JP2008145539A - Radiation-sensitive resist composition - Google Patents

Abstract

A radiation-sensitive resist that is sensitive not only to ultraviolet rays such as i-rays and g-rays but also to radiation such as excimer laser light such as visible rays and KrF, electron beams, extreme ultraviolet rays (EUV), X-rays, and ion beams. A composition is provided.
(A) A polyphenol produced by a condensation reaction between a tri- to tetra-valent aromatic aldehyde having 7 to 38 carbon atoms and a compound having 6 to 15 carbon atoms and having 1 to 3 phenolic hydroxyl groups. (B) a resist compound (A) having a molecular weight of 800 to 5000, selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam It is set as the radiation sensitive resist composition characterized by including the acid generator (B) which generate | occur | produces an acid directly or indirectly by irradiation of any radiation, and an acid crosslinking agent (C).
[Selection figure] None

Description

  The present invention relates to a radiation-sensitive resist composition containing a resist compound represented by a specific chemical structural formula, an acid generator, and an acid crosslinking agent, which are useful as an acid amplification type non-polymeric resist material. The radiation-sensitive resist composition of the present invention is used as a radiation-sensitive material sensitive to radiation such as ultraviolet rays, far ultraviolet rays, electron beams, extreme ultraviolet rays (EUV), and X-rays. Used for

  Conventional general resist materials are polymer materials capable of forming an amorphous thin film. For example, a resist thin film prepared by applying a polymethyl methacrylate solution on a substrate is irradiated with ultraviolet rays, far ultraviolet rays, electron beams, extreme ultraviolet rays (EUV), X-rays, etc., to form a line pattern of about 0.1 μm. Is forming.

  However, since the polymer resist has a large molecular weight of about 10,000 to 100,000 and a wide molecular weight distribution, the lithography using the polymer resist causes roughness on the surface of the fine pattern, making it difficult to control the pattern dimensions. , Yield decreases. Therefore, there is a limit to miniaturization in conventional lithography using a polymer resist material. In order to produce finer patterns, various low molecular weight resist materials have been disclosed.

  Examples of non-polymer resist materials are (1) positive and negative resists derived from fullerenes, (2) positive and negative resists derived from calixarene, and (3) starburst compounds. (4) a positive resist derived from a dendrimer, (5) a positive resist derived from a dendrimer / calixarene, and (6) a positive resist derived from a highly branched starburst compound. (7) a positive resist derived from a starburst type compound having trimesic acid as a central skeleton and having an ester bond; (8) a negative resist derived from a cyclic polyphenol compound; and (9) derived from a polyphenol compound. Derived from negative resist and (10) calix resorcinarene Negative resist and the like.

  About (1), although etching resistance is good, applicability | paintability and a sensitivity have not reached the practical use level (refer patent documents 1-5). About (2), although it is excellent in etching tolerance, since a solubility with respect to a developing solution is bad, a satisfactory pattern is not obtained (refer patent documents 6-8). Regarding (3), the image may be distorted during heat treatment after exposure because of low heat resistance (see Patent Documents 9 to 11). Regarding (4), the manufacturing process is complicated and the heat resistance is low, so the image may be distorted during the heat treatment after exposure, and it cannot be said that it is practical (see Non-Patent Document 1). . Regarding (5), the manufacturing process is complicated and the raw material is expensive, so it cannot be said that it is practical (see Patent Documents 12 and 13). About (6), since a manufacturing process is complicated and a raw material is expensive, it cannot be said that it is practical. Regarding (7), since the heat resistance is low, the image may be distorted during the heat treatment after exposure, and the substrate adhesion is insufficient, so that it cannot be said that it is practical (see Patent Document 14). As for (8) and (9), the amorphous property and the etching resistance are not sufficient, and improvement is desired (see Patent Documents 15 to 17). Regarding (10), the amorphous nature and the safety solvent solubility are not sufficient, and improvement is desired (see Patent Documents 18 to 19).

  In view of the above problems, we have invented a negative resist derived from a specific polyphenol compound (see Patent Document 20). However, although this resist is excellent in performance such as amorphousness, etching resistance, sensitivity, resolution, and low line edge roughness, the demand for line edge roughness is high, and further reduction of line edge roughness is desired.

JP-A-7-134413 JP 9-211182 A JP-A-10-282649 Japanese Patent Application Laid-Open No. 11-143074 Japanese Patent Laid-Open No. 11-258996 JP-A-11-72916 JP-A-11-322656 JP-A-9-236919 JP 2000-305270 A JP 2002-99088 A JP 2002-99089 A JP 2002-49152 A JP 2003-183227 A Japanese Patent Laid-Open No. 2002-328466 Japanese Patent Laid-Open No. 11-153863 JP 2003-207893 A JP 2004-334106 A JP-A-9-236919 JP 2004-18421 A International Publication No. 2005/101127 Pamphlet Proceedings of SPIEvol. 3999 (2000) P1202-1206

  The object of the present invention is not only ultraviolet rays such as i-rays and g-rays, but also sensitivity such as visible rays, excimer laser beams such as KrF, electron beams, extreme ultraviolet rays (EUV), X-rays, ion beams, etc. The object is to provide a radiation resist composition. Still another object of the present invention is to provide a non-polymeric radiation-sensitive resist composition having high sensitivity, high resolution, high heat resistance and solvent solubility by a simple production process.

As a result of intensive research, the inventors of the present invention include a compound that satisfies a specific chemical structural condition, an acid generator that generates an acid directly or indirectly upon irradiation with radiation, and an acid crosslinking agent that crosslinks with an acid. It has been found that the composition is useful for solving the above problems.
That is, the present invention
(A) a polyphenol compound produced by a condensation reaction between a tri- to tetravalent aromatic aldehyde having 7 to 38 carbon atoms and a compound having 6 to 15 carbon atoms and having 1 to 3 phenolic hydroxyl groups, And (b) any radiation selected from the group consisting of a resist compound (A) having a molecular weight of 800 to 5000, visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam It is related with the radiation sensitive resist composition characterized by including the acid generator (B) which generate | occur | produces an acid directly or indirectly by irradiation, and an acid crosslinking agent (C).

  By using the radiation-sensitive composition of the present invention, a resist pattern with high sensitivity and high resolution can be obtained, so that a highly integrated semiconductor element can be manufactured with high productivity.

Hereinafter, the present invention will be described in detail.
The radiation sensitive resist composition of this invention contains a resist compound (A), an acid generator (B), and an acid crosslinking agent (C). The resist compound (A) in the present invention satisfies the following conditions (a) and (b) simultaneously.

Condition (a): The resist compound (A) has 7 to 38 carbon atoms and a tri to tetravalent aromatic aldehyde (hereinafter referred to as aromatic aldehyde (A1)) and 1 to 3 carbon atoms having 6 to 15 carbon atoms. It is the polyphenol compound manufactured by the condensation reaction with the compound (henceforth a phenolic compound (A2)) containing the phenolic hydroxyl group of this.
The resist compound (A) has a tertiary carbon atom in the molecule, and has 3 to 4 chemical structures in which two phenols and one aromatic ring are bonded to the tertiary carbon atom. This chemical structure can provide stable amorphous properties (non-crystalline and non-crystallizable (difficult) properties) over a long period of time, and is necessary for pattern formation as a resist material. It has excellent film properties, light transmissivity, solvent solubility, etching resistance, high resolution and low LER resist pattern.

Condition (b): The molecular weight of the resist compound (A) is 800 to 5000.
The molecular weight is 800 to 5000, preferably 800 to 3000, more preferably 800 to 2000, still more preferably 800 to 1500, and particularly preferably 800 to 1000. By making it in the above-mentioned range, it becomes possible to impart good film formability, and resolution and alkali development performance can be improved.

The resist compound (A) satisfying the above conditions (a) and (b) preferably includes at least two conjugated structures involving benzene rings and / or non-bonded electron pairs of heteroatoms.
By having the above conjugated structure, it is possible to impart performance such as film forming property, high etching resistance, low outgas amount during exposure, and high sensitivity due to a sensitizing effect even though it is a low molecular compound. This sensitization effect is considered to be due to absorption of a part of the energy of radiation such as electron beams and extreme ultraviolet rays (EUV), and then the absorbed energy is efficiently transmitted to the acid generator.

  Examples of the conjugated structure include a biphenyl structure, naphthalene structure, fluorene structure, phenylfluorene structure, diphenylfluorene structure, anthracene structure, phenanthrene structure, pyrene structure, benzopyrene structure, acenaphthene structure, acenaphthylene structure, 1-ketoacenaphthene structure, 9-keto- 9,10-dihydrophenanthrene 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, hexaphene structure , Hexacene structure, rubicene structure, fluoracene structure, acephenanthrylene structure, perylene structure, picene structure, pentaphen structure, heptaphen structure Heptacene structure, pyrantolen structure, phenacene structure, naphthacene structure, pentacene structure, aceanthrene structure, acephenanthrene structure, azulene structure, triphenylene structure, p-terphenyl structure, m-terphenyl structure, 1,3,5-triphenylbenzene Structure, 1,2,3-triphenylbenzene structure, 1,2,4-triphenylbenzene structure, phenylnaphthalene structure, binaphthalene structure, ovalen structure, etc., especially biphenyl structure, naphthalene structure, fluorene structure, phenylfluorene Structure, diphenylfluorene structure, pyrene structure, acenaphthene structure, 1-ketoacenaphthene structure, benzophenone structure, xanthene structure, thioxanthene structure, p-terphenyl structure and m-terphenyl structure Preferable from reasons such as to be introduced from one structure is it is relatively inexpensive raw materials.

  More preferably, the conjugated structure involving at least two benzene rings and / or a non-bonded electron pair of a heteroatom is a condensed ring. By having a conjugated structure which is a condensed ring, it is possible to impart performance such as film formability, high etching resistance, low outgas amount during exposure, and high sensitivity due to a further sensitizing effect.

  The resist compound (A) preferably satisfies F <3.0 (F represents the total number of atoms / (total number of carbon atoms−total number of oxygen atoms)), and more preferably satisfies F <2.5. By satisfying the above conditions, the dry etching resistance is excellent.

