KR100684146B1 - Positive electron beam or x-ray resist composition - Google Patents

Abstract

The present invention provides a positive electron beam or X-ray resist composition having high resolution, capable of providing a rectangular excellent pattern profile, and having low development defects and small PEB temperature dependency.

The positive electron beam or X-ray resist composition of the present invention is characterized in that it contains an onium salt having an electron withdrawing group which generates an acid by irradiation of electron beams or X-rays, and a resin whose solubility in an alkaline developer is increased by the action of an acid.

Description

Positive electron beam or X-ray resist composition {POSITIVE ELECTRON BEAM OR X-RAY RESIST COMPOSITION}

The present invention relates to a positive electron beam or X-ray resist composition, in particular, excellent pattern electron beam or X-ray resist composition obtained by irradiation with electron beam or X-ray, less development defects, PEB temperature dependency It is about.

Background Art In recent years, high integration of large-scale integrated circuits requires a high degree of fine processing, and high-resolution positive electron beam resists have been used. However, although the electron beam resist has a high resolution, the thro ugh-put at the time of electron beam irradiation becomes a problem compared with the conventional i-ray resist, KrF excimer laser resist, ArF excimer laser resist, etc. In order to increase the throughput and the sensitivity of the resist, a chemically amplified resist containing a compound which forms an acid or the like has been developed, but there is a problem that the line width varies depending on the heating temperature after electron beam irradiation. Heating after electron beam irradiation is called PEB (Post Exposure Bake). In other words, a resist having a smaller PEB temperature dependency is required. In addition, X-ray resists developed with a focus on high resolution are also preferably small in PEB temperature dependency.

In addition, there is a problem that the development defect increases with the recent miniaturization of the processing pattern, and thus a resist having less development defects is required.

An object of the present invention is to provide a positive electron beam or X-ray resist composition having a high resolution, which can provide excellent rectangular rectangular pattern profile, and improved development defect, with small PEB temperature dependency.

According to the present invention, the following positive electron beam or X-ray resist composition is provided, and the above object of the present invention is achieved.

(1) an onium salt (a) which generates an acid by irradiation of an electron beam or X-ray and has at least one electron withdrawing group on a substituent at a cation moiety, and

A positive electron beam or X-ray resist composition characterized by containing a resin (b) in which solubility in an alkaline developer is increased by the action of an acid.

(2) an onium salt (a) which generates an acid by irradiation of an electron beam or X-ray and has at least one electron withdrawing group on a substituent at a cation moiety,

Resin (b) whose solubility in alkaline developing solution increases by the action of an acid, and

A positive electron beam or X-ray resist composition, characterized by containing a low molecular weight dissolution inhibiting compound (c) having a molecular weight of 3000 or less, which has a group that can be decomposed by an acid and whose solubility in an alkaline developer is increased by the action of an acid.

(3) an onium salt (a) which generates an acid by irradiation with an electron beam or X-ray and has at least one electron withdrawing group on a substituent at a cation moiety,

A low molecular weight dissolution inhibiting compound (c) having a molecular weight of 3000 or less, having a group that can be decomposed by an acid, and having increased solubility in an alkaline developer by the action of an acid, and

A positive electron beam or X-ray resist composition comprising resin (d) which is insoluble in water and soluble in an alkaline developer.

(4) In any one of said (1)-(3), the onium salt (a) is at least one compound selected from the group consisting of compounds represented by the following general formulas (I) to (III). A positive electron beam or x-ray resist composition, characterized in that.

Wherein at least one of R ₁ to R ₁₅ , at least one of R ₁₆ to R ₄₃ , and at least one of R ₄₄ to R ₅₃ represent an electron withdrawing group. The remaining R ₁ to R ₅₃ are the same or different. Represents a hydrogen atom, an alkyl group which may be branched or cyclic, an alkoxy group which may be branched or cyclic, a hydroxy group, a halogen atom, or a -SR ₅₄ group, R ₅₄ represents an alkyl group or an aryl group which may be branched or cyclic; In addition, two or more of R ₁ to R ₁₅ , R ₁₆ to R ₄₃ , and R ₄₄ to R ₅₃ may be bonded to each other and may be selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom, or You may form the ring containing 2 or more types.

X ⁻ represents an anion of at least one substituted alkanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid.

(5) In the above (4), X ⁻ in General Formulas (I) to (III) is

At least one fluorine atom,

An alkyl group which may be branched or cyclic, substituted with at least one fluorine atom,

An alkoxy group which may be branched or cyclic, substituted with at least one fluorine atom,

An acyl group substituted with at least one fluorine atom,

An acyloxy group substituted with at least one fluorine atom,

Sulfonyl groups substituted with at least one fluorine atom,

Sulfonyloxy groups substituted with at least one fluorine atom,

Sulfonylamino groups substituted with at least one fluorine atom,

An aryl group substituted with at least one fluorine atom,

An aralkyl group substituted with at least one fluorine atom, and

A positive electron beam or X-ray resist composition having at least one selected from an alkoxycarbonyl group substituted with at least one fluorine atom, and being an anion of benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid.

(6) The positive electron beam or X-ray resist composition as described in any one of said (1)-(5) containing fluorine type and / or silicon type surfactant (e).

Hereinafter, the positive electron beam or the X-ray resist composition of the present invention will be described in detail.

In the composition of the present invention, the energy ray for irradiation is an electron beam or X-ray.

[I] an onium salt which generates an acid by irradiation of an electron beam or X-ray and has at least one electron withdrawing group on a substituent of a cation moiety (hereinafter referred to as "component (a)")

Component (a) is an onium salt compound which generates an acid by irradiation with an electron beam or X-ray, and has at least one electron withdrawing group on the substituent at the cation portion of the onium salt. An electron withdrawing group generally refers to a chemical substituent which tends to attract electrons, for example, a substituent that tends to attract electrons from an atom in a position adjacent to the group in the molecule. Terms such as "electron attracting group", "electrical voice group", and "electron withdrawing group (EWG)" have the same meaning as "electron attracting group". Such electron withdrawing groups are known to have a positive sigma value of Hammet when they are bonded at meta positions and para positions with respect to S ⁺ and I ⁺ in general formulas (I) to (III), for example. . Although the number of the electron withdrawing groups in the cation part of the onium salt compound of component (a) is at least 1, Preferably it is 1-5, More preferably, it is 1-3. For example, in General Formula (I)-(III) which is preferable as a component (a), at least 1 of R <_1> -R <_15> , at least 1 of R <_16> -R <_43> , or at least 1 of R <_44> -R <_53> The dog represents an electron withdrawing group, preferably 1 to 5, more preferably 1 to 3 represents an electron withdrawing group.

Examples of such electron withdrawing groups are fluorine atom, chlorine atom, cyano group, trifluoromethyl group, nitro group, sulfonyl group, acyl group, alkoxycarbonyl group, acyloxy group and sulfonyloxy group. Here, an acyl group includes an acetyl group, propionyl group and the like, and an alkoxycarbonyl group includes a methoxycarbonyl group and an ethoxycarbonyl group.

Examples of the onium salt compound include sulfonium salts, iodonium salts, ammonium salts, sulfonium salts, and the like.

In this invention, as (a) component, the onium salt compound represented by general formula (I)-(III) is preferable.

In general formula (I)-(III), as a linear, branched alkyl group of R <_1> -R <_54> , the methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group which may have a substituent, t -There are one to four carbon atoms such as butyl group. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group which may have a substituent.

Examples of the linear or branched alkoxy group of R ₁ to R ₅₃ include methoxy, ethoxy, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t- There exists a C1-C4 thing like a butoxy group.

