JP4687094B2 - Resist compound and radiation-sensitive composition - Google Patents

Description

  The present invention relates to a resist compound represented by a specific chemical structural formula, which is useful as an acid amplification type non-polymer resist material. Moreover, this invention relates to the radiation sensitive composition containing this compound and an acid generator. The compound of the present invention is used as a radiation-sensitive material sensitive to ultraviolet rays, far-ultraviolet rays, extreme ultraviolet rays (EUV), electron beams, and X-rays, for masks used in the manufacture of LSIs and VLSIs in the electronics field.

  Conventional general resist materials are polymer materials capable of forming an amorphous thin film. For example, a line width is obtained by irradiating a resist thin film prepared by applying a polyhydroxystyrene derivative and a solution dissolved in a solvent for dissolving it on a substrate with ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. A line pattern of about 0.08 μm is produced.

  However, conventional polymer resist materials have a large molecular weight of about 10,000 to 100,000, a wide molecular weight distribution, and further entanglement between polymer chains, so that fine processing advances in lithography using polymer resist materials. Then, roughness is generated on the pattern surface, and it becomes difficult to control the pattern dimension, resulting in a decrease in yield and deterioration in transistor characteristics. Therefore, there is a limit to miniaturization with a line width of 0.06 μm or less in conventional lithography using a polymer resist material. Therefore, in order to produce a finer pattern, a material having a small molecular weight distribution and a narrow molecular weight distribution is disclosed.

  Examples of non-polymer resist materials are (1) positive and negative resists derived from fullerene, (2) positive and negative resists derived from calixarene, and (3) derived from starburst compounds. A positive resist, (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, And (7) a positive resist derived from a starburst compound having an ester bond with trimesic acid as the central skeleton.

  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 due to 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 to 13.) Regarding (6), the manufacturing process is complicated, the raw materials are expensive, and a metal catalyst which is hated by semiconductor factories is used, so 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 it cannot be said that it is practical (see Patent Document 14). .

Moreover, the example which uses a low molecular compound as an additive of the photosensitive resin composition is disclosed. Photosensitive resin composition comprising a photoactive compound having a hydrophobic group selected from a hydrocarbon group and a heterocyclic group, a linking group, and a hydrophilic group protected by a protecting group removable by light irradiation (Patent Literature) 15), a resist composition comprising a low-molecular dissolution inhibiting compound having a structure in which two or more triphenylmethane structures are non-conjugatedly linked to a portion other than a group that can be decomposed by the action of an acid (see Patent Document 16). ), A resist resin composition containing a photoactive compound having a fluorene structure (see Patent Document 17) is exemplified, but a composition containing the compound of the present invention described below as a main component is disclosed. Not. Moreover, since both are resist compositions containing a resin, the line edge roughness of the pattern to be formed is large and cannot be said to be sufficient. Further, when the disclosed resist compound is used as a main component, the propylene glycol mono-monohydride generally used in semiconductor factories, having high crystallinity and poor film formability, not having heat resistance to withstand semiconductor processes. It was difficult to use as a single component due to any problems such as poor solubility in safety solvents such as ethyl ether acetate and ethyl lactate and poor substrate adhesion.
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 JP 2002-363123 A JP 2001-312055 A JP 2004-137262 A Proceedings of SPIE vol. 3999 (2000) P1202-1206.

  An object of the present invention is to provide a compound and a radiation-sensitive composition that are sensitive to radiation such as excimer laser light such as KrF, extreme ultraviolet light (EUV), electron beam, and X-ray. Another object of the present invention is to provide a high-sensitivity, high-resolution, high heat resistance, high etching resistance and solvent-soluble non-polymeric radiation-sensitive composition without using a metal catalyst and with a simple production process. There is to do.