  The resist compound (A) is selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate, and is the highest for the resist compound (A) It dissolves in a solvent exhibiting solubility at 23 ° C., preferably at least 1 wt%, more preferably at least 3 wt%, even more preferably at least 5 wt%, particularly preferably at least 10 wt%. By satisfying the above conditions, a safe solvent can be used in the semiconductor manufacturing process.

The resist compound (A) used in the present invention is produced by an acid-catalyzed condensation reaction of a tri to tetravalent aromatic aldehyde (A1) and a phenolic compound (A2). Such acid-catalyzed condensation reactions are known, for example, 1 mol to excess of phenolic compound (A2) to 1 mol of aromatic aldehyde (A1), and suppress acid catalyst (hydrochloric acid or sulfuric acid) and by-products. In the presence of a cocatalyst (thioacetic acid or β-mercaptopropionic acid) to be reacted at 60 to 150 ° C. for about 0.5 to 20 hours. The remaining amount of aromatic aldehyde (A1) was 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 was not decreased. The end point of the reaction can be determined from 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 resist compound (A) is obtained by drying.

The resist compound (A) used in the present invention is produced by a base-catalyzed condensation reaction between a tri- to tetravalent aromatic aldehyde (A1) and a phenolic compound (A2). Such a base-catalyzed condensation reaction is known. For example, an aromatic aldehyde (A1) and a phenolic compound (A2) are converted into an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, potassium carbonate, sodium carbonate or the like. The reaction is carried out in the presence of an alkali metal carbonate, an organic acid alkali salt such as sodium acetate, or an organic amine such as diazabicycloundecane. For example, 1 to 16 moles of the phenolic compound (A2) per 1 mole of the tri to tetravalent aromatic aldehyde (A1), alkali metal hydroxide, potassium carbonate, alkali metal carbonate, organic acid alkali salt or organic amine Is used at a temperature of 50 to 150 ° C. for 20 minutes to 20 hours. The remaining amount of aromatic aldehyde was traced by a known method such as liquid chromatography, gas chromatography, thin layer chromatography, IR analysis, and ¹ H-NMR analysis, and the peak area indicating the remaining amount was not reduced. It can be judged that the reaction has ended. 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 resist compound (A) is obtained by drying.

  The resist compound (A) is produced by reacting the tri- to tetravalent aromatic aldehyde (A1) with a hydrogen halide or a halogen gas and reacting the isolated halide with the phenolic compound (A2). You can also

  In order to reduce the amount of residual metal in the resist compound (A), 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. Purification can be performed by a known method as long as the resist compound (A) 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 resist compound (A) 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 method of vacuum drying and hot air drying under the condition that the resist compound (A) is not denatured.

  Examples of the tri- to tetravalent aromatic aldehyde (A1) include, for example, triformylbenzene, triformyltoluene, triformylxylene, triformylnaphthalene, triformylbiphenyl, tris (4-formylphenyl) methane, tris (4 -Formylphenyl) benzene, triformylterphenyl, triformylanthracene, triformylphenanthrene, triformylpyrene, triformylindacene, triformylphenalene, triformylacenaphthylene, triformylphenalene, triformylnaphthacene, tri Formylpentacene, triformyltriphenylene, triformylpyritrin, triformylimidazole, triformylfuran, triformylthiazole, triformylflavone, triformylisoflavone, Traformylbenzene, tetraformylnaphthalene, tetraformylbiphenyl, tetraformylterphenyl, tetraformylanthracene, tetraformylphenanthrene, tetraformylpyrene, tetraformylindacene, tetraformylphenalene, tetraformylacenaphthylene, tetraformylphenalene, Examples include tetraformylnaphthacene, tetraformylpentacene, tetraformyltetraphenylene, tetraformylpyritetrane, tetraformylimidazole, tetraformylfuran, tetraformylthiazole, tetraformylflavone, and tetraformylisoflavone.

  Among these aromatic aldehydes (A1), triformylbenzene, triformylnaphthalene, triacetylnaphthalene, triformylbiphenyl, tris (4-formylphenyl) methane, tris (4-formylphenyl) benzene, tetraformylbenzene, tetraformyl More preferred are naphthalene, tetraacetylnaphthalene, tetraformylbiphenyl, tetraformylterphenyl, triformylbenzene, tris (4-formylphenyl) methane, tris (4-formylphenyl) benzene, triformylnaphthalene, tetraformylbenzene, tetra Formylnaphthalene is more preferred, and triformylbenzene is particularly preferred.

  These aromatic aldehydes (A1) are produced by any known method. For example, a method in which methyl benzenetricarboxylate is reduced using a reducing agent, a method in which benzenetrinitrile is reduced using a reducing agent or hydrogen and a catalyst, and a side chain methyl group of an alkyl aromatic compound such as trimesin is oxidized by air. A method for oxidizing a chlorinated aromatic compound obtained by photochlorination of a side chain of an alkyl aromatic compound such as trimesin, a method for oxidizing an aromatic carboxylic acid chloride such as trimesic acid chloride using an oxidizing agent And a method of oxidizing trihydroxymethylbenzene using an oxidizing agent.

  Further, tri- to tetravalent aromatic ketones can be used in place of the tri- to tetravalent aromatic aldehyde (A1). However, the tri- to tetravalent aromatic aldehyde (A1) is relatively more reactive than these tri- to tetravalent aromatic ketones, and can suppress by-products and produce a high yield. Further, the resist compound (A) to be produced is preferable because the heat resistance tends to be high and a pattern with high resolution tends to be obtained.

  Examples of tri- to tetravalent aromatic ketones include, for example, triacetylbenzene, tribenzoylbenzene, triacetyltoluene, tribenzoyltoluene, triacetylxylene, tribenzoylxylene, triacetylnaphthalene, tribenzoylnaphthalene, triacetylbiphenyl , Tribenzoyl biphenyl, triacetyl terphenyl, tribenzoyl terphenyl, triacetyl anthracene, tribenzoyl anthracene, triacetyl phenanthrene, tribenzoyl phenanthrene, triacetyl pyrene, tribenzoyl pyrene, triacetyl indacene, tribenzoyl indacene, tri Acetylphenalene, tribenzoylphenalene, triacetylacenaphthylene, tribenzoylacenaphthylene, triacetylphena , Tribenzoylphenalene, triacetylnaphthacene, tribenzoylnaphthacene, triacetylpentacene, tribenzoylpentacene, triacetyltriphenylene, tribenzoyltriphenylene, triacetylpyritrin, tribenzoylpyritrin, triacetylimidazole, tribenzoylimidazole , Triacetylfuran, tribenzoylfuran, triacetylthiazole, tribenzoylthiazole, triacetylflavone, tribenzoylflavone, triacetylisoflavone, tribenzoylisoflavone, tetraacetylbenzene, tetrabenzoylbenzene, tetraacetylnaphthalene, tetrabenzoylnaphthalene, tetra Acetyl biphenyl, tetrabenzoyl biphenyl, tetraacetyl terphe , Tetrabenzoylterphenyl, tetraacetylanthracene, tetrabenzoylanthracene, tetraacetylphenanthrene, tetrabenzoylphenanthrene, tetraacetylpyrene, tetrabenzoylpyrene, tetraacetylindacene, tetrabenzoylindacene, tetraacetylphenalene, tetrabenzoylphenalene Tetraacetylacenaphthylene, tetrabenzoylacenaphthylene, tetraacetylphenalene, tetrabenzoylphenalene, tetraacetylnaphthacene, tetrabenzoylnaphthacene, tetraacetylpentacene, tetrabenzoylpentacene, tetraacetyltetraphenylene, tetrabenzoyltetraphenylene, Tetraacetylpyritetrane, tetrabenzoylpyritetrane, tetraacetyl Examples include ruimidazole, tetrabenzoylimidazole, tetraacetylfuran, tetrabenzoylfuran, tetraacetylthiazole, tetrabenzoylthiazole, tetraacetylflavone, tetrabenzoylflavone, tetraacetylisoflavone, tetrabenzoylisoflavone and the like.

Examples of the phenolic compound (A2) include phenol, (C _1-6 alkyl) phenol (for example, cresols such as o-cresol, m-cresol, and p-cresol), dialkylphenol (for example, 2,3-dimethyl). Phenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 2-ethyl-5-methylphenol, thymol, etc., trialkylphenol (2,3,6-trimethylphenol), alkoxyphenol (eg 2-methoxyphenol) Anisole), arylphenol (eg, phenylphenol such as 3-phenylphenol), cycloalkylphenol (eg, 3-cyclohexylphenol), halogenated phenol (eg, chlorophenol, dichloro) Phenol, chlorocresol, bromophenol, dibromophenol), other phenols (eg, naphthol, 5,6,7,8-tetrahydronaphthol), polyhydric phenols (eg, catechol, alkylcatechol, chlorocatechol, resorcinol, alkyl) And resorcinol, hydroquinone, alkylhydroquinone, chlororesorcinol, chlorohydroquinone, pyrogallol, alkyl pyrogallol, 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 resist compound (A) has a tertiary carbon atom in the molecule by using a tri- to tetravalent aromatic aldehyde (A1) as a raw material, and two phenols and It has 3 to 4 chemical structures to which one aromatic ring is bonded. This chemical structure can provide a stable amorphous property (non-crystalline and non-crystallizable (hard)) property over a long period of time, and is necessary for pattern formation as a resist material. It has excellent film properties, light transmissivity, solvent solubility, etching resistance, high resolution and low LER resist pattern.

  The resist compound (A) 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.

  The resist compound (A) in the present invention is preferably one represented by the following formula (1).