Examples of the cyclic alkoxy group include a cyclopentyloxy group and a cyclohexyloxy group.                     

As a halogen atom of R <_1> -R <_53> , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

As an aryl group of R <_54> , there exists a C6-C14 thing which may have substituents, such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group, for example.

Preferable other substituents include a C1-4 alkoxy group, a C6-10 aryl group, a C2-6 alkenyl group, and the like.

In addition, one or two selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom formed by combining two or more of R ₁ to R ₁₅ , R ₁₆ to R ₄₃ , and R ₄₄ to R ₅₃ . As a ring containing a species or more, a furan ring, a dihydrofuran ring, a pyran ring, a trihydropyran ring, a thiophene ring, a pyrrole ring, etc. are mentioned, for example.

Preferable examples of groups other than the electron withdrawing groups of R ₁ to R ₅₃ are linear, branched and cyclic alkyl groups.

In General Formulas (I) to (III), X ⁻ is an anion of methanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid, which may be substituted. Preferred are anions of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid containing at least one group selected from the following groups.

At least one fluorine atom,

Linear, branched or cyclic alkyl groups substituted with at least one fluorine atom,                     

Linear, branched or cyclic alkoxy groups substituted with at least one fluorine atom,

An acyl group substituted with at least one fluorine atom,

An acyloxy group substituted with at least one fluorine atom,

Sulfonyl groups substituted with at least one fluorine atom,

Sulfonyloxy groups substituted with at least one fluorine atom,

Sulfonylamino groups substituted with at least one fluorine atom,

An aryl group substituted with at least one fluorine atom,

An aralkyl group substituted with at least one fluorine atom and

Alkoxycarbonyl group substituted with at least 1 fluorine atom.

As said linear, branched, or cyclic alkyl group, it is good that it is C1-C12 and is substituted by 1-25 fluorine atoms. Specifically, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, heptafluoroisopropyl group, perfluorobutyl group, perfluorooctyl group, Perfluoro dodecyl group, a perfluoro cyclohexyl group, etc. are mentioned. Especially, the C1-C4 perfluoroalkyl group substituted with the fluorine all is preferable.

The linear, branched or cyclic alkoxy group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specifically, trifluoromethoxy group, pentafluoroethoxy group, heptafluoroisopropyloxy group, perfluorobutoxy group, perfluorooctyloxy group, perfluorododecyloxy group, perfluorocyclohex A siloxy group etc. are mentioned. In this, the C1-C4 perfluoroalkoxy group substituted with the fluorine all is preferable.

As said acyl group, it is preferable that it is C2-C12 and is substituted by 1-23 fluorine atoms. Specifically, a trifluoroacetyl group, a fluoroacetyl group, a pentafluoropropionyl group, a pentafluorobenzoyl group, etc. are mentioned.

The acyloxy group preferably has 2 to 12 carbon atoms and is substituted with 1 to 23 fluorine atoms, specifically, a trifluoroacetoxy group, a fluoroacetoxy group, and a pentafluoropropionyloxy group. And pentafluorobenzoyloxy groups may be mentioned.

The sulfonyl group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specifically, trifluoromethanesulfonyl group, pentafluoroethanesulfonyl group, perfluorobutanesulfonyl group, perfluorooctanesulfonyl group, pentafluorobenzenesulfonyl group, 4-trifluoromethylbenzenesulfonyl group, etc. are mentioned. There is a number.

The sulfonyloxy group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specifically, a trifluoromethanesulfonyloxy group, a perfluorobutanesulfonyloxy group, 4-trifluoromethylbenzenesulfonyloxy group, etc. are mentioned.

The sulfonylamino group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specifically, a trifluoromethanesulfonylamino group, a perfluorobutanesulfonylamino group, a perfluorooctanesulfonylamino group, a pentafluorobenzenesulfonylamino group, etc. are mentioned.

The aryl group preferably has 6 to 14 carbon atoms and is substituted with 1 to 9 fluorine atoms. Specifically, pentafluorophenyl group, 4-trifluoromethylphenyl group, heptafluoronaphthyl group, nonafluoro anthranyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, etc. are mentioned.

The aralkyl group preferably has 7 to 10 carbon atoms and is substituted with 1 to 15 fluorine atoms, specifically, pentafluorophenylmethyl group, pentafluorophenylethyl group, perfluorobenzyl group, and perfluorofe A netyl group is mentioned.

The alkoxycarbonyl group preferably has 2 to 13 carbon atoms and is substituted with 1 to 25 fluorine atoms, specifically, a trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, pentafluorophenoxycarbonyl group, Perfluorobutoxy carbonyl group, a perfluoro octyloxy carbonyl group, etc. are mentioned.

Most preferable X <^-> is a fluorine-substituted benzene sulfonic acid anion, and especially a pentafluorobenzene sulfonic acid anion is especially preferable.

In addition, benzene sulfonic acid, naphthalene sulfonic acid, or anthracene sulfonic acid having the fluorine-containing substituent may be linear, branched or cyclic alkoxy, acyl, acyloxy, sulfonyl, sulfonyloxy, sulfonylamino or aryl. The group, aralkyl group, alkoxycarbonyl group (the carbon number range is the same as above), halogen (excluding fluorine atom), hydroxyl group, nitro group and the like may be substituted.

The specific example of component (a) represented by general formula (I) is shown below.                     

The specific example of component (a) represented by general formula (II) is shown below.

The specific example of component (a) represented by general formula (III) is shown below.

You may use component (a) 1 type or in combination or 2 or more types.

The content of component (a) is generally 0.1 to 20% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight, based on the solids of the entire composition of the positive electron beam or X-ray resist composition of the present invention. %to be.

The compounds of the general formulas (I) and (II) are sulfonic acids and salts corresponding to triarylsulfonium halides obtained by, for example, reacting an aryl grignard reagent such as aryl magnesium bromide with a substituted or unsubstituted phenyl sulfoxide. Exchange method, substituted or unsubstituted phenylsulfoxide and the corresponding aromatic compound are condensed and salt-exchanged using an acid catalyst such as methanesulfonic acid / diphosphate or aluminum chloride, or diaryl iodonium salt and diaryl sulfide It can synthesize | combine by the method of condensation, salt exchange, etc. using catalysts, such as copper acetate.

The compound of formula (III) can be synthesized by reacting an aromatic compound with a periodate.

In addition, the sulfonic acid or sulfonic acid salt used for salt exchange can be obtained by hydrolyzing commercially available sulfonic acid chloride, reacting aromatic compounds with chlorosulfonic acid, reacting aromatic compounds with sulfamic acid, and the like. .

[II] Acid-generating compounds which can be used in combination other than component (a)

In the present invention, in addition to the component (a), a compound which is decomposed by irradiation with energy rays and generates an acid may be used in combination.

The usage-amount of the compound which decomposes | disassembles by irradiation of an energy ray and produces | generates acid which can be used together with the component (a) of this invention is a molar ratio (acid generator other than component (a) /), and is generally 100/0- 20/80, Preferably it is 100 / 0-40 / 60, More preferably, it is 100 / 0-50 / 50.

Such acid generating compounds that can be used together are known compounds which generate acid by irradiation of energy rays used in photoinitiators of photocationic polymerization, photoinitiators of photoradical polymerization, photochromic agents of pigments, photochromic agents, or microresists. And mixtures thereof.