（式（２）中、
Ｒ ^１ は、それぞれ独立に、メトキシメチル基、メチルチオメチル基、エトキシメチル基、エチルチオメチル基、メトキシエトキシメチル基、ベンジルオキシメチル基、ベンジルチオメチル基、フェナシル基、４−ブロモフェナシル基、４−メトキシフェナシル基、ピペロニル基、メトキシカルボニルメチル基、エトキシカルボニルメチル基、ｎ−プロポキシカルボニルメチル基、ｉ−プロポキシカルボニルメチル基、ｎ−ブトキシカルボニルメチル基、ｔｅｒｔ−ブトキシカルボニルメチル基、１−メトキシエチル基、１−メチルチオエチル基、１，１−ジメトキシエチル基、１−エトキシエチル基、１−エチルチオエチル基、１，１−ジエトキシエチル基、１−フェノキシエチル基、１−フェニルチオエチル基、１，１−ジフェノキシエチル基、１−シクロペンチルオキシエチル基、１−シクロヘキシルオキシエチル基、１−フェニルエチル基、１，１−ジフェニルエチル基、１−メトキシ−ｎ−プロピル基、１−エトキシ−ｎ−プロピル基、イソプロピル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、１，１−ジメチルプロピル基、１−メチルブチル基、１，１−ジメチルブチル基、トリメチルシリル基、エチルジメチルシリル基、メチルジエチルシリル基、トリエチルシリル基、ｔｅｒｔ−ブチルジメチルシリル基、ｔｅｒｔ−ブチルジエチルシリル基、ｔｅｒｔ−ブチルジフェニルシリル基、トリ−ｔｅｒｔ−ブチルシリル基、トリフェニルシリル基、アセチル基、フェノキシアセチル基、プロピオニル基、ブチリル基、ヘプタノイル基、ヘキサノイル基、バレリル基、ピバロイル基、イソバレリル基、ラウリロイル基、アダマンチル基、ベンゾイル基、ナフトイル基、１−シクロペンチルメトキシメチル基、１−シクロペンチルエトキシメチル基、１−シクロヘキシルメトキシメチル基、１−シクロヘキシルエトキシメチル基、１−シクロオクチルメトキシメチル基、１−アダマンチルメトキシメチル基、テトラヒドロピラニル基、テトラヒドロフラニル基、テトラヒドロチオピラニル基、テトラヒドロチオフラニル基、４−メトキシテトラヒドロピラニル基、４−メトキシテトラヒドロチオピラニル基、メトキシカルボニル基、エトキシカルボニル基、ｎ−プロポキシカルボニル基、ｉ−プロポキシカルボニル基、ｎ−ブトキシカルボニル基およびｔｅｒｔ−ブトキシカルボニル基からなる群から選択される酸解離性官能基である。
Ｒ ^２ は、それぞれ独立に、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；
Ｒ ^３ は、それぞれ独立に水素原子または炭素数１〜６のアルキル基であり；
Ｒ ^５ は、それぞれ独立に炭素数１〜６のアルキル基であり；
ｍ０、ｎ０は０〜３の整数であり；
ｍ１、ｎ１は０〜３の整数であり；
ｍ２、ｎ２は０〜４の整数であり；
１≦ｍ０＋ｍ１＋ｍ２≦５、 １≦ｎ０＋ｎ１＋ｎ２≦５、 １≦ｍ１＋ｎ１≦６、 1≦ｍ０＋ｍ1≦３、 1≦ｎ０＋ｎ1≦３、 ０≦ｌ≦４の条件を満たす。） As a result of intensive studies, the present inventors have found that a compound represented by a specific chemical structural formula is useful for solving the above problems. That is, the present invention relates to a compound represented by formula (2) and a radiation sensitive composition. The radiation sensitive composition of this invention contains the compound shown by Formula (2) , and an acid generator.

(In the formula (2),
R ¹ is independently methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, 4-bromophenacyl group, 4- Methoxyphenacyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, tert-butoxycarbonylmethyl group, 1-methoxyethyl Group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group 1,1-diphenoxyethyl Group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxy-n-propyl group, 1-ethoxy-n-propyl group, isopropyl Group, sec-butyl group, tert-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiethylsilyl group, tert-butyldiphenylsilyl group, tri-tert-butylsilyl group, triphenylsilyl group, acetyl group, phenoxyacetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl Group, valeryl group, Loyl group, isovaleryl group, laurylyl group, adamantyl group, benzoyl group, naphthoyl group, 1-cyclopentylmethoxymethyl group, 1-cyclopentylethoxymethyl group, 1-cyclohexylmethoxymethyl group, 1-cyclohexylethoxymethyl group, 1-cyclooctyl Methoxymethyl group, 1-adamantylmethoxymethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, methoxy Selected from the group consisting of carbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group and tert-butoxycarbonyl group It is a dissociative functional group.
R ² is independently 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, or a nitro group. Represents a substituent selected from the group consisting of:
Each R ³ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Each R ⁵ is independently an alkyl group having 1 to 6 carbon atoms;
m0 and n0 are integers of 0 to 3;
m1 and n1 are integers of 0 to 3;
m2 and n2 are integers of 0 to 4;
1 ≦ m0 + m1 + m2 ≦ 5, 1 ≦ n0 + n1 + n2 ≦ 5, 1 ≦ m1 + n1 ≦ 6, 1 ≦ m0 + m1 ≦ 3, 1 ≦ n0 + n1 ≦ 3, 0 ≦ l ≦ 4. )

  By using the radiation-sensitive composition according to the present invention, a high-resolution and high-sensitivity pattern can be produced, so that a highly integrated semiconductor element can be produced with high productivity.

本発明において、酸解離性官能基とは、酸の存在下で開裂して、フェノール性水酸基を生じる特性基をいい、アルキル基、アルキルシリル基、アシル基、アルコキシカルボニル基、フェノキシカルボニル基等が挙げられる。前記酸解離性官能基は、更に高感度・高解像度なパターン形成を可能にするために、酸の存在下で連鎖的に開裂反応を起こす性質を有することが好ましい。
式（２）中、Ｒ^１は、それぞれ独立に、置換メチル基、１−置換エチル基、１−置換−ｎ−プロピル基、１−分岐アルキル基、シリル基、アシル基、１−置換アルコキシメチル基、環状エーテル基、およびアルコキシカルボニル基からなる群から選択される酸解離性官能基である。 Hereinafter, the present invention will be described in detail.
The compound of the present invention (hereinafter referred to as compound (A)) is a compound represented by formula (2) .

In the present invention, the acid dissociable functional group means a characteristic group that is cleaved in the presence of an acid to generate a phenolic hydroxyl group, and includes an alkyl group, an alkylsilyl group, an acyl group, an alkoxycarbonyl group, a phenoxycarbonyl group, and the like. Can be mentioned. The acid-dissociable functional group preferably has a property of causing a chain-breaking reaction in the presence of an acid in order to enable pattern formation with higher sensitivity and higher resolution.
In formula (2) , each R ¹ independently represents a substituted methyl group, a 1-substituted ethyl group, a 1-substituted n-propyl group, a 1-branched alkyl group, a silyl group, an acyl group, or a 1-substituted alkoxymethyl. An acid dissociable functional group selected from the group consisting of a group, a cyclic ether group, and an alkoxycarbonyl group.