（式（１）中、Ｒ²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^２は同一でも異なっていてもよく；
Ｒ^１は置換基を有していても良い、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の三価の基を表し、ｋ３、ｊ３、ｍ３、ｎ３、ｘ３、ｙ３は１〜３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を満たす。）

(In the formula (1), R ² represents a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyloxy group, an aryloyloxy group, a cyano group, and a nitro group. Represents a substituent selected from the group consisting of groups, and a plurality of R ² may be the same or different;
R ¹ represents a trivalent group having 6 to 20 carbon atoms having a benzene structure, naphthalene structure, terphenyl structure, phenanthrene structure or anthracene structure, which may have a substituent, and k3, j3, m3, n3 , X3, y3 are integers of 1 to 3, k5, j5, m5, n5, x5, y5 are integers of 0 to 4, 1 ≦ k3 + k5 ≦ 5, 1 ≦ j3 + j5 ≦ 5, 1 ≦ m3 + m5 ≦ 5 1 ≦ n3 + n5 ≦ 5, 1 ≦ x3 + x5 ≦ 5, and 1 ≦ y3 + y5 ≦ 5 are satisfied. )

In the substituent R ² , the halogen atom includes a chlorine atom, a bromine atom and an iodine atom; the alkyl group includes 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 group , Sec-butoxy groups, tert-butoxy groups and the like, and alkoxy groups having 1 to 4 carbon atoms; aryloxy groups include phenoxy groups; alkenyl groups include vinyl groups, propenyl groups, allyl groups, An alkenyl group having 2 to 4 carbon atoms such as a butenyl group; an acyl group having 1 to 6 carbon atoms such as a formyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, an isovaleryl group, and a pivaloyl group; An aliphatic acyl group, and an aromatic acyl group such as a benzoyl group and a toluoyl group; examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, Butoxycarbonyl group, sec-butoxycarbonyl group, t an alkoxycarbonyl group having 2 to 5 carbon atoms such as an rt-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 ² 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, x is an integer of 0 to 3, and satisfies 1 ≦ n5 + n6 ≦ 5. A plurality of n5, n6, and x may be the same or different. R ³ 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. Examples thereof include alkyl groups having 1 to 4 carbon atoms such as butyl group; examples of cycloalkyl groups include cyclohexyl group, norbornyl group, adamantyl group, etc .; examples of aryl groups include phenyl group, tolyl group, xylyl group, and naphthyl 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, isopropoxy group, n -Butoxy group, isobutoxy group, sec-butoxy group an alkoxy group having 1 to 4 carbon atoms such as a tert-butoxy group; an oxy group such as a phenoxy group as an aryloxy group; a carbon atom such as a vinyl group, a propenyl group, an allyl group, or a butenyl group as an alkenyl group; 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. Aromatic acyl groups such as benzoyl group, toluoyl group and the like; examples of the 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 ³ may be the same or different.

R ² represents a methyl group substituted at the 2-position, 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 It is preferably a methyl group substituted at the 5-position, and R ² is a methyl group substituted at the 2-position, 2,5-position, 2,6-position or 2,3,6-position of the phenolic hydroxyl group More preferably, R ² is more preferably a methyl group substituted at the 2,6 position or the 2,3,6 position of the phenolic hydroxyl group. By satisfying the above conditions, crystallinity can be suppressed, film formability can be improved, and an alkaline developer solubility can be obtained and a pattern having a good shape can be obtained.

As the substituent for R ¹ , those similar to the substituent R ² can be used.

  Although the compound of formula (1) is a low molecular compound, it has good film formability, heat resistance, and dry etching resistance, and has little outgas. Therefore, it can be used as a main resist component, and has high resolution, high sensitivity, and low resistance. A line-edge roughness radiation-sensitive resist composition can be obtained.

  The resist compound (A) in the present invention is more preferably a compound represented by the following formula (3).

（式（３）中、Ｒ２、ｋ３、ｊ３、ｍ３、ｎ３、ｘ３、ｙ３、ｋ５、ｊ５、ｍ５、ｎ５、ｘ５、ｙ５は前記と同様である。）

(In formula (3), R2, k3, j3, m3, n3, x3, y3, k5, j5, m5, n5, x5, and y5 are the same as described above.)

  The resist compound (A) in the present invention is more preferably a compound represented by the following formula (4).

（式（４）中、Ｒ^４は水素原子またはメチル基であり、複数個のＲ^４は同一でも異なっていてもよい。）

(In Formula (4), R ⁴ is a hydrogen atom or a methyl group, and a plurality of R ⁴ may be the same or different.)

  Further, the resist compound (A) in the present invention is particularly preferably a compound represented by the following formula (5).

（式（５）中、Ｒ^４は水素原子またはメチル基であり、複数個のＲ^４は同一でも異なっていてもよい。）

(In Formula (5), R ⁴ is a hydrogen atom or a methyl group, and a plurality of R ⁴ may be the same or different.)

  When the resist compound (A) has a condensed ring, sensitivity and resolution are improved.

  Cross-linking reactivity that causes a cross-linking reaction to the resist compound (A) in the present invention by irradiation with visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, ion beam or chemical reaction induced thereby. Groups may be introduced. The introduction is performed, for example, by reacting the resist compound (A) with a crosslinking reactive group introduction reagent in the presence of a base catalyst. Examples of the crosslinking reactive group include a carbon-carbon multiple bond, an epoxy group, an azide group, a halogenated phenyl group, and a chloromethyl group. Examples of the crosslinking reactive group introduction reagent include acids, acid chlorides, acid anhydrides, carboxylic acid derivatives such as dicarbonates and alkyl halides having such a crosslinking reactive group. A radiation sensitive resist composition containing a resist compound (A) having a crosslinking reactive group is also useful as a non-polymeric radiation sensitive resist composition having high resolution, high heat resistance and solvent solubility.

  The resist compound (A) 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 resist compound (A). Is possible.

  The resist compound (A) 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 resist compound (A) 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. Further, there is an effect of reducing LER and reducing defects.

  The glass transition temperature of the resist compound (A) 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 obtained by differential scanning calorimetry of the glass transition temperature of the resist compound (A) 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 resist compound (A) is useful as a negative resist material that becomes a compound that is hardly soluble in an alkaline developer by irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. It is considered that the resist compound (A) 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.

  The radiation-sensitive resist composition of the present invention contains one or more resist compounds (A) described above. When one type of resist compound is used, high sensitivity and high resolution can be obtained. When two or more types of resist compounds are used, film formability and substrate adhesion are improved.

  In the radiation-sensitive resist composition of the present invention, preferably the solid component is 1 to 80% by weight and the solvent is 20 to 99% by weight, more preferably the solid component is 1 to 50% by weight and the solvent is 50 to 99% by weight, and further preferably. Is 2 to 40% by weight of the solid component and 60 to 98% by weight of the solvent, particularly preferably 2 to 10% by weight of the solid component and 90 to 98% by weight of the solvent. The amount of the resist compound (A) is preferably 3 to 96.9% by weight, more preferably 50 to 96.9% by weight, still more preferably 65 to 96.9% by weight, particularly preferably the total weight of the solid component. Is 81-96.9 wt%. When the blending ratio is as described above, high resolution is obtained and the line edge roughness is reduced.

The composition of the present invention generates an acid directly or indirectly by irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. One or more acid generators (B) are included.
The resist compound (A) is an acid amplification type compound. When an acid coexists, the acid cross-linking agent and the resist compound (A) are cross-linked between molecules or within the molecule to become an alkali-insoluble material. Since the portion where no acid coexists becomes an alkali-soluble material, it can be used as a negative resist capable of alkali development. The method for generating the acid is not particularly limited, but for example, an acid is generated in a radiation exposure part such as ultraviolet rays and high energy by coexisting an acid generator.
That is, in the present invention, as long as an acid is generated in the system, the method for generating the acid is not limited. If an excimer laser is used instead of ultraviolet rays such as g-rays and i-rays, finer processing is possible, and if high-energy rays are used, electron beams, extreme ultraviolet rays (EUV), X-rays, and ion beams are used. Further fine processing is possible.

式（１１）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。 The acid generator (B) is preferably at least one selected from the group consisting of compounds represented by the following formulas (11) to (18).

In formula (11), 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, hydroxyl A 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 (11) includes 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-butoxyphenylsulfonium nona Fluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethanesulfur 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-trifluoromethylbenze Sulfonate, 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 one selected from the group consisting of imidates It is preferable that a class.
In the formula (12), 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, hydroxyl Represents a group or a halogen atom. X ⁻ is the same as described above.
The compound represented by the formula (12) includes bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butyl). Phenyl) 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-bu Tilphenyl) iodonium hexafluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyl Iodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyliodonium-2,4-difluorobenzenesulfonate , Diphenylyo Donium 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（１３）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（１３）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。

Formula (13) 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 (13) 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（１４）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（１４）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 (14), 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 (14) is 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（１５）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（１５）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（１６）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 (15), 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 (15) 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 (16), 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（１７）および（１８）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（１９）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（２０）で示される基である。

In formulas (17) and (18), 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, a cyclopentyl group, or a cyclohexyl group. A cycloalkyl group such as methoxy group, ethoxy group, propoxy group or the like, or an aryl group such as phenyl group, toluyl group or naphthyl group, preferably aryl having 6 to 10 carbon atoms. It is a group. 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 (19), a carbonyl group, an ester group, an amide group or an ether group, and Y ¹⁹ is A hydrogen atom, an alkyl group or an aryl group, and X ²⁰ is independently a group represented by the following formula (20).

式（２０）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 (20), Z < ²² > is an alkyl group, a cycloalkyl group, or an aryl group each independently, R < ²² > is an alkyl group, a cycloalkyl group, or an alkoxyl group, and r is an integer of 0-3.

  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, an acid generator having an aromatic ring is more preferable. Further, an acid generator represented by the formula (11) or (12), wherein X ⁻ is a sulfonate ion having an aryl group or a halogen-substituted aryl group is more preferable, and a sulfonate ion having an aryl group The acid generator is particularly preferred, and the most preferred acid generator is diphenyltrimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium p-toluenesulfonate. LER can be reduced by using the acid generator.

  The acid generator (B) can be used alone or in combination of two or more. In the composition of the present invention, the amount of the acid generator used is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, and still more preferably 1 part per 100 parts by weight of the resist compound (A). ~ 15 parts by weight. The above range is preferable because the sensitivity, resolution, and cross-sectional shape of the resist pattern are good.

  The radiation-sensitive resist composition of the present invention also contains one or more acid crosslinking agents (C). The acid crosslinking agent (C) is a compound that can crosslink the resist compound (A) within a molecule or between molecules in the presence of an acid generated from the acid generator (B). Examples of such a crosslinking agent (C) include compounds having one or more substituents having crosslinking reactivity with the resist compound (A) (hereinafter referred to as “crosslinkable substituents”). .