For example, SI Schlesinger, Photogr. Sci. Eng. , Diazonium salts described in TS Bal et al., Polymer , 21, 423 (1980), US Pat. Nos. 4,069,055, 4,069,056 and Re27,992, WO 3-140140, and the like. Ammonium salts described, DC Necker et al., Macromolecules , 17, 2468 (1984), CS Wen et al., Teh, Proc.conf. Rad. Phosphonium salts described in Curing ASIA , p. 478, Tokyo, Oct. (1988), US Pat. Nos. 4, 069, 055 and 4,069,056, JV Crivello et al., Macromolecules , 10 (6) 1307 (1977) , Chem. & Eng. News , Nov. 28, p. 31 (1988), European Patent No. 104,143, US Patent No. 339,049, and 410, 201, Japanese Patent Application Laid-Open No. 2-150848, Japanese Patent Application Laid-Open No. 2-296514, etc., JV Crivello et al., Polymer J. 17, 73 (1985), JV Crivello et al., J. Org. Chem. , 43, 3055 (1978), WR Watt et al., J. Polymer Sci., Polymer Chem. Ed. , 22, 1789 (1984), JV Crivello et al., Polymer Bull. , 14, 279 (1985), JV Crivello et al., Macromolecules , 14 (5), 1141 (1981), JV Crivello et al., J. Polymer Sci., Polymer Chem. Ed. , 17, 2877 (1979), EP 370,693, EP 3,902,114, EP 233,567, EP 297,443, EP 297,442, EP 4,933,377 EP 161,811, EP 410,201, EP 339,049, EP 4,760,013 , 4,734,444 and East 2,833,827, DE Patent No. 2,904,626, copper 3.60458 million call, and the same sulfonium salt according 3,604,581 arc or the like, JV Crivello et al., Macromolecules , 10 (6), 1307 (1977), JV Crivello et al ., J. Polymer Sci., Polymer Chem. Ed. , 17, 1047 (1979) et al. And selenium salts and CS Wen et al., Teh, Proc. Conf. Rad. Curing ASIA , p. 478, Tokyo, Oct. Onium salts such as arsonium salts described in (1988) and the like; U.S. Patent No. 3,905,815, Japanese Patent Application No. 46-4605, Japanese Patent Application No. 48-36281, Japanese Patent Application No. 55-32070, Japanese Patent Application No. 60-239736, Japanese Patent Application No. 61-169835, Japanese Patent Application No. 61-169837 Organic halogen compounds described in 62-58241, Japanese Patent Laid-Open No. 62-212401, Japanese Patent Laid-Open No. 63-70243, Japanese Patent Laid-Open 63-298339 and the like; K. Meier et al., J. Rad. Curing , 13 (4), 26 (1986), TP Gill et al., Inorg. Chem. , 19, 3007 (1980), D. Astruc, Acc, Chem. Res. Organometallic / organic halides as described in US Pat. S. Hayase et al., J. Polymer Sci. , 25, 753 (1987), E. Reichmanis et al., J. Polymer Sci., Polymer Chem. Ed. , 23, 1 (1985), QQ Zhu et al., J. Photochem. , 36, 85, 39, 317 (1987), B. Amit et al., Tetrahedron Lett. , (24) 2205 (1973), DH R Barton et al., J. Chem. Soc. , 3571 (1965), PM Collins et al J. Chem. Soc., Perkin I, 1695 (1975), M. Rudinstein et al., Tetrahedron Lett. , (17), 1445 (1975), JW Walker et al., J. Am. Chem. Soc. , 110, 7170 (1988), SC Busman et al., J. Imaging Technol. , 11 (4), 191 (1985), HM Houlihan et al., Macromolecules , 21, 2001 (1988), PM Collins et al., J. Chem. Soc., J. Chem. Commun. , 532 (1972), S. Hayase et al., Macromolecules , 18, 1799 (1985), E. Reichmanis et al., J. Eletrochem. Soc., Solid State Sci. Technol. , 130 (6), FM Houlihan et al., Macromolecules , 21, 2001 (1988), European Patent Nos. 0,290,750, 046,083, 156,535, 271,851, and 0,388,343 and US Patents 3,901,710 and Photoacid generators having o-nitrobenzyl-type protecting groups described in 4,181,531, JP-A 60-198538, JP-A 53-133022, and the like; M. TUNOOKA et al., Polymer Preprints Japan , 35 (8), G. Berner et al., J. Rad. Curing , 13 (4), WJ Mijs et al., Coating Technol. , 55 (697), 45 (1983), Akzo, H. Adachi et al., Polymer Preprints, Japan , 37 (3), European Patent Nos. 0,199,672, 84,515, 199,672, 044,115, 0101 Photorepresented by iminosulfonates, such as those described in US Pat. No. 122, US Pat. No. 618,564, US Pat. Nos. 4,371,605 and 4,431,774, WO 64-18143, WO 2-245756, WO 3-140109, and the like. The disulfone compound as described in the compound which produces sulfonic acid, Unexamined-Japanese-Patent No. 61-166544, etc. are mentioned.

In addition, a compound in which an acid is generated by irradiation of energy rays or a compound introduced into the main chain or the side chain of the polymer, for example, ME Woodhouse et al., J. Am. Chem. Soc. , 104, 5586 (1982), SP Pappas et al., J. Imaging Sci. , 30 (5), 218 (1986), S. Kondo et al., Makromol. Chem., Rapid Commun. , 9, 625 (1988), Y. Yamada et al., Makromol. Chem. , 152, 153, 163 (1972), JV Crivello et al., J. Polymer Sci., Polymer Chem. Ed. , 17, 3845 (1979), US Patent No. 3,849,137, German Patent No. 3,914,407, Japanese Patent Application No. 63-26653, Japanese Patent Application No. 55-164824, Japanese Patent Application No. 62-69263, Japanese Patent Application No. 63-146038 The compound described in 63-163452, Unexamined-Japanese-Patent No. 62-153853, Unexamined-Japanese-Patent No. 63-146029, etc. can be used.

In addition, VNR Pillai, Synthesis , (1), 1 (1980), A. Abad et al., Tetrahedron Lett. , (47) 4555 (1971), DHR Barton et al., J. Chem. Soc. (C), 329 (1970), U.S. Patent No. 3,779,778, European Patent No. 126,712 and the like can be used a compound capable of generating an acid by light.

Among the compounds which can be used in combination, which are decomposed by irradiation with energy rays to generate an acid, will be described below.                     

(1) An oxazole derivative represented by the following general formula (PAG1) substituted with a trihalomethyl group or an S-triazine derivative represented by the general formula (PAG2).

In the formula, R ²⁰¹ represents a substituted or unsubstituted aryl group, alkenyl group, and R ²⁰² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group, -C (Y) ₃ . Y represents a chlorine atom or a bromine atom.

Although the following compounds are specifically mentioned, It is not limited to these.

(2) Iodonium salt represented by the following general formula (PAG3), or sulfonium salt represented by general formula (PAG4).

Here, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include alkyl groups, cycloalkyl groups, aryl groups, alkoxy groups, carboxyl groups, hydroxy groups, and mercapto groups.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group and an aryl group. Preferably, they are a C6-C14 aryl group, a C1-C8 alkyl group, and these substituted derivatives. Preferable substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a carboxyl group and a hydroxyl group for the aryl group, and an alkoxy group having 1 to 8 carbon atoms, a carboxyl group and an alkoxycarbonyl group for the alkyl group.

Z ^- is an anion pairs shown, and for example _{^{BF 4 -, AsF 6 -,}} PF 6 -, SbF 6 -, SiF 6 2-, ClO 4 -, CF 3 SO 3 - alkanoic acid perfluoroalkyl such as Condensed polynuclear aromatic sulfonic acid anions, anthraquinonesulfonic acid anions, sulfonic acid group-containing dyes such as anions, pentafluorobenzenesulfonic acid anions, naphthalene-1-sulfonic acid anions, and the like, but are not limited thereto.

