from the polyphenol compound (A1) according to claim 1
A radiation-sensitive composition comprising 1 to 49% by weight of a solid component and 51 to 99% by weight of a solvent. The polyphenol compound (A1), the compound (B1), and the quinonediazide sulfonic acid ester compound (E1) include a conjugated structure in which at least two benzene rings and / or non-bonded electron pairs of heteroatoms are involved. The radiation-sensitive composition described. The radiation-sensitive composition according to claim 8, wherein the conjugated structure is a naphthalene structure.