The substituted methyl group, methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, 4-bromophenacyl group, 4-Metokishifena sill group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n- propoxycarbonylmethyl group, i- propoxycarbonyl methyl group is that of the n- butoxycarbonyl methyl group or tert- butoxycarbonyl methyl group.

The specific examples of the 1-substituted ethyl group, 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxy Ethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1-phenylethyl group or 1,1-diphenyl is that of an ethyl group.

The 1-substituted -n- propyl group, for example, is that of 1-methoxy -n- propyl or 1-ethoxy -n- propyl.

The 1-branched alkyl group, an isopropyl group, sec- butyl group, tert- butyl group, 1,1-dimethylpropyl group, is that of a 1-methylbutyl group or a 1,1-dimethylbutyl group.

Silyl group means trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiethylsilyl group, tert-butyldiphenylsilyl group, tri-tert-butylsilyl group or is that of a triphenylsilyl group.

The acyl group is that of the acetyl group, phenoxyacetyl group, a propionyl group, a butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauroyl group, an adamantyl group, a benzoyl group or a naphthoyl group.

The 1-substituted alkoxymethyl group means 1-cyclopentylmethoxymethyl group, 1-cyclopentylethoxymethyl group, 1-cyclohexylmethoxymethyl group, 1-cyclohexylethoxymethyl group, 1-cyclooctylmethoxymethyl group or 1-adamantyl. It means a methoxymethyl group.

Further, a cyclic ether group, is that the tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 4-methoxy-tetrahydropyranyl group or a 4-methoxy tetrahydrothiopyranyl group.

Furthermore, the alkoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, n- propoxycarbonyl group, i- propoxycarbonyl group, n- butoxycarbonyl group or tert- butoxycarbonyl group.

  Among these acid dissociable functional groups, tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-cyclohexyloxyethyl group, 1-phenylethyl group, tert- A butyl group, a trimethylsilyl group, a tetrahydropyranyl group and a 1-cyclohexylmethoxymethyl group are preferred.

R ² each independently represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, or an aryloyloxy group. And a substituent selected from the group consisting of a cyano group and a nitro group.
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, cycloalkyl groups include cyclohexyl group, norbornyl group, adamantyl group and the like, and aryl groups include phenyl group, tolyl group, xylyl group and naphthyl group. The aralkyl group includes a benzyl group, the alkoxy group includes a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, sec An abutene having 1 to 4 carbon atoms such as a butoxy group or a tert-butoxy group; Examples of the aryloxy group include a phenoxy group. Examples of the alkenyl group include an alkenyl group having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group, and a butenyl group, and an acyl group. Examples thereof include an aliphatic acyl group having 1 to 6 carbon atoms such as formyl group, acetyl group, propionyl group, butyryl group, valeryl group, isovaleryl group and pivaloyl group, and aromatic acyl groups such as benzoyl group and toluoyl group. Alkoxycarbonyl groups include carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, etc. Number 2-5 alkoxycarbo Examples of the alkyloyloxy group include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group valeryloxy group, isovaleryloxy group, pivaloyloxy group, and the like. An oxy group etc. are mentioned.

R ² is preferably substituted at the ortho position of the phenolic hydroxyl group. The ortho-position R ² suppresses the crystallinity of the compound (A) and improves the film formability. In addition, since the solubility of the compound (A) in an alkaline developer is suppressed, the acid dissociation protection rate of the resist compound can be reduced, so that solvent solubility and substrate adhesion are improved, and resist sensitivity is further improved. Sometimes. R ² effective for this purpose is preferably a bulky structure and / or an electron donating group, and is an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a phenyl group, a benzyl group, a cyclohexyl group, a norbornyl group). , An adamantyl group, etc.), an alkoxy group (for example, a methoxy group, an ethoxy group, an isopropoxy group, a phenoxy group, etc.). An electron-withdrawing functional group such as halogen may increase the solubility of the compound (A) in an alkaline developer.

R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, and cyclohexyl. Straight chain, branched or cyclic alkyl groups such as groups.
R ⁵ represents an alkyl group having 1 to 6 carbon atoms.

Since the phenanthrene structure is a rigid and asymmetric structure by being induced into a polyphenol structure, the resist material can have both heat resistance and amorphous properties (film forming properties). In addition, since the π-conjugate has a wide structure, the energy transfer efficiency to the acid generator is good due to the sensitizing action, so that high sensitivity can be obtained. In addition, the structure has a high carbon density, so it has good light transmittance for EUV light, small outgas amount for high energy rays, and excellent dry etching resistance.
In Formula (2) , m0 and n0 are integers of 0 to 3, m1 and n1 are integers of 0 to 3,
m2 and n2 are integers of 0 to 4, 1 ≦ m0 + m1 + m2 ≦ 5, 1 ≦ n0 + n1 + n2 ≦
5, 1 ≦ m1 + n1 ≦ 6, 1 ≦ m0 + m1 ≦ 3, 1 ≦ n0 + n1 ≦ 3 , 0 ≦ l ≦ 4 .

（式中、Ｒ^１は、独立に水素原子、または置換メチル基、１−置換エチル基、１−置換−ｎ−プロピル基、１−分岐アルキル基、シリル基、アシル基、１−置換アルコキシメチル基、環状酸解離性官能基、およびアルコキシカルボニル基からなる群から選択される酸解離性官能基であって少なくとも一つは水素原子以外の酸解離性官能基であり，R^６は水素原子またはメチル基である。）
上記化合物は、感度、耐熱性、解像性に優れる。また比較的安価なフェノール類から製造でき、更に単離精製が容易であることから品質管理の面でも優れている。 The compound (A) is more preferably a compound represented by the formula (3).