  Specific examples of such crosslinkable substituents include (i) hydroxyalkyl such as hydroxy (C1-C6 alkyl group), C1-C6 alkoxy (C1-C6 alkyl group), acetoxy (C1-C6 alkyl group) and the like. A group or a substituent derived therefrom; (ii) a carbonyl group such as formyl group, carboxy (C1-C6 alkyl group) or a substituent derived therefrom; (iii) a dimethylaminomethyl group, a diethylaminomethyl group, a di Nitrogen-containing substituents such as methylolaminomethyl group, diethylolaminomethyl group, morpholinomethyl group; (iv) glycidyl group-containing substituents such as glycidyl ether group, glycidyl ester group, glycidylamino group; (v) benzyloxy C1-C6 allyloxy (C1-C) such as methyl group, benzoyloxymethyl group 6 alkyl groups), substituents derived from aromatic groups such as C1-C6 aralkyloxy (C1-C6 alkyl groups); (vi) substituents containing polymerizable multiple bonds such as vinyl groups and isopropenyl groups. be able to. As the crosslinkable substituent of the crosslinking agent of the present invention, a hydroxyalkyl group, an alkoxyalkyl group, and the like are preferable, and an alkoxymethyl group is particularly preferable.

  Examples of the acid crosslinking agent (C) having a crosslinkable substituent include (i) a methylol group-containing melamine compound, a methylol group-containing benzoguanamine compound, a methylol group-containing urea compound, a methylol group-containing glycoluril compound, and a methylol group-containing phenol compound. (Ii) alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycoluril compounds, alkoxyalkyl group-containing phenol compounds, etc. Containing compound; (iii) carboxymethyl group-containing melamine compound, carboxymethyl group-containing benzoguanamine compound, carboxymethyl group-containing urea compound, carboxymethyl group-containing Carboxymethyl group-containing compounds such as recall uril compounds and carboxymethyl group-containing phenol compounds; (iv) bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolak resin epoxy compounds, resole resin epoxy compounds And epoxy compounds such as poly (hydroxystyrene) -based epoxy compounds.

  As the acid crosslinking agent (C), it is further possible to use a compound having a phenolic hydroxyl group, and a compound and a resin imparted with a crosslinking property by introducing the crosslinking substituent into an acidic functional group in the alkali-soluble resin. it can. The introduction rate of the crosslinkable substituent in that case is usually 5 to 100 mol%, preferably 10 to 60 mol%, more preferably 10 to 60 mol%, based on the total acidic functional groups in the compound having a phenolic hydroxyl group and the alkali-soluble resin. Preferably, it is adjusted to 15 to 40 mol%. Within the above range, the cross-linking reaction occurs sufficiently, and a decrease in the remaining film ratio, a pattern swelling phenomenon, meandering, and the like can be avoided.

  In the radiation-sensitive resist composition of the present invention, the acid crosslinking agent (C) is preferably an alkoxyalkylated urea compound or a resin thereof, or an alkoxyalkylated glycoluril compound or a resin thereof. Particularly preferred acid crosslinking agents (C) include compounds represented by the following formulas (21) to (23) and alkoxymethylated melamine compounds (acid crosslinking agent (C1)).

（上記式中、Ｒ^７はそれぞれ独立して、水素原子、アルキル基、またはアシル基を表し；Ｒ^８〜Ｒ^１１はそれぞれ独立して、水素原子、水酸基、アルキル基、またはアルコキシル基を示し；Ｘ^２は、単結合、メチレン基、または酸素原子を示す。）

(In the above formula, each R ⁷ independently represents a hydrogen atom, an alkyl group, or an acyl group; each of R ^{8 to} R ¹¹ independently represents a hydrogen atom, a hydroxyl group, an alkyl group, or an alkoxyl group; X ² represents a single bond, a methylene group, or an oxygen atom.)

In formulas (21) to (23), R ⁷ is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms is more preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The acyl group having 2 to 6 carbon atoms is more preferably an acyl group having 2 to 4 carbon atoms, and examples thereof include an acetyl group and a propionyl group. R ^{8 to} R ¹¹ in Formula (21) are preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 3 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group. X ² represents a single bond, a methylene group, or an oxygen atom, and preferably a single bond or a methylene group. R ^{7 to} R ¹¹ and X ² each have a substituent such as an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, a hydroxyl group or a halogen atom in addition to the groups exemplified above. You may do it. The plurality of R ⁷ and R ^{8 to} R ¹¹ may be the same or different.

  Specific examples of the compound represented by the formula (21) include the compounds shown below.

  Specific examples of the compound represented by the formula (22) include N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) glycoluril, N , N, N, N-tetra (n-propoxymethyl) glycoluril, N, N, N, N-tetra (isopropoxymethyl) glycoluril, N, N, N, N-tetra (n-butoxymethyl) glycol Examples include uril, N, N, N, N-tetra (t-butoxymethyl) glycoluril and the like. Among these, N, N, N, N-tetra (methoxymethyl) glycoluril is particularly preferable.

  Specific examples of the compound represented by the formula (23) include the compounds shown below.

  Specific examples of the alkoxymethylated melamine compound include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, N-hexa (ethoxymethyl) melamine N, N, N, N, N, N-hexa (n-propoxymethyl) melamine, N, N, N, N, N, N-hexa (isopropoxymethyl) melamine, N, N, N, N, Examples thereof include N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine and the like. Among these, N, N, N, N, N, N-hexa (methoxymethyl) melamine is particularly preferable.

  The acid cross-linking agent (C1) is obtained by, for example, condensing a urea compound or glycoluril compound and formalin to introduce a methylol group, and then ether with lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol. Then, the reaction solution is cooled and the precipitated compound or its resin is recovered. The acid cross-linking agent (C1) can also be obtained as a commercial product such as CYMEL (trade name, manufactured by Mitsui Cyanamid) or Nicarac (manufactured by Sanwa Chemical Co., Ltd.).

  Further, as other particularly preferable acid crosslinking agent (C), the molecule has 1 to 6 benzene rings, and has at least two hydroxyalkyl groups and / or alkoxyalkyl groups in the molecule, and the hydroxyalkyl group and A phenol derivative in which an alkoxyalkyl group is bonded to any one of the benzene rings can be mentioned (acid crosslinking agent (C2)). Preferably, the molecular weight is 1500 or less, the molecule has 1 to 6 benzene rings, and the hydroxyalkyl group and / or alkoxyalkyl group has 2 or more in total, and the hydroxyalkyl group and / or alkoxyalkyl group is the benzene. A phenol derivative formed by bonding to any one or a plurality of benzene rings can be given.

  As a hydroxyalkyl group couple | bonded with a benzene ring, C1-C6 things, such as a hydroxymethyl group, 2-hydroxyethyl group, and 2-hydroxy-1-propyl group, are preferable. As an alkoxyalkyl group couple | bonded with a benzene ring, a C2-C6 thing is preferable. Specifically, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, sec-butoxymethyl group, t-butoxymethyl group, 2-methoxyethyl And a 2-methoxy-1-propyl group are preferred.

  Among these phenol derivatives, particularly preferable ones are listed below.

In the above formula, L ^{1 to} L ⁸ may be the same or different and each independently represents a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group. A phenol derivative having a hydroxymethyl group can be obtained by reacting a phenol compound not having a corresponding hydroxymethyl group (a compound in which L ^{1 to} L ⁸ are hydrogen atoms in the above formula) with formaldehyde in the presence of a base catalyst. it can. At this time, in order to prevent resinification or gelation, the reaction temperature is preferably 60 ° C. or lower. Specifically, they can be synthesized by the methods described in JP-A-6-282067, JP-A-7-64285 and the like.

  A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, in order to prevent resinification and gelation, the reaction temperature is preferably 100 ° C. or lower. Specifically, it can be synthesized by the method described in EP632003A1 and the like.

  A phenol derivative having a hydroxymethyl group and / or an alkoxymethyl group synthesized in this manner is preferable in terms of stability during storage, but a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage. preferable. The acid crosslinking agent (C2) may be used alone or in combination of two or more.

Another particularly preferable acid crosslinking agent (C) is a compound having at least one α-hydroxyisopropyl group (acid crosslinking agent (C3)). The structure is not particularly limited as long as it has an α-hydroxyisopropyl group. In addition, the hydrogen atom of the hydroxyl group in the α-hydroxyisopropyl group is one or more acid dissociable groups (R—COO— group, R—SO ₂ — group, etc., R is a straight chain having 1 to 12 carbon atoms) A hydrocarbon group, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a 1-branched alkyl group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms Which represents a substituent selected from the group consisting of: Examples of the compound having the α-hydroxyisopropyl group include one or two kinds such as a substituted or unsubstituted aromatic compound, diphenyl compound, naphthalene compound, and furan compound containing at least one α-hydroxyisopropyl group. The above is mentioned. Specifically, for example, a compound represented by the following general formula (24) (hereinafter referred to as “benzene compound (24)”), a compound represented by the following general formula (25) (hereinafter referred to as “diphenyl type”). Compound (25) "), a compound represented by the following general formula (26) (hereinafter referred to as" naphthalene compound (26 ")), and a compound represented by the following general formula (27) (hereinafter referred to as" Furan compound (27) ").

In the general formulas (24) to (27), each A ² independently represents an α-hydroxyisopropyl group or a hydrogen atom, and at least one A ² is an α-hydroxyisopropyl group. In General Formula (24), R ⁵¹ represents a hydrogen atom, a hydroxyl group, a linear or branched alkylcarbonyl group having 2 to 6 carbon atoms, or a linear or branched alkoxy group having 2 to 6 carbon atoms. A carbonyl group is shown. Further, in the general formula (25), R ⁵² represents a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —CO—, or —COO—. Moreover, in General formula (27), ^R53 and ^R54 show a hydrogen atom or a C1-C6 linear or branched alkyl group mutually independently.