In addition, two of R ²⁰³ , R ²⁰⁴ , and R ²⁰⁵ and Ar ¹ , Ar ² may be bonded via a single bond or a substituent.

Although the compound shown below specifically, there is no limitation to such a thing.

The onium salts represented by the formulas (PAG3) and (PAG4) are known and are described, for example, in JW Knapczyk et al., J. Am. Chem. Soc. , 91, 145 (1969), AL Maycok et al., J. Org. Chem. , 35, 2532 (1970), E. Goethas et al., Bull. Soc. Chem. Belg. , 73, 546 (1964), HM Leicester, J. Ame. Chem. Soc. 51, 3587 (1929), JV Crivello et al., J. Polym. Chem. Ed. , 18, 2677 (1980), US Pat. Nos. 2,807,648 and 4,247,473, Japanese Patent Application Laid-Open No. 53-101331 and the like.

(3) a disulfonic acid derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (PAG6):

Wherein Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group, R ²⁰⁶ represents a substituted or unsubstituted alkyl group, an aryl group, and A represents a substituted or unsubstituted alkylene group or an alkenylene group , Arylene group.

Specific examples include compounds shown below, but are not limited only to these examples.

[III] Resin (b) (hereinafter referred to as "component (b)") whose solubility in an alkaline developer is increased by the action of an acid

As the resin (component (b)), which is used in the positive electron beam or X-ray resist composition of the present invention, the solubility in an alkali developer is increased by an acid, which can be decomposed to an acid in the main chain or the side chain, or both the main chain and the side chain of the resin. Resin having a group. Among these, resins having a group in the side chain that can be decomposed in an acid are more preferable.

Preferable examples of the group that can be decomposed to an acid include a -COOA ⁰ and -OB ⁰ group, and examples of the group containing the acid include a group represented by -R ⁰ -COOA ⁰ or -A _r -OB ⁰ .

Here, A ⁰ is -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), -Si (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -C (R ⁰⁴ ) (R ⁰⁵ ) -OR ⁰⁶ Is displayed. B ⁰ represents an A ⁰ or -CO-OA ⁰ group (R ⁰ , R ⁰¹ to R ⁰⁶ , and Ar are as follows).

Preferable acid-decomposable groups include silyl ether groups, cumyl ester groups, acetal groups, tetrahydropyranyl ether groups, enol ether groups, enol ester groups, tertiary alkyl ether groups, tertiary alkyl ester groups, and tertiary Tea of the alkyl carbonate group. More preferably, they are a tertiary alkyl ester group, tertiary alkyl carbonate group, cumyl ester group, acetal group, and tetrahydropyranyl ether group.

Next, as a matrix resin in the case of groups are bonded to a side chain which may be decomposed to such acids are, for side chain -OH- or -COOH, preferably an alkali-soluble group holding -R ⁰ -COOH or -A _r -OH Resin. For example, alkali-soluble resin mentioned later is mentioned.

It is preferable that the alkali dissolution rate of such alkali-soluble resin is 170 Pa / sec or more as measured (23 degreeC) by 0.261N tetramethylammonium hydroxide (TMAH). Especially preferably, it is 330 microseconds / sec or more.

From this point of view, particularly preferred alkali-soluble resins are o-, m-, p-poly (hydroxy styrene) and copolymers thereof, hydrogenated poly (hydroxy styrene), halogen or alkyl substituted poly (hydroxy styrene), Part of poly (hydroxystyrene), O-alkylated or O-acylates, styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers and hydrogenated novolac resins.

Component (b) to be used in the present invention is a group which can be decomposed to an acid, as disclosed in EP 254853, WO 2-25850, WO 3-223860, WO 4-251259, and the like. The precursor may be obtained by reacting an alkali soluble resin or copolymerizing a bonded alkali soluble resin monomer of a group capable of decomposing to an acid with various monomers.

Although the specific example of component (b) used for this invention is shown below, it is not limited to this.

The content of the group that can be decomposed in the acid is the number of groups (B) which can be decomposed in the acid in the resin and the number (S) of alkali-soluble groups which are not protected by the group which can be decomposed in the acid, B / (B + S). The content rate is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and most preferably 0.05 to 0.40. At B / (B + S)> 0.7, film shrinkage after PEB and adhesion to the substrate are poor or cause scum, which is not preferable. On the other hand, as B / (B + S) <0.01, standing waves may remain remarkably on the pattern side wall, which is not preferable.

The weight average molecular weight (Mw) of component (b) is preferably in the range of 2,000 to 200,000. If it is less than 2,000, the film reduction tends to be large due to the development of the unexposed portion, and if it exceeds 200,000, the dissolution rate of the alkali-soluble resin itself to alkali increases, which tends to decrease the sensitivity. More preferably, it is the range of 5,000-100,000, Most preferably, it is the range of 8,000-50,000. Further, the molecular weight distribution (Mw / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 2.0, most preferably 1.0 to 1.6, and the smaller the dispersion degree, the more heat resistance and image formability (pattern profile, deamination) Focus latitude) becomes good.

Here, the weight average molecular weight is defined as polystyrene conversion value of gel permeation chromatography.

In addition, component (b) can also be used in combination of 2 or more type. The usage-amount of such a component in this invention is 40 to 99 weight% with respect to solid content of the whole composition, Preferably it is 60 to 95 weight%. Moreover, in order to adjust alkali solubility, you may mix alkali-soluble resin which does not have the group which can decompose | disassemble in an acid.

Similarly, you may mix | blend the following acid-decomposable low molecular weight inhibitory compound (c) with the composition of this invention. In this case, the content of the dissolution inhibiting compound is 3 to 45% by weight, preferably 5 to 30% by weight, more preferably 10 to 20% by weight based on the solids of the entire composition.

[IV] Fluorine-based and / or silicon-based surfactant (e) (hereinafter referred to as "(e) component)

Next, the fluorine-based surfactant and the silicon-based surfactant which are (e) component which can be used for the positive electron beam or energy ray resist composition of this invention are demonstrated.

The composition of this invention can contain any or all of a fluorine-type surfactant and a silicon type surfactant. This makes the effect of the present invention more remarkable.

As such (e) component, For example, Unexamined-Japanese-Patent No. 62-36663, Unexamined-Japanese-Patent No. 61-226745, Unexamined-Japanese-Patent No. 62-170950, No. 63-34540, Unexamined-Japanese-Patent No. 7- Although the surfactant of 230165, Unexamined-Japanese-Patent No. 8-62834, Unexamined-Japanese-Patent No. 9-54432, and Unexamined-Japanese-Patent No. 9-5988 is mentioned, the following commercially available surfactant can also be used as it is.

Commercially available surfactants include Eftop EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florad FC430 and 431 (manufactured by Sumimoto 3M Company), Megafac F171, F173, F176, F189, and R08 (Dainippon Ink & Chemicals). Company products) and fluorine-based surfactants or silicon-based surfactants such as Surflon S-382, SC101, 102, 103, 104, 105 and 106 (Asahi Glass Company). In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

The compounding quantity of (e) component is 0.00001-2 weight% normally with respect to solid content of the whole composition in the composition of this invention, Preferably it is 0.0001-1 weight%.

These surfactant can also be used individually by 1 type or in combination of 2 or more types.                     