(In the formula, R ¹ is independently a hydrogen atom, or a substituted methyl group, 1-substituted ethyl group, 1-substituted n-propyl group, 1-branched alkyl group, silyl group, acyl group, 1-substituted alkoxymethyl. An acid dissociable functional group selected from the group consisting of a group, a cyclic acid dissociable functional group, and an alkoxycarbonyl group, at least one of which is an acid dissociable functional group other than a hydrogen atom, and R ⁶ is a hydrogen atom or It is a methyl group.)
The above compound is excellent in sensitivity, heat resistance, and resolution. In addition, it can be produced from relatively inexpensive phenols, and is easy to isolate and purify, so it is excellent in terms of quality control.

（式中、R^６は水素原子またはメチル基である。）
上記化合物は，特に感度，解像性に優れる。 The compound (A) is particularly preferably a compound represented by the formula (4).

(In the formula, R ⁶ is a hydrogen atom or a methyl group.)
The above compounds are particularly excellent in sensitivity and resolution.

  Compound (A) includes a step in which a carbonyl compound having a phenanthrene structure and a phenol are subjected to a condensation reaction in the presence of a catalyst system composed of thiols and sulfuric acid, and a crystallization step in which a bisphenol compound is crystallized from the reaction mixture. And a step of introducing an acid-dissociable functional group into the bisphenol compound.

  In the reaction between the carbonyl compound and the phenol, the purity of the carbonyl compound is not particularly limited, and is usually 95% by weight or more, preferably 99% by weight or more.

  Specific examples of the carbonyl compound having a phenanthrene structure include, for example, phenanthrenecarbaldehyde, methylphenanthrenecarbaldehyde, dimethylphenanthrenecarbaldehyde, trimethylphenanthrenecarbaldehyde, acetylphenanthrene, acetylmethylphenanthrene, acetyldimethylphenanthrene, acetyltrimethylphenanthrene, and the like. It is done.

  Of these carbonyl compounds, phenanthrene-9-carbaldehyde, 3-acetylphenanthrene and 9-acetylphenanthrene are preferred.

Specific examples of the phenols include, for example, phenol, C _1-4 alkylphenol (eg, cresols such as o-cresol, m-cresol, p-cresol), dialkylphenol (eg, 2,3-dimethylphenol, 2,5 -Dimethylphenol, 2,6-dimethylphenol, 2,6-di-tert-butylphenol, etc.), trialkylphenol, alkoxyphenol (eg, anisole such as o-methoxyphenol), arylphenol (eg, o-, m-) Phenylphenol such as phenylphenol), cycloalkylphenol (eg 2-cyclohexylphenol), chlorophenol, dichlorophenol, chlorocresol, bromophenol, dibromophenol; catechol, al Le catechol, chloro catechol, resorcinol, alkyl resorcinol, hydroquinone, alkyl hydroquinone, chloro resorcinol, chlorohydroquinone, pyrogallol, alkyl pyrogallol, etc. 1,2,4-trihydroxy phenols can be exemplified. You may use phenols individually or in combination of 2 or more types. The purity of the phenols is not particularly limited, but is usually 95% by weight or more, preferably 99% by weight or more.

Of these phenols, phenol, C _1-4 alkylphenol, such as 2-C _1-4 alkylphenol (such as o-cresol), are preferable, 2,5-xylenol, 2,6-xylenol, 2,3,6 trimethyl. Phenol is particularly preferred.

  The bisphenol compound is composed of 1 mol to an excess of phenols such as phenol and o-cresol, thioacetic acid or β-mercaptopropionic acid, and an acid with respect to 1 mol of a carbonyl compound having a phenanthrene structure such as phenanthrene-9-carbaldehyde. Using a catalyst (hydrochloric acid or sulfuric acid), the reaction is carried out at 60 to 150 ° C. for about 0.5 to 20 hours. After completion of the reaction, toluene is added to the reaction solution and heated to 60 to 80 ° C. for 0.5 to 2 hours. After stirring, the mixture is cooled to room temperature, filtered, separated, and dried. Next, a compound for introducing an acid dissociable functional group such as ethoxyethyl group is added to the bisphenol compound, and the reaction is carried out under a catalyst such as pyridinium p-toluenesulfonate at normal pressure, 20 to 60 ° C. for 6 to 72 hours, The reaction solution is added to distilled water to precipitate a white solid, which is washed with distilled water, purified by silica gel column chromatography as necessary, and dried to produce the compounds of formulas (1) and (2). .

  As the compound for introducing the acid dissociable functional group used above, an active carboxylic acid derivative compound such as acid chloride, acid anhydride or dicarbonate having an acid dissociable functional group; alkyl halide; vinyl alkyl ether, Although unsaturated ethers, such as dihydropyran, etc. are mentioned, it does not specifically limit.

  The compound represented by the formula (3) can be produced by the above method by using phenanthrene-9-carbaldehyde as the carbonyl compound and 2,5-xylenol as the phenol.

  The compound represented by the formula (4) can be produced by the above method by introducing 1 mol of an ethoxyethyl group as an acid dissociable functional group.

The compounds represented by the formulas (2) to (4) are acid amplification type compounds. When an acid coexists, the acid dissociable functional group is eliminated and converted to a phenolic hydroxyl group. Since the elimination of phenolic hydroxyl group effectively proceeds with the autocatalytic effect and becomes an alkali-soluble material, it can be used as a positive resist capable of alkali development. The method for generating the acid is not particularly limited. For example, the acid is generated in the ultraviolet light or high-energy exposed portion by coexisting a photoacid generator.