  Specific examples of the benzene compound (24) include α-hydroxyisopropylbenzene, 1,3-bis (α-hydroxyisopropyl) benzene, 1,4-bis (α-hydroxyisopropyl) benzene, 1,2 , 4-Tris (α-hydroxyisopropyl) benzene, α-hydroxyisopropylbenzenes such as 1,3,5-tris (α-hydroxyisopropyl) benzene; 3-α-hydroxyisopropylphenol, 4-α-hydroxyisopropylphenol , 3,5-bis (α-hydroxyisopropyl) phenol, α-hydroxyisopropylphenols such as 2,4,6-tris (α-hydroxyisopropyl) phenol; 3-α-hydroxyisopropylphenyl methyl ketone, 4-α -Hydroxyisopropyl Phenyl methyl ketone, 4-α-hydroxyisopropylphenyl ethyl ketone, 4-α-hydroxyisopropylphenyl n-propyl ketone, 4-α-hydroxyisopropylphenyl isopropyl ketone, 4-α-hydroxyisopropylphenyl n-butyl ketone, 4-α-hydroxyisopropylphenyl · t-butylketone, 4-α-hydroxyisopropylphenyl · n-pentylketone, 3,5-bis (α-hydroxyisopropyl) phenyl · methylketone, 3,5-bis (α-hydroxyisopropyl) ) Phenyl ethyl ketone, α-hydroxyisopropylphenyl alkyl ketones such as 2,4,6-tris (α-hydroxyisopropyl) phenyl methylketone; 3-α-hydroxyisopropylbenzoic acid , Methyl 4-α-hydroxyisopropyl benzoate, ethyl 4-α-hydroxyisopropyl benzoate, n-propyl 4-α-hydroxyisopropyl benzoate, isopropyl 4-α-hydroxyisopropyl benzoate, 4-α-hydroxyisopropyl N-butyl benzoate, t-butyl 4-α-hydroxyisopropylbenzoate, n-pentyl 4-α-hydroxyisopropylbenzoate, methyl 3,5-bis (α-hydroxyisopropyl) benzoate, 3,5-bis Examples include 4-α-hydroxyisopropyl benzoate alkyls such as ethyl (α-hydroxyisopropyl) benzoate and methyl 2,4,6-tris (α-hydroxyisopropyl) benzoate.

  Specific examples of the diphenyl compound (25) include 3-α-hydroxyisopropylbiphenyl, 4-α-hydroxyisopropylbiphenyl, 3,5-bis (α-hydroxyisopropyl) biphenyl, 3,3 ′. -Bis (α-hydroxyisopropyl) biphenyl, 3,4'-bis (α-hydroxyisopropyl) biphenyl, 4,4'-bis (α-hydroxyisopropyl) biphenyl, 2,4,6-tris (α-hydroxyisopropyl ) Biphenyl, 3,3 ′, 5-tris (α-hydroxyisopropyl) biphenyl, 3,4 ′, 5-tris (α-hydroxyisopropyl) biphenyl, 2,3 ′, 4,6, -tetrakis (α-hydroxy) Isopropyl) biphenyl, 2,4,4 ′, 6, -tetrakis (α-hydroxyiso) Propyl) biphenyl, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) biphenyl, 2,3 ′, 4,5 ′, 6-pentakis (α-hydroxyisopropyl) biphenyl, 2,2 ′, 4 , 4 ′, 6,6′-hexakis (α-hydroxyisopropyl) biphenyl and the like α-hydroxyisopropylbiphenyls; 3-α-hydroxyisopropyldiphenylmethane, 4-α-hydroxyisopropyldiphenylmethane, 1- (4-α-hydroxy) Isopropylphenyl) -2-phenylethane, 1- (4-α-hydroxyisopropylphenyl) -2-phenylpropane, 2- (4-α-hydroxyisopropylphenyl) -2-phenylpropane, 1- (4-α- Hydroxyisopropylphenyl) -3-phenylpropane, 1- 4-α-hydroxyisopropylphenyl) -4-phenylbutane, 1- (4-α-hydroxyisopropylphenyl) -5-phenylpentane, 3,5-bis (α-hydroxyisopropyldiphenylmethane, 3,3′-bis ( α-hydroxyisopropyl) diphenylmethane, 3,4′-bis (α-hydroxyisopropyl) diphenylmethane, 4,4′-bis (α-hydroxyisopropyl) diphenylmethane, 1,2-bis (4-α-hydroxyisopropylphenyl) ethane 1,2-bis (4-α-hydroxypropylphenyl) propane, 2,2-bis (4-α-hydroxypropylphenyl) propane, 1,3-bis (4-α-hydroxypropylphenyl) propane, 2, , 4,6-Tris (α-hydroxyisopropyl) diphe Lumethane, 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenylmethane, 3,4 ′, 5-tris (α-hydroxyisopropyl) diphenylmethane, 2,3 ′, 4,6-tetrakis (α-hydroxyisopropyl) Diphenylmethane, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenylmethane, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) diphenylmethane, 2,3 ′, 4,5 ′, 6 Α-hydroxyisopropyldiphenylalkanes such as pentakis (α-hydroxyisopropyl) diphenylmethane, 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenylmethane; 3-α-hydroxyisopropyldiphenyl ether 4-α-hydroxyisopro Rudiphenyl ether, 3,5-bis (α-hydroxyisopropyl) diphenyl ether, 3,3′-bis (α-hydroxyisopropyl) diphenyl ether, 3,4′-bis (α-hydroxyisopropyl) diphenyl ether, 4,4′-bis (Α-hydroxyisopropyl) diphenyl ether, 2,4,6-tris (α-hydroxyisopropyl) diphenyl ether, 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenyl ether, 3,4 ′, 5-tris (α- Hydroxyisopropyl) diphenyl ether, 2,3 ′, 4,6-tetrakis (α-hydroxyisopropyl) diphenyl ether, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenyl ether, 3,3 ′, 5,5 ′ -Tetrakis α-hydroxyisopropyl) diphenyl ether, 2,3 ′, 4,5 ′, 6-pentakis (α-hydroxyisopropyl) diphenyl ether, 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) Α-hydroxyisopropyl diphenyl ethers such as diphenyl ether; 3-α-hydroxyisopropyl diphenyl ketone, 4-α-hydroxyisopropyl diphenyl ketone, 3,5-bis (α-hydroxyisopropyl) diphenyl ketone, 3,3′-bis (α -Hydroxyisopropyl) diphenylketone, 3,4'-bis (α-hydroxyisopropyl) diphenylketone, 4,4'-bis (α-hydroxyisopropyl) diphenylketone, 2,4,6-tris (α-hydroxyisopropyl) Diphenyl , 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenyl ketone, 3,4 ′, 5-tris (α-hydroxyisopropyl) diphenyl ketone, 2,3 ′, 4,6-tetrakis (α-hydroxy) Isopropyl) diphenyl ketone, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenyl ketone, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) diphenyl ketone, 2,3 ′, 4 , 5 ′, 6-pentakis (α-hydroxyisopropyl) diphenyl ketone, α-hydroxyisopropyl diphenyl ketones such as 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenyl ketone; Phenyl 3-α-hydroxyisopropyl benzoate, 4-α-hydroxyisopropyl benzoate Phenyl benzoate, 3-α-hydroxyisopropylphenyl benzoate, 4-α-hydroxyisopropylphenyl benzoate, phenyl 3,5-bis (α-hydroxyisopropyl) benzoate, 3-α-hydroxyisopropylbenzoate 3-α -Hydroxyisopropylphenyl, 3-α-hydroxyisopropylbenzoic acid 4-α-hydroxyisopropylphenyl, 4-α-hydroxyisopropylbenzoic acid 3-α-hydroxyisopropylphenyl, 4-α-hydroxyisopropylbenzoic acid 4-α-hydroxy Isopropyl phenyl, 3,5-bis (α-hydroxyisopropyl) phenyl benzoate, phenyl 2,4,6-tris (α-hydroxyisopropyl) benzoate, 3,5-bis (α-hydroxyisopropyl) benzoic acid 3- α-hydroxy Sopropylphenyl, 3,5-bis (α-hydroxyisopropyl) benzoate 4-α-hydroxyisopropylphenyl, 3-α-hydroxyisopropylbenzoate 3,5-bis (α-hydroxyisopropyl) phenyl, 4-α- 3,5-bis (α-hydroxyisopropyl) phenyl hydroxyisopropylbenzoate, 2,4,6-tris (α-hydroxyisopropyl) phenyl benzoate, 2,4,6-tris (α-hydroxyisopropyl) benzoic acid 3 -Α-hydroxyisopropylphenyl, 2,4,6-tris (α-hydroxyisopropyl) benzoic acid 4-α-hydroxyisopropylphenyl, 3,5-bis (α-hydroxyisopropyl) benzoic acid 3,5-bis (α -Hydroxyisopropyl) phenyl, 3-α-hydroxyisopropyl Pyrbenzoate 2,4,6-tris (α-hydroxyisopropyl) phenyl, 4-α-hydroxyisopropylbenzoate 2,4,6-tris (α-hydroxyisopropyl) phenyl, 2,4,6-tris (α -Hydroxyisopropyl) benzoic acid 3,5-bis (α-hydroxyisopropyl) phenyl, 3,5-bis (α-hydroxyisopropyl) benzoic acid 2,4,6-tris (α-hydroxyisopropyl) phenyl, 2,4 , 6-tris (α-hydroxyisopropyl) benzoic acid 2,4,6-tris (α-hydroxyisopropyl) phenyl and the like α-hydroxyisopropylbenzoic acid phenyls and the like.

  Further, specific examples of the naphthalene compound (26) include 1- (α-hydroxyisopropyl) naphthalene, 2- (α-hydroxyisopropyl) naphthalene, 1,3-bis (α-hydroxyisopropyl) naphthalene, 1,4-bis (α-hydroxyisopropyl) naphthalene, 1,5-bis (α-hydroxyisopropyl) naphthalene, 1,6-bis (α-hydroxyisopropyl) naphthalene, 1,7-bis (α-hydroxyisopropyl) Naphthalene, 2,6-bis (α-hydroxyisopropyl) naphthalene, 2,7-bis (α-hydroxyisopropyl) naphthalene, 1,3,5-tris (α-hydroxyisopropyl) naphthalene, 1,3,6-tris (Α-hydroxyisopropyl) naphthalene, 1,3,7-tris (α Hydroxyisopropyl) naphthalene, 1,4,6-tris (α-hydroxyisopropyl) naphthalene, 1,4,7-tris (α-hydroxyisopropyl) naphthalene, 1,3,5,7-tetrakis (α-hydroxyisopropyl) And naphthalene.