[V] Low Asset Degradable Dissolution Inhibitory Compound (c) (hereinafter referred to as "(c) component")

In this invention, you may use (c) component. The component (c) is a low molecular weight inhibiting compound having a molecular weight of 3000 or less, which has a group that can be decomposed by an acid, and whose solubility in an alkaline developer is increased by the action of an acid.

Preferred component (c) to be incorporated into the composition of the present invention has at least two groups that can be decomposed to an acid in its structure, and at least the bonding atoms excluding the acid-decomposable group at a position where the distance between the acid-decomposable groups is the least. It is a compound having eight gasolines.

More preferred component (c) has at least two groups which can be decomposed to an acid in its structure, and at least 10, preferably from at least 10 bond atoms, except for the acid-decomposable group, at a position where the distance between the acid-decomposable groups is the least. A compound having at least 11, more preferably at least 12, or at least 3 acid-decomposable groups, and at least 9, preferably at least 9 binding atoms, excluding the acid-decomposable group at a position where the distance between the acid-decomposable groups is the least. Preferably at least 10, more preferably at least 11 compounds. The upper limit of the number of the binding atoms is preferably 50, more preferably 30.

(c) the acid-decomposable dissolution inhibiting compound having three or more acid-decomposable groups, preferably four or more acid-decomposable groups, and also in the case of having two acid-decomposable groups, the acid-decomposable groups alternately fall by a predetermined distance or more. There is a tendency for the dissolution inhibiting property to alkali-soluble resins to increase significantly.

In addition, the distance between acid-decomposable groups is represented by the number of bonding atoms which pass through except the acid-decomposable group. For example, in the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bonding atoms, and in compound (3), 12 bonding atoms are each.

The acid-decomposable dissolution inhibiting compound of the component (c) preferably has a plurality of acid-decomposable groups on one benzene ring, but is preferably composed of a skeleton having one acid-decomposable group on one benzene ring. Compound. The molecular weight of the acid-decomposable dissolution inhibiting compound of the present invention is 3,000 or less, preferably 300 to 3,000, and more preferably 500 to 2,500.

In a preferred embodiment of the present invention, a group which can be decomposed by an acid, that is, a group containing a -COOA ⁰ , -OB ⁰ group is represented by -R ⁰ -COO-A ⁰ , or -Ar-OB ⁰ have.

Here, A ⁰ is -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), -Si (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -C (R ⁰⁴ ) (R ⁰⁵ ) -OR ⁰⁶ Is displayed. B ⁰ represents an A ⁰ or -CO-OA ⁰ group.

R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ may be the same or different, respectively, and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, and R ⁰⁶ represents an alkyl group or an aryl group. However, at least two of R ⁰¹ to R ⁰³ may be a group other than a hydrogen atom, and two groups of R ⁰¹ to R ⁰³ and R ⁰⁴ to R ⁰⁶ may combine to form a ring. R <^0> represents the bivalent or more aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- represents the bivalent or more aromatic group which may have a monocyclic or polycyclic substituent.

Here, the alkyl group preferably has 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, and cycloalkyl group is cyclopropyl group, cyclobutyl group, cyclohex. It is preferable that it is C3-C10 like a real group and an adamantyl group, As an alkenyl group, it is preferable that it is C2-C4 like a vinyl group, a propenyl group, an allyl group, butenyl group, and an aryl group is a phenyl group and a xylyl group It is preferable that it is C6-C14, such as a toluyl group, cumenyl group, a naphthyl group, and anthracenyl group.

Examples of the substituent include hydroxyl group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, Alkoxy groups such as alkoxy groups such as n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, and aralkyl jade Acyl groups, such as acyl groups, such as a formyl group, an acetyl group, butyryl group, a benzoyl group, a cyanyl group, and a valeryl group, and an acyloxy group, such as butyryloxy group, the said alkenyl group, vinyloxy group, propenyloxy group, and aryloxy group Alkenyloxy groups, such as a butenyloxy group, aryloxy groups, such as the said aryl group and phenoxy group, and aryloxycarbonyl groups, such as a benzoyloxy group, are mentioned.

As the acid-decomposable group, preferably, silyl ether group, cumyl ester group, acetal group, tetrahydropyranyl ether group, enol ether group, enol ester group, tertiary alkyl ether group, tertiary alkyl ester group, and tertiary Primary alkyl carbonate groups and the like. More preferably, there is a tertiary alkyl ester group, tertiary alkyl carbonate group, cumyl ester group, and tetrahydropyranyl ether group.

Preferable examples of the component (c) include Japanese Patent Application Laid-Open No. 1-289946, Japanese Patent Application Laid-Open No. 1-289947, Japanese Patent Application Laid-Open No. 2-2560, Japanese Patent Application Laid-Open No. 3-158855, Japanese Patent Application Laid-Open No. 3-179353 Japanese Patent Application Laid-Open No. 3-191351, Japanese Patent Laid-Open No. 3-200251, Japanese Patent Laid-Open No. 3-200252, Japanese Patent Laid-Open No. 3-200253, Japanese Patent Laid-Open No. 3-200255, Japanese Patent Laid-Open No. 3-259149, Japanese Patent Application Laid-Open No. 3-279958, Japanese Patent Laid-Open No. 3-279959, Japanese Patent Laid-Open No. 4-1651, Japanese Patent Laid-Open No. 4-1651, Japanese Patent Laid-Open No. 4-11356, Japanese Patent Laid-Open No. 4-12357 Wonpyeong 3-33229, Wonpyeong 3-230790, Wonpyeong 3-320438, Wonpyeong 4-25157, Wonpyeong 4-52732, Wonpyeong 4-103215, Wonpyeong 4-104542, Wonpyeong A group in which part or all of the phenolic OH groups of the polyhydroxy compound described in the specification, such as 4-107885, Japanese Patent Application No. 4-107889, and Japanese Patent No. 4-152195, are displayed thereon, -R ⁰ -COO-A ⁰ Or a protected compound by binding to a B ⁰ group.

More preferably, Japanese Patent Application Laid-Open No. 1-289946, JP-A 3-128959, JP-A 3-158855, JP-A 3-179353, JP-A 3-200251, JP-A 3-200252, JP-A-3. -200255, Japanese Patent Application Laid-Open No. 3-259149, Japanese Patent Application Laid-Open No. 3-279958, Japanese Patent Application Laid-Open No. 4-1650, Japanese Patent Application Laid-Open No. 4-11260, Japanese Patent Application Laid-Open No. 4-12356, Japanese Patent Application Laid-Open No. 4-12357 The polyhydroxy compound described in the specification of 25157, Unexamined-Japanese-Patent 4-103215, Unexamined-Japanese-Patent No. 4-104542, Unexamined-Japanese-Patent No. 4-107885, Unexamined-Japanese-Patent 4-107889, and 4-152195 is used.

More specifically, there exist a compound represented by general formula [I]-[XVI].                     

Here, R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ , R ^{130 may be the} same or different, and a hydrogen atom, -R ⁰ -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), except that R ⁰ , R ⁰¹ , R ⁰² and R ⁰³ are defined as above.