  The radiation-sensitive composition of the present invention is directly or indirectly irradiated with one or more of the above compounds and radiation such as visible light, ultraviolet light, extreme ultraviolet light (EUV), excimer laser, electron beam, X-ray, or ion beam. One or more acid generators that generate acid are included.

  The acid generator is preferably at least one selected from the group consisting of compounds represented by the following formulas (5) to (12).

In the formula (5), R ²³ 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 (5) is triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium 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 nonafluoro-n-butanesulfonate, diphenyl-4- Hydroxyphenylsulfonium trifluoromethanesulfonate, bis (4-fluorophenyl) -4-hydroxyphenylsulfoniu Trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, tri (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (4-fluoro Phenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium benzenesulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2 -Trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-4 Trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenylnaphthylsulfonium trifluoromethanesulfonate, diphenyl It is preferably at least one selected from the group consisting of -4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, and diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate.

In the formula (6), R ²⁴ 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.

  The compound represented by the formula (6) 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-tert-butylphenyl) iodonium p-toluenesulfonate, bis (4-tert-butylphenyl) iodoniumbenzenesulfonate, bis (4-tert-butylphenyl) iodonium- 2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluorobenzenesulfonate, bis (4- t-Butyl Nyl) 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 To diphenyliodonium Safluorobenzenesulfonate, di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, di (4-trifluoromethylphenyl) iodonium perfluoro- The group consisting of n-octanesulfonate, di (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, di (4-trifluoromethylphenyl) iodoniumbenzenesulfonate and di (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate It is preferable that it is at least one selected from.

In the formula (7), Q is an alkylene group, an arylene group or an alkoxylene group, and R ²⁵ is an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.

  The compound represented by the formula (7) 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- (1 -Camphorsulfonyloxy) naphthylimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) naphthyl Imido, 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-dicarboxiimi 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) naphthyl Imide, 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-5-ene Is preferably 2,3-dicarboximide and N- at least one selected from the group consisting of (perfluoro--n- octane sulfonyloxy) naphthylimide.

In formula (8), R ²⁶ 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 (8) includes diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone, di It is at least one selected from the group consisting of (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone and di (4-toluromethylphenyl) disulfone. preferable.

In formula (9), R ²⁷ 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 (9) 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 (10), R ²⁸ 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.

In formulas (11) and (12), R ²⁹ and R ³⁰ 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 ²⁹ and L ³⁰ 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 ²⁹ 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 (13), a carbonyl group, an ester group, an amide group or an ether group, and Y ²⁹ is A hydrogen atom, an alkyl group or an aryl group, and X ²⁹ and X ³⁰ are each independently a group represented by the following formula (14).

In formula (14), Z ³² is each independently an alkyl group, a cycloalkyl group or an aryl group, R ³² 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) ) Bissulfonyldiazomethanes such as diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, 2- (4-methoxyphenyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3 5-triazine, tris (2,3-dibromopropyl) Halogen-containing triazine derivatives, such as isocyanurate and the like.

  Moreover, an acid generator can be used individually or in mixture of 2 or more types. 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, still more preferably 1 to 15 parts by weight per 100 parts by weight of the compound. Part. If the amount is less than 0.1 part by weight, the sensitivity and resolution tend to decrease. On the other hand, if the amount exceeds 30 parts by weight, the cross-sectional shape of the resist pattern tends to decrease.

  The radiation-sensitive composition of the present invention comprises a solid component of 1 to 80% by weight and a solvent of 20 to 99% by weight, preferably a solid component of 1 to 50% by weight and a solvent of 50 to 99% by weight, particularly preferably solid. Contains 5-40% by weight of components and 60-95% by weight of solvent. The total content of the compound (B) and the dissolution accelerator is 50 to 99.999% by weight, preferably 60 to 99% by weight, particularly preferably 80 to 99% by weight, based on the total weight of the solid components. is there. The blending ratio of the dissolution accelerator is preferably 0 to 80% by weight, more preferably 20 to 80% by weight, and particularly preferably 30 to 70% by weight based on the total weight of the solid component. With the above blending ratio, high sensitivity and high resolution can be obtained, and the line edge roughness becomes small.

  Examples of the solvent used in the radiation-sensitive composition of the present invention include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; ethylene glycol monomethyl ether and ethylene glycol monoethyl. Ethylene glycol monoalkyl ethers such as ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether Propylene glycol monoalkyl ethers; methyl lactate, lactate ester Lactic acid esters such as ruthenium (EL); Aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate Other esters such as ethyl 3-ethoxypropionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; Cyclic ethers such as tetrahydrofuran and dioxane There is no particular limitation. These solvents can be used alone or in combination of two or more.

  When the solubility of the compound (A) in a developing solution such as an alkali is relatively low, the dissolution accelerator has an action of increasing the solubility of the compound (A) during development by appropriately increasing the solubility. It is an ingredient. As such a dissolution accelerator, those that do not chemically change in steps such as baking of the resist film, electron beam irradiation, and development are preferable. Examples of the dissolution accelerator include low molecular weight phenolic compounds. Specific examples include bisphenols, tris (hydroxyphenyl) methane, and tetrakisphenols. Examples of bisphenols include biphenol, bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methanone, methylene bisphenol, ethylidene bisphenol, cyclohexylidene bisphenol, and phenylethylidene bisphenol. Tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenylbenzene) and the like can be mentioned, and tetrakisphenols are 4,4 ′, 4 ″, 4 ′ ″. -(1,2-ethanediylidene) tetrakisphenol, 4,4 ', 4' ', 4' ''-(1,2-phenylenedimethylidyne) tetrakisphenol, calix [4] arene, tetrakis (bicyclohexylidene) F Nord, and the like. These dissolution promoters can be used alone or in admixture of two or more.