  Specific examples of the furan compound (27) include 3- (α-hydroxyisopropyl) furan, 2-methyl-3- (α-hydroxyisopropyl) furan, 2-methyl-4- (α- Hydroxyisopropyl) furan, 2-ethyl-4- (α-hydroxyisopropyl) furan, 2-n-propyl-4- (α-hydroxyisopropyl) furan, 2-isopropyl-4- (α-hydroxyisopropyl) furan, 2 -N-butyl-4- (α-hydroxyisopropyl) furan, 2-t-butyl-4- (α-hydroxyisopropyl) furan, 2-n-pentyl-4- (α-hydroxyisopropyl) furan, 2,5 -Dimethyl-3- (α-hydroxyisopropyl) furan, 2,5-diethyl-3- (α-hydroxyisopropyl) fura 3,4-bis (α-hydroxyisopropyl) furan, 2,5-dimethyl-3,4-bis (α-hydroxyisopropyl) furan, 2,5-diethyl-3,4-bis (α-hydroxyisopropyl) ) Furan etc. can be mentioned.

  The acid crosslinking agent (C3) is preferably a compound having two or more free α-hydroxyisopropyl groups, a benzene compound (24) having two or more α-hydroxyisopropyl groups, and two or more α-hydroxyisopropyl groups. More preferred are diphenyl compounds (25), naphthalene compounds (26) having two or more α-hydroxyisopropyl groups, α-hydroxyisopropylbiphenyls having two or more α-hydroxyisopropyl groups, and α-hydroxyisopropyl groups. A naphthalene compound (27) having two or more is particularly preferred.

The acid cross-linking agent (C3) is usually a method of hydrolyzing after a methylation by reacting a acetyl group-containing compound such as 1,3-diacetylbenzene with a Grignard reagent such as CH ₃ MgBr, or 1,3 It can be obtained by a method in which an isopropyl group-containing compound such as diisopropylbenzene is oxidized with oxygen or the like to generate a peroxide and then reduced.

  In the present invention, the blending ratio of the acid crosslinking agent (C) is 0.5 to 70 parts by weight, preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight per 100 parts by weight of the resist compound (A). It is. When the blending ratio of the acid crosslinking agent (C) is 0.5 parts by weight or more, the effect of suppressing the solubility of the resin (A) in an alkaline developer is improved, the remaining film ratio is reduced, or the pattern is swollen. And 70 mean by weight or less are preferable because the reduction in heat resistance as a resist can be suppressed.

    Further, the blending ratio of at least one compound selected from the acid crosslinking agent (C1), the acid crosslinking agent (C2), and the acid crosslinking agent (C3) in the acid crosslinking agent (C) is not particularly limited. Various ranges can be used depending on the type of substrate used when forming the pattern.

  In the total acid crosslinking agent component, the alkoxymethylated melamine compound and / or the compound represented by (21) to (23) is 50 to 99% by weight, preferably 60 to 99% by weight, more preferably 70 to 98% by weight. More preferably, the content is 80 to 97% by weight. Since the resolution can be improved by setting the alkoxymethylated melamine compound and / or the compound represented by (21) to (23) to 50% by weight or more of the total acid crosslinking agent component, it is preferably 99% by weight or less. By doing so, it is preferable because it is easy to obtain a rectangular cross-sectional shape as the pattern cross-sectional shape.

  In the radiation-sensitive resist composition of the present invention, an acid diffusion control agent, a dissolution control agent, a dissolution accelerator, and a sensitizer as an optional component (D) within the range not impairing the object of the present invention. , Surfactants, and various additives such as organic carboxylic acids or phosphorus oxo acids or derivatives thereof can be added.

[1] Acid Diffusion Control Agent An undesirable chemical reaction in an unexposed region by controlling the diffusion phenomenon in the resist film of the acid generated from the photoacid generator by irradiation with the radiation sensitive resist composition of the present invention. You may mix | blend the acid diffusion control agent which has the effect | action etc. which control this. By using such an acid diffusion control agent, the storage stability of the radiation-sensitive resist composition is improved, the resolution is improved, and the holding time before irradiation and the holding time after irradiation are reduced. Changes in the line width of the resist pattern due to fluctuations can be suppressed, and the process stability is extremely excellent.

  Examples of the acid diffusion controller include nitrogen-containing organic compounds and basic compounds that decompose upon exposure. Examples of the nitrogen-containing organic compound include the following general formula (28):

で表される化合物（以下、「含窒素化合物（Ｉ）」という。）、同一分子内に窒素原子を２個有するジアミノ化合物（以下、「含窒素化合物（ＩＩ）」という。）、窒素原子を３個以上有するポリアミノ化合物や重合体（以下、「含窒素化合物（ＩＩＩ）」という。）、アミド基含有化合物、ウレア化合物、及び含窒素複素環式化合物等を挙げることができる。尚、上記酸拡散制御剤は、１種単独で用いてもよく、２種以上を併用してもよい。

(Hereinafter referred to as “nitrogen-containing compound (I)”), a diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (II)”), and a nitrogen atom. Examples thereof include polyamino compounds and polymers having three or more compounds (hereinafter referred to as “nitrogen-containing compound (III)”), amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds. In addition, the said acid diffusion control agent may be used individually by 1 type, and may use 2 or more types together.

In the general formula (28), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group, or aralkyl group may be unsubstituted or substituted with another functional group such as a hydroxyl group. Here, examples of the linear, branched or cyclic alkyl group include those having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, specifically, methyl group, ethyl group, n- Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group , N-ethylhexyl group, n-nonyl group, n-decyl group and the like. Moreover, as said aryl group, a C6-C12 thing is mentioned, Specifically, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, 1-naphthyl group, etc. are mentioned. Furthermore, examples of the aralkyl group include those having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, and specific examples include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.

  Specific examples of the nitrogen-containing compound (I) include mono-cyclohexane such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine and cyclohexylamine. ) Alkylamines; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine , Methyl-n-dodecylamine, di-n-dodecylmethyl, cyclohexylmethylamine, dicyclohexylamine and the like di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n- Pentylamine, tri-n-hexylamine, tri-n-heptylamine, -Tri (cyclo) alkylamines such as n-octylamine, tri-n-nonylamine, tri-n-decylamine, dimethyl-n-dodecylamine, di-n-dodecylmethylamine, dicyclohexylmethylamine, tricyclohexylamine; Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine , Aromatic amines such as triphenylamine and 1-naphthylamine.

  Specific examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, Tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) ) Propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl)- 2- (4-Hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and the like.

  Specific examples of the nitrogen-containing compound (III) include polyethyleneimine, polyallylamine, N- (2-dimethylaminoethyl) acrylamide polymer, and the like.

  Specific examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N- And methylpyrrolidone.

  Specific examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri- Examples thereof include n-butylthiourea.

  Specific examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, 2-phenylbenzimidazole; pyridine, 2-methylpyridine. 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline And pyridines such as acridine; and pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2. ] Octane etc. It can gel.

Moreover, as a basic compound decomposed | disassembled by the said exposure, the following general formula (29):

で表されるスルホニウム化合物、及び下記一般式（３０）：

A sulfonium compound represented by the following general formula (30):

で表されるヨードニウム化合物等を挙げることができる。

The iodonium compound etc. which are represented by these can be mentioned.

In the general formulas (29) and (30), R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyl having 1 to 6 carbon atoms. A group, a hydroxyl group or a halogen atom; Z ⁻ represents HO ⁻ , R—COO ⁻ (wherein R represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 6 carbon atoms, or an alkaryl group having 1 to 6 carbon atoms) or the following general formula. (31):

で表されるアニオンを示す。

An anion represented by

  Specific examples of the basic compound that decomposes upon exposure include triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, and diphenyl-4-hydroxyphenyl. Sulfonium acetate, diphenyl-4-hydroxyphenylsulfonium salicylate, bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium hydro Oxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium salicylate, 4-t-butylphenyl 4- hydroxyphenyl iodonium hydroxide, 4-t-butylphenyl-4-hydroxyphenyl iodonium acetate, include 4-t-butylphenyl-4-hydroxyphenyl iodonium salicylate and the like.

  The compounding amount of the acid diffusion controller is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight, still more preferably 0.01 to 3 parts by weight per 100 parts by weight of the resist compound (A). It is. By making the blending amount 0.001 part by weight or more, resolution, pattern shape, dimensional fidelity, etc. are further improved, and even if the holding time from radiation irradiation to heating after radiation irradiation becomes long, the pattern The pattern shape of the upper layer portion can be improved. When the blending amount is 10 parts by weight or less, it is possible to prevent the resist sensitivity, the developability of the unexposed part, and the like from being lowered.

[2] Solubility control agent When the resist compound (A) is too soluble in a developing solution such as an alkali, the solubilization control agent acts to control the solubility and moderately reduce the dissolution rate during development. It is a component that has. As such a dissolution controlling agent, those which do not chemically change in steps such as baking of resist film, irradiation with radiation, and development are preferable.

  Examples of the dissolution control agent include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. Can be mentioned. These dissolution control agents can be used alone or in combination of two or more.

  The blending amount of the dissolution control agent is appropriately adjusted according to the type of the resist compound (A) to be used, but is preferably 30 parts by weight or less, more preferably 10 parts by weight or less per 100 parts by weight of the resist compound (A). It is.

[3] Dissolution Accelerator The dissolution accelerator increases the solubility of the resist compound (A) during development when the solubility of the resist compound (A) in a developing solution such as alkali is too low. It is a component having an action of increasing moderately. Examples of the dissolution accelerator include low molecular weight phenolic compounds having about 2 to 6 benzene rings, and specific examples include bisphenols, tris (hydroxyphenyl) methane, and the like. it can. These dissolution promoters can be used alone or in admixture of two or more.

  The blending amount of the dissolution accelerator is appropriately adjusted according to the type of the resist compound (A) to be used, but is preferably 30 parts by weight or less, more preferably 10 parts by weight or less per 100 parts by weight of the resist compound (A). It is.

[4] Sensitizer The sensitizer absorbs the energy of the irradiated radiation and transmits the energy to the acid generator (B), thereby increasing the amount of acid generated. It is a component that improves the apparent sensitivity. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes.