R ¹⁰⁰ : -CO-, -COO-, -NHCONH-, -NHCOO-, -O-, -S-, -SO-, -SO _2- , -SO _3- , or

Where, G = 2 ~ 6, if inde, provided that, G = 2 days, at least one of R ^150, R ¹⁵¹ is an alkyl group,

R ¹⁵⁰ , R ¹⁵¹ : may be the same or different, hydrogen atom, alkyl group, alkoxy group, -OH, -COOH, -CN, halogen atom, -R ¹⁵² -COOR ¹⁵³ or -R ¹⁵⁴ -OH,

R ¹⁵² , R ¹⁵⁴ : alkylene group,

R ¹⁵³ : hydrogen atom, alkyl group, aryl group, or aralkyl group,

R ⁹⁹ , R ¹⁰³ to R ¹⁰⁷ , R ¹⁰⁹ , R ¹¹¹ to R ¹¹⁸ , R ¹²¹ to R ¹²³ , R ¹²⁸ to R ¹²⁹ , R ¹³¹ to R ¹³⁴ , R ¹³⁸ to R ¹⁴¹ and R ¹⁴³ : may be the same or different, Hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, halogen atom, nitro group, carboxyl group, cyano group, or -N (R ¹⁵⁵ ) ( R ¹⁵⁶ ), wherein R ¹⁵⁵ , R ¹⁵⁶ : H, an alkyl group, or an aryl group

R ¹¹⁰ : single bond, alkylene group, or

R ¹⁵⁷ and R ^{159 may be the} same or different, and are a single bond, an alkylene group, -O-, -S-, -CO-, or a carboxyl group,

R ¹⁵⁸ : a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, a nitro group, a hydroxyl group, a cyano group, or a carboxyl group, provided that the hydroxyl group is an acid-decomposable group (e.g., t-butoxycarbonyl Methyl group, tetrahydropyranyl group, 1-ethoxy-1-ethyl group, 1-t-butoxy-1-ethyl group).

R ¹¹⁹ and R ^{120 may be the} same or different and are a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, except that the lower alkyl group refers to an alkyl group having 1 to 4 carbon atoms,

R ¹²⁴ to R ¹²⁷ : may be the same or different, a hydrogen atom or an alkyl group,

R ¹³⁵ to R ¹³⁷ : may be the same or different, a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, or an acyloxy group,

R ¹⁴² : hydrogen atom, -R ⁰ -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or

R ¹⁴⁴ , R ¹⁴⁵ : the same as or different from each other, a hydrogen atom, a lower alkyl group, a lower haloalkyl group, or an aryl group,

R ¹⁴⁶ to R ¹⁴⁹ : may be same or different, hydrogen atom, hydroxyl group, halogen atom, nitro group, cyano group, carbonyl group, alkyl group, alkoxy group, alkoxycarbonyl group, aralkyl group, aralkyloxy group, acyl group, acyloxy group, alke A substituent group of four identical symbols may be the same group, such as a silyl group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group.

Y: -CO-, or -SO _2- ,

Z, B: single bond, or -O-,

A: methylene group, lower alkyl substituted methylene group, halomethylene group, or haloalkyl group,

E: single bond or oxymethylene group,

a to z, a1 to y1: In the case of a plurality, the groups in parentheses may be the same or different.

a to q, s, t, v, g1 to i1, k1 to m1, o1, q1, s1, u1: an integer of 0 or 1 to 5,

r, u, w, x, y, z, a1 to f1, p1, r1, t1, v1 to x1: an integer of 0 or 1 to 4,

j1, n1, z1, a2, b2, c2, d2: 0 or an integer of 1 to 3,                     

at least one of z1, a2, c2, and d2 is one or more,

y1: an integer from 3 to 8,

(a + b), (e + f + g), (k + l + m), (q + r + s), (w + x + y), (c1 + d1), (g1 + h1 + i1 + j1), (o1 + p1), (s1 + t1) ≥2,

(j1 + n1) ≤ 3,

(r + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1 + f1), (p1 + r1), (t1 + v1), (x1 + w1) ≤ 4, except that in the general formula [V], (w + z), (x + a1) ≤5,

(a + c), (b + d), (e + h), (f + i), (g + j), (k + n), (l + o), (m + p), (q + t), (s + v), (g1 + k1), (h1 + l1), (i1 + m1), (o1 + q1), and (s1 + u1) ≦ 5.

Where R ^{160 is an} organic group, a single bond, -S-, -SO- or

R ¹⁶¹ : hydrogen atom, monovalent organic group or

R ¹⁶² to R ^{166 may be the} same or different and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, -OR ⁰ -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -O- CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), but at least two are -OR ⁰ -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -O-CO-OC (R ⁰¹ (R ⁰² ) (R ⁰³ ). In addition, substituents of four or six identical symbols may be the same group.

X: a divalent organic group,

e2: 0 or 1 is displayed.

From here,

R ¹⁶⁷ to R ^{170 may be the} same or different, and a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, or an alkenyl group, provided that the substituents of each of 4 to 6 identical symbols may be the same group.

R ¹⁷¹ , R ¹⁷² : hydrogen atom, alkyl group or

R ¹⁷³ : at least two are -OR ⁰ -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) groups or -O-CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) groups, The other is a hydroxyl group.

f2, h2: 0 or 1,

g2: The integer of 0 or 1-4 is represented.

From here,

R ¹⁷⁴ to R ¹⁸⁰ : may be the same or different, hydrogen atom, hydroxyl group, halogen atom, alkyl group, alkoxy group, nitro group, alkenyl group, aryl group, aralkyl group, alkoxycarbonyl group, arylcarbonyl group, acyloxy group, acyl group, aral A cheloxy group or an aryloxy group, provided that the six substituents of the same symbol may be the same group.

R ¹⁸¹ : at least two are -OR ⁰ -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -O-CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) Display hydroxyl groups.

From here,

R ¹⁸² : hydrogen atom or alkyl group, but all may be the same.

R ¹⁸³ to R ¹⁸⁶ : a hydroxyl group, a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, provided that each of the three same symbol substituents may be the same group.

R ¹⁸⁷ : at least two are -OR ⁰ -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) groups or -O-CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) groups, Otherwise, a hydroxyl group is represented.

The specific example of a preferable compound skeleton is shown below.

R in compounds (1) to (44) is a hydrogen atom,

를 표시한다. 단, 적어도 2개, 또는 구조에 의해 3개는 수소원자 이외의 기이고, 각 치환기 R은 동일한 기로 되어있어도 좋다.

Is displayed. However, at least two or three may be groups other than a hydrogen atom by the structure, and each substituent R may be the same group.

[V] Resin (d) which is not dissolved in water and soluble in alkaline developer (hereinafter referred to as "(d) component" or "(d) alkali-soluble resin)

In the positive electron beam or X-ray resist composition of the present invention, as the component (d), a resin insoluble in water and soluble in an aqueous alkali solution can be used. When using (d) component, it is not necessary to mix | blend resin which the solubility with respect to alkaline developing solution increases by the action of the acid which is the said (b) component. Of course, combined use with (b) component is not excluded.

As (d) alkali-soluble resin used for this invention, a novolak resin, a hydrogenated novolak resin, acetone pyrogarol resin, o-polyhydroxy styrene, m-polyhydroxy styrene, p-poly Hydroxystyrene, hydrogenated polyhydroxystyrene, halogen or alkyl substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer, polyhydroxystyrene Some O-alkylates (e.g., 5-30 mole% O-methylate, O- (1-methoxy) ethylate, O- (1-ethoxy) ethylate, O-2 -Tetrahydropyranylide, O- (t-butoxycarbonyl) methylate, etc.) or O-acylide (e.g., 5-30 mol% o-acetylate, O- (t-butoxy) Carbonylide, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing metak Resin and there can be a derivative thereof, polyvinyl alcohol derivatives, but is not limited in this respect.

Particularly preferred alkali-soluble resins (d) include novolak resins and o-polyhydroxystyrenes, m-polyhydroxystyrenes, p-polyhydroxystyrenes and copolymers thereof, alkyl substituted polyhydroxystyrenes, and polyhydroxys. Some O-alkylated, or O-acylates, styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers of styrene. The novolak resin can be obtained by addition condensation with aldehydes based on a predetermined monomer in the presence of an acidic catalyst.