（式（２５）中、Ｒ^２、Ｒ^３、およびＲ^４は前記と同様であり、
ｍ３、ｎ３はそれぞれ１〜３の整数であり；
ｍ４、ｎ４はそれぞれ０〜４の整数であり；
１≦ｍ３＋ｍ４≦５、1≦ｎ３＋ｎ４≦５である。） The low molecular weight phenolic compound is preferably a compound of the following formula (25).

(In Formula (25), R ² , R ³ , and R ⁴ are the same as described above,
m3 and n3 are each an integer of 1 to 3;
m4 and n4 are each an integer of 0 to 4;
1 ≦ m3 + m4 ≦ 5 and 1 ≦ n3 + n4 ≦ 5. )

（式（２６）中、Ｒ^３は前記と同様であり、ｎは０〜３の整数である。） The low molecular weight phenolic compound is particularly preferably a compound of the following formula (26).

(In formula (26), R ³ is the same as described above, and n is an integer of 0 to ^3. )

  Various additives such as an acid diffusion controller, a dissolution controller, a sensitizer, and a surfactant can be added to the radiation-sensitive composition of the present invention.

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

  The blending amount of the acid diffusion controller is preferably 0 to 10% by weight, more preferably 0.001 to 5% by weight, particularly preferably 0.001 to 3% by weight, based on the total weight of the solid component. is there. When the compounding amount of the acid diffusion control agent is 0.001% by weight, depending on the process conditions, the resolution, pattern shape, and dimensional fidelity tend to decrease, and further, from electron beam irradiation to post-irradiation heating. If the holding time of the pattern becomes longer, the pattern shape tends to deteriorate in the upper layer portion of the pattern. On the other hand, when the compounding amount of the acid diffusion control agent exceeds 10% by weight, the sensitivity of the resist composition, the developability of the unexposed area, and the like tend to decrease.

  The dissolution control agent is a component having an action of appropriately reducing the dissolution rate during development by controlling the solubility when the solubility of the compound (A) in a developing solution such as an alkali is relatively high. As such a dissolution control agent, those that do not chemically change in steps such as baking of the 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 amount of the dissolution control agent is appropriately adjusted according to the type of the compound (A) to be used, but is preferably 0 to 50% by weight, more preferably 0.1% based on the total weight of the solid component. -20% by weight, particularly preferably 1-10% by weight.

  The sensitizer absorbs the energy of the irradiated radiation and transmits the energy to the photoacid generator, thereby increasing the amount of acid generated and improving the apparent sensitivity of the resist. It is. 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 0 to 50% by weight based on the total weight of the solid component, more preferably 0.1 to 20% by weight, and particularly preferably 1 to 10% by weight.

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

    The blending amount of the surfactant is preferably 0 to 2% by weight based on the total weight of the solid component, more preferably 0.0001 to 1% by weight, and particularly preferably 0.001 to 0.1% by weight. It is. Further, by blending a dye or a pigment, the latent image in the exposed area can be visualized, and the influence of halation during exposure can be reduced. Furthermore, the adhesiveness with a board | substrate can be improved by mix | blending an adhesion aid.

  In addition to the above-mentioned additives, the radiation-sensitive composition of the present invention is a resin that is insoluble in water and soluble in an alkaline aqueous solution, or is insoluble in water and soluble in an alkaline aqueous solution by the action of an acid, and developed with an alkaline aqueous solution. You may add resin which becomes possible. Examples of the resin that can be added include a phenol resin or a resin in which an acid-dissociable functional group is introduced into a phenol resin; a resin in which an acid-dissociable functional group is introduced into a novolac resin or a novolac resin; O-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof or o-polyhydroxystyrene, m-polyhydroxystyrene, p- Resins having acid-dissociable functional groups introduced into polyhydroxystyrene and copolymers thereof; resins having acid-dissociable functional groups introduced into alkyl-substituted polyhydroxystyrene or alkyl-substituted polyhydroxystyrene; polyhydroxystyrene or polyhydroxy Styrene has acid-dissociable functional groups Incorporated resin; Resin in which part of polyhydroxystyrene is o-alkylated or Resin in which part of polyhydroxystyrene is o-alkylated; Resin having functional group capable of acid dissociation; Styrene-hydroxystyrene Resin having an acid-dissociable functional group introduced into a copolymer or a styrene-hydroxystyrene copolymer; an acid-dissociative functional group into an α-methylstyrene-hydroxystyrene copolymer or an α-methylstyrene-hydroxystyrene copolymer A resin in which an acid-dissociable functional group is introduced into a polyalkyl methacrylate resin or polyalkyl methacrylate, a polyolefin, a polyester, a polyamide, a polyurea, and a polyurethane. However, since the line edge roughness increases with the amount of resin added, a better pattern profile tends to be obtained when it is not added as much as possible.

  The radiation-sensitive composition of the present invention is obtained by stirring and mixing the compound (A), a solvent, an acid generator and other additives. There is no particular limitation on the stirring, mixing method and order of addition, and it can be easily produced based on the ordinary knowledge of those skilled in the art.

  In order to form a resist pattern using the radiation-sensitive composition of the present invention, first, a radiation-sensitive composition is spin-coated on a substrate such as a silicon wafer, a gallium arsenide wafer, or a wafer coated with aluminum. A resist film is formed by coating by a coating means such as spread coating or roll coating.