  These sensitizers can be used alone or in combination of two or more. The blending amount of the sensitizer is preferably 30 parts by weight or less, more preferably 10 parts by weight or less per 100 parts by weight of the resist compound (A).

[5] Surfactant The surfactant is a component having an action of improving the coating property and striation of the radiation-sensitive resist composition of the present invention, the developability of the resist, and the like. Such a surfactant may be anionic, cationic, nonionic or amphoteric. A preferred surfactant is a nonionic surfactant. Nonionic surfactants have better affinity with the solvent used in the production of the radiation-sensitive resist composition, and are more effective. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers and higher fatty acid diesters of polyethylene glycol, but are not particularly limited. Commercially available products include the following product names: F-top (manufactured by Gemco), Mega-Fac (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Examples include Pepol (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), and the like.

  The blending amount of the surfactant is preferably 2 parts by weight or less as an active ingredient of the surfactant per 100 parts by weight of the resist compound (A).

[6] Organic carboxylic acid or phosphorus oxo acid or derivative thereof For the purpose of preventing sensitivity deterioration or improving resist pattern shape, retention stability, etc., organic carboxylic acid or phosphorus oxo acid or derivative thereof as an optional component Can be contained. In addition, it can be used in combination with an acid diffusion controller, or may be used alone. 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 derivative thereof may be used alone or in combination of two or more. The amount of the organic carboxylic acid or phosphorus oxo acid or derivative thereof 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 component, and 0 to 1%. Weight percent is particularly preferred.

[7] Acid diffusion control agent, dissolution accelerator, dissolution control agent, sensitizer, surfactant, and other additives other than organic carboxylic acid or phosphorus oxo acid or derivatives thereof Further negative type of the present invention In the radiation-sensitive resist composition, additives other than the above acid diffusion controller, dissolution accelerator, dissolution controller, sensitizer, and surfactant, if necessary, within a range not impairing the object of the present invention 1 type, or 2 or more types can be mix | blended. Examples of such additives include dyes, pigments, and adhesion aids. For example, it is preferable to add a dye or a pigment because the latent image in the exposed area can be visualized and the influence of halation during exposure can be reduced. In addition, it is preferable to add an adhesion assistant because the adhesion to the substrate can be improved. Furthermore, examples of other additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improving agent, and the like, specifically 4-hydroxy-4′-methylchalcone.

  The radiation-sensitive resist composition of the present invention is usually prepared by dissolving each component in a solvent at the time of use to make a uniform solution, and then filtering by, for example, a filter having a pore size of about 0.2 μm as necessary. Is done. The total solid concentration in the homogeneous solution is usually 50% by weight or less, preferably 1 to 50% by weight, more preferably 1 to 30% by weight, and still more preferably 1 to 10% by weight.

  Examples of the solvent used in the preparation of the radiation sensitive resist composition of the present invention include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n. Ethylene glycol monoalkyl ether acetates such as butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n -Propyl ether acetate, propylene glycol mono-n-butyl ether acetate Propylene glycol monoalkyl ether acetates such as propylene glycol; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate Lactic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate, and the like; 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-meth Other esters such as sibutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate and ethyl pyruvate; aromatics such as toluene and xylene Hydrocarbons; ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; A lactone such as γ-lactone can be exemplified, but is not particularly limited. These solvents can be used alone or in combination of two or more.

The radiation-sensitive resist composition of the present invention can contain a compound and / or resin that is soluble in an alkaline aqueous solution as long as the object of the present invention is not impaired. Although it does not specifically limit as a compound soluble in alkaline aqueous solution, For example, the phenolic compound which has phenolic hydroxyl groups, such as a polyphenol compound, is mentioned, As a resin soluble in alkaline aqueous solution, a novolak resin, polyvinylphenols , Polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as monomer units, or derivatives thereof. The compounding amount of the compound and / or resin that is soluble in the alkaline aqueous solution is appropriately adjusted according to the type of the resist compound to be used, and is preferably 30 parts by weight or less per 100 parts by weight of the resist compound (A). More preferred is 10 parts by weight or less, further preferred is 5 parts by weight or less, and particularly preferred is 0 part by weight.
In addition, a crosslinking reaction that causes a crosslinking reaction by irradiation with visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray and ion beam or a chemical reaction induced thereby without departing from the object of the present invention. A compound having a vinyl group, an allyl group, a cinnamoyl group, a vinylsilyl group, an epoxy group, a chloromethyl group, or a halogenated phenyl group and / or a resin can be included. The compound and / or resin having a crosslinking reactive group is not particularly limited, and is produced by reacting a compound and / or resin that is soluble in the alkaline aqueous solution with a crosslinking reactive group introduction reagent in the presence of a base catalyst. Compounds and / or polymers, or derivatives thereof. The term “crosslinking reactive group introduction reagent” as used herein refers to an acid having a crosslinking reactive group, an acid chloride, an acid anhydride, a carboxylic acid derivative compound such as dicarbonate, an alkyl halide, or the like. Of these, acid chlorides are particularly preferred. One or more of these may be used.

  The composition of the radiation-sensitive resist composition of the present invention (resist compound (A) / acid generator (B) / acid cross-linking agent (C) / optional component (D)) is preferably% by weight based on solids, 3-96.9 / 0.1-30 / 3-65 / 0-93.9, more preferably 65-96.9 / 0.1-30 / 0.3-34.9 / 0-30, Preferably 65-96.9 / 0.1-30 / 0.3-34.9 / 0-10, particularly preferably 65-96.9 / 0.1-30 / 0.6-34.9 / 0. -5, most preferably 65-96.9 / 0.1-30 / 0.6-30 / 0. When the above composition is used, the performance such as sensitivity, resolution and alkali developability is excellent.

When the optional component (D) is not included, the composition of all solids in the radiation-sensitive resist composition of the present invention is:
(A) 3-96.9 wt%, (B) 0.1-30 wt%, (C) 0.3-96.9 wt% ((A) + (B) + (C) = 100 wt% Is preferred,
(A) 65-96.9 wt%, (B) 0.1-32 wt%, (C) 0.3-34.9 wt%, ((A) + (B) + (C) = 100 wt% %) Is more preferable,
(A) 70-96.9 wt%, (B) 0.1-27 wt%, (C) 3.0-29.9 wt%, ((A) + (B) + (C) = 100 wt% %) Is more preferable,
(A) 80-96.9 wt%, (B) 0.1-17 wt%, (C) 3.0-19.9 wt% ((A) + (B) + (C) = 100 wt% ) Is particularly preferred,
(A) 90-96.9 wt%, (B) 0.1-7 wt%, (C) 3.0-9.9 wt%, ((A) + (B) + (C) = 100 wt% %) Is most preferred. By setting it within the above range, the performance such as sensitivity, resolution, and alkali developability is excellent.

  In the present invention, the resist substrate is a substrate on which a resist film made of the radiation-sensitive resist composition is formed, and the pattern formation substrate is a pattern formed by exposing and developing the resist film on the resist substrate. It is a substrate that has been made into. The “pattern forming material” refers to a composition formed on a resist substrate and capable of forming a pattern by irradiation with light, an electron beam or radiation, and is synonymous with “resist film”. A “pattern wiring substrate” is a substrate having a patterned wiring obtained by etching a pattern forming substrate.

  In order to form a resist pattern, first, the radiation-sensitive resist composition of the present invention is applied on a substrate such as a silicon wafer or a wafer coated with aluminum by a coating means such as spin coating, cast coating, roll coating or the like. Thus, a resist film is formed. If necessary, a surface treatment agent such as hexamethylene disilazane may be applied on the substrate in advance.

  Next, the coated substrate is heated as necessary. Although heating conditions change with the compounding composition of a radiation sensitive resist composition, 20-250 degreeC is preferable, More preferably, it is 20-150 degreeC. Heating may improve the adhesion of the resist to the substrate, which is preferable. Next, the resist film is exposed to a desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. The exposure conditions and the like are appropriately selected according to the composition of the radiation-sensitive resist composition. In the present invention, in order to stably form a high-precision fine pattern in exposure, heating is preferably performed after irradiation with radiation. Although heating conditions change with the compounding composition of a radiation sensitive resist composition, 20-250 degreeC is preferable, More preferably, it is 20-150 degreeC.

  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 in which one or more compounds are dissolved so as to have a concentration of preferably 1 to 10% by mass, more preferably 1 to 5% by mass is used. When the concentration of the alkaline aqueous solution is 10% by mass or less, it is preferable because the exposed portion can be prevented from being dissolved in the developer.

  In addition, an appropriate amount of alcohols such as methanol, ethanol, isopropyl alcohol, and the surfactant can be added to the alkaline developer. Of these, it is particularly preferable to add 10 to 30% by mass of isopropyl alcohol. This is preferable since the wettability of the developer with respect to the resist can be improved. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans with water after image development.

  After forming the resist pattern, the pattern wiring board is obtained by etching. The etching can be performed by a known method such as dry etching using plasma gas and wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like.

  Plating can be performed after forming the resist pattern. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.

  The residual resist pattern after etching can be peeled off with an organic solvent or a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate) and the like. As the strong alkaline aqueous solution, for example, 1 to 20% by mass of sodium hydroxide aqueous solution or 1-20 mass% 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.

  The wiring board obtained by the present invention can also be formed by a method of depositing a metal in vacuum after forming a resist pattern and then dissolving the resist pattern with a solution, that is, a lift-off method.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

In the following synthesis examples, the structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 1 and 2.

Synthesis Example 1: Synthesis of Compound 1 (Formula (51))

  2,3,6-trimethylphenol (196.0 g / 1.44 mol) and 1,3,5-triformylbenzene (20.0 g / 0.12 mol) were mixed and dissolved by heating to about 100 ° C. 36 ml, 3-mercaptopropionic acid 2.3 ml and toluene 100 ml were added and reacted with stirring. After confirming the 1,3,5-triformylbenzene conversion rate of 100%, the solid which was cooled and precipitated was filtered under reduced pressure, and then stirred and washed with hot water at 60 ° C. to obtain 111.0 g of the desired product.