Predetermined monomers include cresols such as phenol, m-cresol, p-cresol and o-cresol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2, Alkyl phenols such as xylenols such as 3-xylenol, m-ethylphenol, p-ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol and 2,3,5-trimethylphenol, p -Methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-prop Alkoxyphenols such as foxyphenol, m-butoxyphenol and p-butoxyphenol, bisalkylphenols such as 2-methyl-4-isopropylphenol, m-chlorophenol, p-chlorophenol, o-chlorophenol, di Although hydroxy aromatic compounds, such as hydroxy biphenyl, bisphenol A, phenyl phenol, resorcinol, naphthol, can be used individually or in mixture of 2 or more types, it is not limited to these.

-페닐프로필알데히드,

-페닐프로필알데히드, o-히드록시벤즈알데히드, m-히드록시벤즈알데히드, p-히드록시벤즈알데히드, o-클로로벤즈알데히드, m-클로로벤즈알데히드, p-클로로벤즈알데히드, o-니트로벤즈알데히드, m-니트로벤즈알데히드, p-니트로벤즈알데히드, o-메틸벤즈알데히드, m-메틸벤즈알데히드, p-메틸벤즈알데히드, p-에틸벤즈알데히드, p-n-부틸벤즈알데히드, 푸르푸랄, 클로로아세트알데히드 및 이들의 아세탈체, 예를 들면, 클로로아세트알데히드디에틸아세탈 등을 사용할 수 있지만, 이것들 중 에서 포름알데히드를 사용하는 것이 바람직하다.As aldehydes, For example, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde,

Phenylpropylaldehyde,

-Phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-hydroxybenzaldehyde Nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde and their acetals such as chloroacetaldehyde diethyl Although etc. can be used, it is preferable to use formaldehyde among these.

These aldehydes are used individually or in combination of 2 or more types. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

The weight average molecular weight of the novolak resin thus obtained is preferably in the range of 1,000 to 30,000. If it is less than 1,000, the film reduction after development of the unexposed part tends to be large, and if it exceeds 30,000, the development speed tends to be small. It is especially preferable that it is the range of 2,000-20,000.

Moreover, the weight average molecular weights of the said polyhydroxy styrene other than novolak resin, its derivative (s), and copolymer are 2,000 or more, Preferably it is 5000-200000, More preferably, it is 5000-100000.

Here, a weight average molecular weight is defined by the polystyrene conversion value of gel permeation chromatography.

In this invention, you may use these alkali-soluble resin (d) in mixture of 2 or more types.

The use amount of alkali-soluble resin (d) is 40-97 weight% with respect to solid content of the whole composition of a positive electron beam or an X-ray resist composition, Preferably it is 60-95 weight%.

[VI] Other ingredients used in the present invention

In the positive electron beam or X-ray resist composition of the present invention, if necessary, a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, an organic base compound, a compound having two or more phenolic OH groups which promote solubility in a developer, etc. It may further contain.

The compound having two or more phenolic OH groups which can be used in the present invention is preferably a phenol compound having a molecular weight of 1,000 or less. It is also necessary to have at least two phenolic hydroxyl groups in the molecule, but if it exceeds 10, the effect of improving the development latitude is lost. In addition, when the ratio of the phenolic hydroxyl group and the aromatic ring is less than 0.5, the film thickness dependency becomes large, and the development latitude tends to be narrowed. When this ratio exceeds 1.4, the safety of the composition is deteriorated, and it is difficult to obtain high resolution and good film thickness dependency, which is not preferable.

The addition amount of the said phenolic compound is 2-50 weight% with respect to alkali-soluble resin (d), More preferably, it is 5-30 weight%. At an added amount exceeding 50% by weight, the development residue deteriorates, and a new defect that causes deformation of the pattern during development occurs, which is not preferable.

Such phenolic compounds with an added amount of 1000 or less can be easily used by those skilled in the art by referring to methods described in, for example, Japanese Patent Application Laid-Open No. 4-122938, 2-28531, US Patent No. 4916210, European Patent No. 219294, and the like. Can be synthesized.

Although the specific example of a phenol compound is shown below, the compound which can be used for this invention is not limited to this.

Resorcin, phloroglucin, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,3 ', 4', 5'- Hexahydroxyphenone, acetone-pyrogallol condensation resin, phlologlucoside, 2,4,2 ', 4'-biphenylterol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2 ', 4,4'-tetrahydroxydiphenylether, 2,2', 4,4'-tetrahydroxydiphenylsulfoxide, 2,2 ', 4,4'-tetrahydroxydiphenyl Sulfone, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4- (α-methylbenzylidene) bisphenol, α, α ', α' '-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, α, α ', α' '-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1,2 , 2-tris (hydroxyphenyl) propane, 1,1,2-tris (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) Hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3-tris (hydroxyphenyl) butane, La [α, α, α ', α'- tetrakis (4-hydroxyphenyl)] - xylene, and the like.

Preferred organic basic compounds which can be used in the present invention are compounds which are more basic than phenol. Among these, a nitrogen-containing basic compound is preferable.

As a preferable chemical environment, the following formula (A)-(E) structure is mentioned.

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are the same or different, hydrogen atom, alkyl group of 1 to 6 carbon atoms, aminoalkyl group of 1 to 6 carbon atoms, hydroxyalkyl group of 1 to 6 carbon atoms or 6 to 20 carbon atoms or An unsubstituted aryl group, wherein R ²⁵⁴ and R ²⁵⁵ may combine with each other to form a ring.

(Wherein, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ are the same or different and represent an alkyl group having 1 to 6 carbon atoms.)

More preferred compounds are nitrogen-containing basic compounds having at least two nitrogen atoms of different chemical environments in one molecule, particularly preferably compounds containing both substituted or unsubstituted amino groups and ring structures containing nitrogen atoms or alkylamino groups It is a compound having. Specific examples are preferably substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, substituted or substituted Unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted pipepe Razin, substituted or unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, and the like. Preferred examples of the substituent include an amino group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, and a cyano group. Particularly preferred compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4- Dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino- 6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpyrrolidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3 -Amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine , 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,8-diazabicyclo [5.4.0] undeca-7-ene, 1,5-diazabicyclo [4.3.0] nona-5-ene, 2, 4,5-triphenylimidazole and the like, but among these, 1,8-diazabicyclo [5.4.0] undeca-7-ene, 1,5-diazabicyclo [4,3,0 ] Nona-5-ene, 2,4,5-triphenylimidazole and the like are preferred, but are not limited thereto.

Such nitrogen-containing basic compounds may be used alone or in combination of two or more thereof. The usage-amount of the basic compound containing a nitrogen atom is 0.001-10 weight% normally, Preferably it is 0.01-5 weight% with respect to solid content of the whole composition in the composition of this invention. If it is less than 0.001 weight%, the addition effect of the said compound is not acquired. On the other hand, when it exceeds 10 weight%, there exists a tendency for the fall of a sensitivity and the developability of a non-exposed part to deteriorate.

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The electron beam or X-ray resist composition of the present invention is dissolved in a solvent for dissolving each of the above components, and then coated on a support. At this time, as a solvent to be used, ethylene chloride, cyclohexanone, cyclopentanone, 2-heptanone, (gamma) -butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methok Sidiethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate , Propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents may be used alone or in combination.