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

  The thickness of the resist film is not particularly limited, and is preferably 0.01 to 10 μm, more preferably 0.05 to 1 μm, and particularly preferably about 0.08 to 0.5 μm.

  If necessary, a resist protective film may be formed to prevent intrusion of amine or the like floating in the air after the resist film is formed. By forming a resist protective film, the acid generated by radiation reacts with a compound that reacts with an acid such as amine floating as an impurity in the atmosphere and deactivates, and the resist image deteriorates and sensitivity decreases. This can be suppressed. The material for the resist protective film is preferably a water-soluble and acidic polymer. Examples thereof include polyacrylic acid and polyvinyl sulfonic acid.

  Next, the resist film is exposed to a desired pattern by radiation such as ultraviolet rays, extreme ultraviolet rays (EUV), and electron beams. In the exposed compound (A), the acid-dissociable functional group is cleaved to become a phenolic hydroxyl group, which changes to a compound soluble in an alkali developer. The exposure conditions and the like are appropriately selected according to the composition of the radiation sensitive composition. In the present invention, in order to stably form a high-precision fine pattern in exposure, heating is preferably performed after irradiation with radiation. The heating conditions vary depending on the composition of the radiation sensitive composition, but are preferably 20 to 250 ° C, more preferably 40 to 150 ° C.

  Next, the exposed resist film is developed with an alkaline developer to form a predetermined resist pattern. Examples of the alkaline developer include alkaline such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), choline and the like. An alkaline aqueous solution 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.

  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. 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 remaining resist pattern 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 the PGMEA, PGME, and EL, and examples of the strong alkaline aqueous solution include a 1 to 20% by mass sodium hydroxide aqueous solution and a 1 to 20% by mass potassium hydroxide aqueous solution. 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 using the radiation-sensitive composition of the present invention can also be formed by a method of depositing a metal in a 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 particularly limited to these examples.

<Synthesis Example 1>
(1) Synthesis of Compound (1-1) 2,5-xylenol 49 g (0.4 mol) (Honshu Chemical Industry) and phenanthrene-9-carbaldehyde 18 g (0.1 mol) (Aldrich reagent) were mixed, After dissolution by heating to about 60 ° C., 0.1 ml of sulfuric acid and 0.8 ml of 3-mercaptopropionic acid were slowly added dropwise and reacted with stirring. After confirming a conversion rate of 100% by GC, 100 ml of toluene was added, cooled and the precipitated solid was filtered under reduced pressure, further washed again with toluene, filtered under reduced pressure and dried under reduced pressure to obtain 39 g of the desired product. The target product was confirmed by 400 MHz- ¹ H-NMR.

(2) Synthesis of resist compound (1-2) 4.32 g (10 mmol) of compound (1-1) synthesized as described above, 0.87 (12 mmol) of ethyl vinyl ether, 0.54 g of pyridinium p-toluenesulfonate A solution obtained by adding 10 ml of anhydrous acetone to the mixture was stirred at room temperature for 72 hours. The reaction solution was separated and purified by column chromatography and dried under reduced pressure to obtain a white powder. 0.53 g of the target compound (1-2) was obtained. It was confirmed by 400 MHz- ¹ H-NMR that it had the chemical structure of formula (1-2).
¹ H-NMR: (400 MHz, d-DMSO, internal standard TMS)
δ (ppm) 9.1 (1H 2 O— H ), 8.8 to 7.0 (9H phenanthrene) 7.1 to 6.1 (4H—Ph H (CH ₃ ) ₂ ), 6.4 (1H − C H- ), 3.3 (2H -C H ₂ CH ₃ ), 2.1 to 1.9 (12H Ph-C H ₃ ) 1.4 (3H -CH-C H ₃ ), 1.1 ( 3H -CH ₂ C H ₃₎

<Synthesis Example 2>
(1) Synthesis of compound (2-1) 2,3,6-trimethylphenol 49 g / 0.4 mol (manufactured by Honshu Chemical Industry) and 9-phenanthrenecarbaldehyde 18 g / 0.1 mol (aldrich reagent) were mixed, After dissolution by heating to about 60 ° C., 0.1 ml of sulfuric acid and 0.8 ml of 3-mercaptopropionic acid were slowly added dropwise and reacted with stirring. After confirming a conversion rate of 100% by GC, 100 ml of toluene was added, cooled and the precipitated solid was filtered under reduced pressure, further washed again with toluene, filtered under reduced pressure and dried under reduced pressure to obtain 39 g of the desired product. The target product was confirmed by 400 MHz- ¹ H-NMR.

(2) Synthesis of resist compound (2-2) 4.60 g (10 mmol) of compound (2-1) synthesized as described above, 0.87 (12 mmol) of ethyl vinyl ether, 0.54 g of pyridinium p-toluenesulfonate A solution obtained by adding 10 ml of anhydrous acetone to the mixture was stirred at room temperature for 72 hours. The reaction solution was separated and purified by column chromatography and dried under reduced pressure to obtain a white powder. 0.53 g of the target compound (2-2) was obtained. It was confirmed by 400 MHz- ¹ H-NMR that it had the chemical structure of formula (2-2).
¹ H-NMR: (400 MHz, d-DMSO, internal standard TMS)
δ (ppm) 9.1 (1H 2 O— H ), 8.8 to 7.0 (9H phenanthrene) 7.1 to 6.3 (2H—Ph H (CH ₃ ) ₂ ), 6.4 (1H − C H- ), 3.3 (2H -C H ₂ CH ₃ ), 2.1 to 1.8 (18H Ph-C H ₃ ) 1.4 (3H -CH-C H ₃ ), 1.1 ( 3H -CH ₂ C H ₃₎

Examples (1) Preparation of Resist Compound (1-1) / (1-2) = 1/1 0.08 g, Tolyldiphenylsulfonium Nanofluorobutanesulfonate (Reagent manufactured by Wako Pure Chemical Industries, Ltd.) 0.008 g Then, after preparing a homogeneous solution of propylene glycol monomethyl ether acetate (PGMEA) / ethyl lactate (EL) = 2/5 2.2 g, the solution was filtered through a Teflon (registered trademark) membrane filter having a pore size of 0.2 μm to obtain a resist solution. Prepared.