Synthesis Example 2: Synthesis of Compound 2 (Formula (52))

  The reaction of 175.8 g / 1.44 mol of 2,6-xylenol and 20.0 g / 0.12 mol of 1,3,5-triformylbenzene was carried out in the same manner as in Synthesis Example 1 to obtain 98.3 g of the desired product.

Synthesis Example 3: Synthesis of Compound 3 (Formula (53))

  The reaction of 175.8 g / 1.44 mol of 2,5-xylenol and 20.0 g / 0.12 mol of 1,3,5-triformylbenzene was carried out in the same manner as in Synthesis Example 1 to obtain 79.3 g of the desired product.

Synthesis Example 4: Synthesis of Compound 4 (Formula (54))

  The reaction of 155.7 g / 1.44 mol of o-cresol and 20.0 g / 0.1 mol of 1,3,5-triformylbenzene was carried out in the same manner as in Synthesis Example 1 to obtain 78.9 g of the desired product.

Examples 1-10 and Comparative Examples 1-2
After making the resist compound (A), acid generator (B), acid crosslinking agent (C), other additives (D), and solvent shown in Table 3 into a uniform solution, Teflon (registered trademark) having a pore size of 0.2 μm It filtered with the membrane filter made, and prepared the radiation sensitive resist composition.

(1) Evaluation of film formability of resist film A radiation sensitive resist composition is spin-coated on a silicon wafer with a spin coater to form a resist film, and then 10 × under the conditions shown in Table 4 using a hot plate. A 10 mm square resist film was evaluated according to the following criteria.
A: Good surface property C: Partly whitened or uneven on the surface

(2) Patterning test (2-1) Resolution evaluation After spin-coating a radiation-sensitive resist composition on a clean silicon wafer, the resist is baked (PB) in an oven and exposed to 0.1 μm thickness. A film was formed. The resist film was irradiated with an electron beam with a line-and-space setting of 1: 1 at intervals of 30 nm, 40 nm, and 50 nm using an electron beam drawing apparatus (ELS-7500, manufactured by Elionix Co., Ltd.). After irradiation, each was heated at a predetermined temperature for 90 seconds and developed in a 2.38 wt% TMAH aqueous solution for 60 seconds. Thereafter, it was washed with water for 30 seconds and dried to form a negative resist pattern. The obtained line and space was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technology Corporation). The dose amount (μC / cm ² ) at that time was defined as sensitivity.
(2-2) Evaluation of pattern shape The obtained cross-sectional photograph of 1: 1 line and space with an interval of 50 nm 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)
(2-3) Evaluation of line edge roughness (LER) SEM terminal PC V5 offline length measurement software for Hitachi Semiconductor at arbitrary 300 points in the length direction (0.75 μm) of 1: 1 line and space at 50 nm intervals (Hitachi Science Systems Co., Ltd.) 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) ≦ 3.5 nm (good LER)
B: 3.5 nm <LER (3σ) ≦ 4.5 nm (almost good LER)
C: 4.5 nm <LER (3σ) <LER (3σ) (not good LER)
(2-4) Etching resistance The resist film obtained with the negative pattern is dry-etched by using tetrafluoromethane as an etching gas and etching conditions of 70 sccm, 50 W and 20 Pa using an RIE etching apparatus. Then, the etching rate of the resist pattern was determined. The results were compared with the etching rate when polyhydroxystyrene (PHS) was used as the resist compound.
A: Etching rate is 1 / 1.3 or less of PHS B: Etching rate is 1 / 1.1-1 / 1.2 of PHS
C: Etching rate equal to or less than PHS

(3) Safety solvent solubility test of compound The solubility test of the compound obtained in Synthesis Examples 1 to 4 in a safety solvent was performed at 23 ° C. 1. It is selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate, and the amount dissolved in the most soluble solvent is evaluated. It was confirmed that 5 wt% or more was dissolved.

化合物１２：

（Ｂ）酸発生剤
ＰＡＧ−１：トリフェニルベンゼンスルホニウム ノナフルオロブタンスルホネート
（みどり化学（株））
ＰＡＧ−２：ジフェニルトリメチルフェニルスルホニウム ｐ−トルエンスルホネート
（和光純薬工業（株））
（Ｃ）架橋剤
Ｃ−１ ニカラックＭＷ−１００ＬＭ(三和ケミカル(株))
Ｃ−２ ニカラックＭＸ−２７０（三和ケミカル(株))
Ｃ−３ ニカラックＭＸ−２９０(三和ケミカル(株))
Ｃ−４ ２，６−ビス（ヒドロキシメチル）−ｐ−クレゾール（東京化成工業(株))
（Ｄ）その他の添加剤
Q−１ トリオクチルアミン（東京化成工業（株））
Q−２ ロフィン（東京化成工業（株））
Ｄ−１：メガファックＲ−０８（大日本インキ化学工業（株）製）
Ｄ−２：ＢＹＫ−３０２（ビック・ケミージャパン（株）製）

溶媒
Ｓ−１ プロピレングリコールモノメチルモノアセテート（東京化成工業(株))
Ｓ−２ プロピレングリコールモノメチルエーテル（東京化成工業(株))
Ｓ−３ プロピオン酸エチル（東京化成工業(株)) (A) Compound 11: Te25XMTDA (the following formula (55), the synthesis method is described in WO2005 / 101127)
12: Te236TMP27NDA (the following formula (56), the synthesis method is described in WO2005 / 101127)
13: Polyhydroxystyrene (Mw = 8000) (Kanto Chemical Co., Inc.)
Compound 11:

Compound 12:

(B) Acid generator PAG-1: Triphenylbenzenesulfonium nonafluorobutanesulfonate (Midori Chemical Co., Ltd.)
PAG-2: Diphenyltrimethylphenylsulfonium p-toluenesulfonate (Wako Pure Chemical Industries, Ltd.)
(C) Crosslinking agent C-1 Nicalak MW-100LM (Sanwa Chemical Co., Ltd.)
C-2 Nicarak MX-270 (Sanwa Chemical Co., Ltd.)
C-3 Nicarak MX-290 (Sanwa Chemical Co., Ltd.)
C-4 2,6-bis (hydroxymethyl) -p-cresol (Tokyo Chemical Industry Co., Ltd.)
(D) Other additives
Q-1 Trioctylamine (Tokyo Chemical Industry Co., Ltd.)
Q-2 Lofine (Tokyo Chemical Industry Co., Ltd.)
D-1: Megafuck R-08 (Dainippon Ink Chemical Co., Ltd.)
D-2: BYK-302 (manufactured by Big Chemie Japan Co., Ltd.)

Solvent S-1 Propylene glycol monomethyl monoacetate (Tokyo Chemical Industry Co., Ltd.)
S-2 Propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.)
S-3 Ethyl propionate (Tokyo Chemical Industry Co., Ltd.)

Claims (10)

(A) a polyphenol compound produced by a condensation reaction between a tri- to tetravalent aromatic aldehyde having 7 to 38 carbon atoms and a compound having 6 to 15 carbon atoms and having 1 to 3 phenolic hydroxyl groups, And (b) any radiation selected from the group consisting of a resist compound (A) having a molecular weight of 800 to 5000, visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam The radiation sensitive resist composition characterized by including the acid generator (B) which generate | occur | produces an acid directly or indirectly by irradiation, and an acid crosslinking agent (C). The resist compound (A) is represented by the following formula (1):

(In the formula (1), R ² represents a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyloxy group, an aryloyloxy group, a cyano group, and a nitro group. Represents a substituent selected from the group consisting of groups, and a plurality of R ² may be the same or different;
R ¹ represents a trivalent group having 6 to 20 carbon atoms having a benzene structure, naphthalene structure, terphenyl structure, phenanthrene structure or anthracene structure, which may have a substituent, and k3, j3, m3, n3 , X3, y3 are integers of 1 to 3, k5, j5, m5, n5, x5, y5 are integers of 0 to 4, 1 ≦ k3 + k5 ≦ 5, 1 ≦ j3 + j5 ≦ 5, 1 ≦ m3 + m5 ≦ 5 1 ≦ n3 + n5 ≦ 5, 1 ≦ x3 + x5 ≦ 5, and 1 ≦ y3 + y5 ≦ 5 are satisfied. )
The radiation-sensitive resist composition according to claim 1, wherein The resist compound (A) is represented by the following formula (3):

(In formula (3), R ² , k 3, j 3, m 3, n 3, x 3, y 3, k 5, j 5, m 5, n 5, x 5, y 5 are the same as described above.)
The radiation-sensitive resist composition according to claim 1, wherein The resist compound (A) is represented by the following formula (4):

(In Formula (4), R ⁴ is a hydrogen atom or a methyl group, and a plurality of R ⁴ may be the same or different.)
The radiation-sensitive resist composition according to claim 1, wherein The acid generator (B) is represented by the following formula (11) and / or (12):

(In formula (11), 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, X ⁻ represents 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, and R ¹⁴ is the same in formula (12). But it may be different, each independently, a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, .X representing a hydroxyl group or a halogen atom ^- is the Is the same.)
The radiation-sensitive resist composition according to any one of claims 1 to 4, which is at least one compound selected from the group consisting of compounds represented by: 6. The radiation-sensitive resist composition according to claim 5, wherein X < ^- > is a sulfonate ion having an aryl group having 6 to 12 carbon atoms. The acid crosslinking agent (C) is represented by the following formulas (21) to (23):

(In the above formula, each R ⁷ independently represents a hydrogen atom, an alkyl group, or an acyl group; each of R ^{8 to} R ¹¹ independently represents a hydrogen atom, a hydroxyl group, an alkyl group, or an alkoxyl group; X ² represents a single bond, a methylene group, or an oxygen atom)
The radiation-sensitive resist composition according to any one of claims 1 to 6, which is at least one compound selected from the group consisting of a compound represented by formula (1) and an alkoxymethylated melamine compound. The radiation-sensitive resist composition according to claim 7, wherein the acid crosslinking agent (C) is an alkoxymethylated melamine compound. The radiation-sensitive resist composition according to claim 1, comprising 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent component. The solid component is 65 to 96.9% by weight of a resist compound (A), 0.1 to 30% by weight of an acid generator (B), 0.3 to 34.9% by weight of an acid crosslinking agent (C), an optional component (D) The radiation sensitive resist composition of Claim 9 which consists of 0-30 weight%.