(2) Resist Pattern Test After the obtained resist solution was spin-coated on a clean silicon wafer, it was baked at 110 ° C. to form a resist film having a thickness of about 0.1 μm. The resist film was exposed at 27 μC / cm ² using an electron beam drawing apparatus. Thereafter, post-exposure heat treatment (PEB) was performed at 90 ° C. for 60 seconds on a hot plate, and development was performed at 23 ° C. for 60 seconds by using a 2.38 wt% tetramethylammonium hydroxide aqueous solution. Thereafter, the film was washed with water for 30 seconds, dried and observed with an electron microscope. As a result, formation of a 100 nm line-and-space positive resist pattern with extremely small line edge roughness was observed.

Claims (6)

A compound represented by formula (2).

(In the formula (2),
R ¹ is independently methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, 4-bromophenacyl group, 4- Methoxyphenacyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, tert-butoxycarbonylmethyl group, 1-methoxyethyl Group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group 1,1-diphenoxyethyl Group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxy-n-propyl group, 1-ethoxy-n-propyl group, isopropyl Group, sec-butyl group, tert-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiethylsilyl group, tert-butyldiphenylsilyl group, tri-tert-butylsilyl group, triphenylsilyl group, acetyl group, phenoxyacetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl Group, valeryl group, Loyl group, isovaleryl group, laurylyl group, adamantyl group, benzoyl group, naphthoyl group, 1-cyclopentylmethoxymethyl group, 1-cyclopentylethoxymethyl group, 1-cyclohexylmethoxymethyl group, 1-cyclohexylethoxymethyl group, 1-cyclooctyl Methoxymethyl group, 1-adamantylmethoxymethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, methoxy carbonyl group is selected ethoxycarbonyl, n- propoxycarbonyl group, i- propoxycarbonyl group, from the group consisting of n- butoxycarbonyl group and tert- butoxycarbonyl group It is a dissociative functional group.
R ² is independently 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, or a nitro group. Represents a substituent selected from the group consisting of:
Each R ³ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Each R ⁵ is independently an alkyl group having 1 to 6 carbon atoms;
m0 and n0 are integers of 0 to 3;
m1 and n1 are integers of 0 to 3;
m2 and n2 are integers of 0 to 4;
1 ≦ m0 + m1 + m2 ≦ 5, 1 ≦ n0 + n1 + n2 ≦ 5, 1 ≦ m1 + n1 ≦ 6, 1 ≦ m0 + m1 ≦ 3, 1 ≦ n0 + n1 ≦ 3, 0 ≦ l ≦ 4. ) The compound of Claim 1 shown by Formula (3).

(In the formula, each R ¹ is independently a hydrogen atom or a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group, a benzyloxymethyl group, a benzylthiomethyl group, or phenacyl. Group, 4-bromophenacyl group, 4-methoxyphenacyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, tert- Butoxycarbonylmethyl group, 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group, 1-phenoxy Ethyl group, 1-phenylthioethyl group 1,1-diphenoxyethyl group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxy-n-propyl group, 1-ethoxy -N-propyl group, isopropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, trimethylsilyl group, ethyldimethylsilyl group, methyldiethyl Silyl group, triethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiethylsilyl group, tert-butyldiphenylsilyl group, tri-tert-butylsilyl group, triphenylsilyl group, acetyl group, phenoxyacetyl group, propionyl group, Butyryl, heptanoyl, hex Noyl, valeryl, pivaloyl, isovaleryl, laurylyl, adamantyl, benzoyl, naphthoyl, 1-cyclopentylmethoxymethyl, 1-cyclopentylethoxymethyl, 1-cyclohexylmethoxymethyl, 1-cyclohexylethoxymethyl Group, 1-cyclooctylmethoxymethyl group, 1-adamantylmethoxymethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydro group Thiopyranyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group and tert-butoxycarbonyl An acid-dissociable functional group selected from the group consisting of at least one is an acid dissociable functional group other than a hydrogen atom, R ⁶ is hydrogen atom or a methyl group. ) The acid dissociable functional group includes a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-cyclohexyloxyethyl group, a 1-phenylethyl group, and a tert-butyl group. The compound according to claim 1, selected from the group consisting of, trimethylsilyl group, tetrahydropyranyl group, and 1-cyclohexylmethoxymethyl group. The compound of Claim 1 shown by Formula (4).

(In the formula, R ⁶ is a hydrogen atom or a methyl group.)   The radiation sensitive composition containing 1 or more types of compounds chosen from the compound group of Claims 1-4, and an acid generator.   A radiation-sensitive composition comprising 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent, comprising one or more compounds selected from the group of compounds according to claims 1 to 4, wherein the compound and the solution are accelerated. The radiation-sensitive composition according to claim 5, wherein the total amount of the agent is 50 to 99.999% by weight based on the total weight of the solid components.