You may use together surfactant other than the fluorine type and / or silicon type surfactant which is the said (e) component to the said solvent. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl Polyoxyethylene alkylaryl ethers such as phenol ethers, polyoxyethylene-polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tri Sorbitan fatty acid esters such as oleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan triol Latex, polyoxyethylene sorbitan tristeare Examples thereof include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyacrylate, acrylic acid or methacrylic acid-based (co) polymerized polyflow-No.75, No.95 (manufactured by Kyoisei Oil & Chemical Co., Ltd.), and the like. Can be mentioned.

The compounding quantity of such surfactant is 2 weight% or less normally with respect to solid content of the whole composition in the composition of this invention, Preferably it is 1 weight% or less.

The said surfactant can be used individually or in addition, and can also be added in combination of 2 or more type.

After applying the positive electron beam or the X-ray resist composition of the present invention to a substrate (for example, silicon / silicon dioxide film) used for the manufacture of precision integrated circuit devices by a suitable coating method such as a spinner, coater, etc., a predetermined mask is applied. By exposing through baking and developing, a good resist pattern can be obtained.

Examples of the developer of the electron beam or X-ray resist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia water, first amines such as ethylamine and n-propylamine, and diethyl. Second amines such as amines and di-n-butylamine, third amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide Alkaline aqueous solutions, such as quaternary ammonium salts, such as a roxide, cyclic amines, such as a pyrrole and a piperidine, can be used.

Moreover, alcohol and surfactant can also be added and used to the said alkaline aqueous solution suitably.
(Example)

Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not limited to this.

Synthesis Example 1 Synthesis of Poly (p-hydroxystyrene / styrene) Copolymer]

Based on the general method, 35.25 g (0.2 mol) of dehydrated, distilled and purified p-tert-butoxystyrene monomer and 5.21 g (0.05 mol) of styrene monomer were dissolved in 100 ml of tetrahydrofuran. Under nitrogen stream and stirring, 0.033 g of azobisisobutyronitrile (AIBN) was added three times at an interval of 2.5 hours at 80 ° C, and the polymerization reaction was then continued by further stirring for 5 hours. The reaction solution was poured into 1200 ml of hexane to precipitate a white resin. The obtained resin was dried and dissolved in 150 ml of tetrahydrofuran.

To this was added 4N hydrochloric acid, heated to reflux for 6 hours to hydrolyze, and again immersed in 5 L of ultrapure water, and the resin was filtered out and washed with water and dried. The solution was further dissolved in 200 ml of tetrahydrofuran, and dripped and reprecipitated with vigorous stirring in 5 L of ultrapure water. This reprecipitating operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / styrene) copolymer.

Synthesis Example 2: Synthesis of Resin Example (b-21)

32.4 g (0.2 mol) of p-acetoxy styrene and 7.01 g (0.07 mol) of methacrylic acid t-butoxy were dissolved in 120 ml of butyl acetate, and azobisisobutyronitrile (at 80 ° C under nitrogen stream and stirring) A polymerization reaction was carried out by adding 0.033 g of AIBN) three times at 2.5 hour intervals, followed by further stirring for 5 hours. The reaction solution was poured into 1200 ml of hexane to precipitate a white resin. The obtained resin was dried and then dissolved in 200 ml of methanol.

An aqueous solution of 7.7 g (0.19 mol) of sodium hydroxide / 50 ml of water was added thereto, and the mixture was hydrolyzed by heating under reflux for 1 hour. Then, 200 ml of water was added thereto, diluted, and neutralized with hydrochloric acid to precipitate a white resin. The resin was filtered out, washed with water and dried. The solution was further dissolved in 200 ml of tetrahydrofuran, and dripped and reprecipitated with vigorous stirring in 5 L of ultrapure water. This reprecipitating operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / t-butyl methacrylate) copolymer.

Synthesis 3: Synthesis of Resin Example (b-3)

10 g of poly (p-hydroxystyrene) (VP-8000 manufactured by Nippon Kogyo Co., Ltd.) was dissolved in 50 ml of pyridine, and 3.63 g of bicarbonate-t-butyl was added dropwise thereto while stirring at room temperature.

After stirring for 3 hours at room temperature, the mixture was added dropwise to a solution of 1 L of ion-exchanged water and 20 g of concentrated hydrochloric acid. The precipitated powder was filtered, washed with water and dried to obtain Resin Example (b-3).

Synthesis 4: Synthesis of Resin Example (b-33)

83.1 g (0.5 mole) of p-cyclohexylphenol was dissolved in 300 ml of toluene, and then 150 g of 2-chloroethyl vinyl ether, 25 g of sodium hydroxide, 5 g of tetrabutylammonium bromide, and 60 g of triethylamine were added thereto at 120 ° C. The reaction was time. The reaction solution was washed with water, excess chloroethyl vinyl ether and toluene were distilled off, and the oil thus obtained was purified by distillation under reduced pressure to obtain 4-cyclohexylphenoxyethyl vinyl ether.

20 g of poly (p-hydroxystyrene) (VP-8000 manufactured by Nippon Procurement Co., Ltd.) and 6.5 g of 4-cyclohexylphenoxyethyl vinyl ether are dissolved in 80 ml of THF, and 0.01 g of p-toluenesulfonic acid is dissolved therein. Was added and reacted at room temperature for 18 hours. The reaction solution was added dropwise while stirring vigorously with 5 L of distilled water, and the precipitated powder was filtered and dried to obtain a resin example (b-33).

Resin examples (b-4), (b-28) and (b-30) were also synthesize | combined by the same method using the corresponding stem polymer and vinyl ether.

(Synthesis example-1 of a dissolution inhibitor compound: synthesis of compound example 16)

42.4 g (0.10 mol) of 1- [α-methyl-α (4'-hydroxyphenyl) ethyl] -4- [α ', α'-bis (4''-hydroxyphenyl) ethyl] benzene It dissolved in 300 ml of N-dimethylacetamide, and 49.5 g (0.35 mol) of potassium carbonate and 84.8 g (0.33 mol) of bromoacetic acid cumyl ester were added to this. Then, the mixture was stirred at 120 ° C. for 7 hours. The reaction mixture was poured into 2 L of ion-exchanged water, neutralized with acetic acid and then precipitated with ethyl acetate. The ethyl acetate precipitate was concentrated and purified to obtain 70 g of Compound Example 16 (wherein R is a -CH ₂ COOC (CH ₃ ) ₂ C ₆ H ₅ group).

(Synthesis example-2 of a dissolution inhibitor compound: synthesis of compound 41)

44 g of 1,3,3,5-tetrakis- (4-hydroxyphenyl) pentane are dissolved in 250 ml of N, N-dimethylacetamide, and 70.7 g of potassium carbonate and 90.3 g of t-butyl bromoacetate are added thereto. It was added and stirred at 120 ° C. for 7 hours. The reaction mixture was poured into 2 L of ion-exchanged water, and the resulting viscous product was washed with water. This was purified by column chromatography to obtain 87 g of Compound Example 41 (R is -CH ₂ COOC ₄ H ₉ (t)).

(Synthesis Example 3 of the Dissolution Inhibitor Compound: Synthesis of Compound Example 43)

20 g of α, α, α ', α', α '', α '', and -hexakis (4-hydroxyphenyl) -1,3,5-triethylbenzene were dissolved in 400 mL of diethyl ether. 42.4 g of 3,4-dihydro-2H-pyran, catalytic amount of hydrochloric acid were added to this solution under nitrogen stream, and the mixture was refluxed for 24 hours. After completion of the reaction, a small amount of sodium hydroxide was added, followed by filtration. The filtrate was concentrated and purified by column chromatography to obtain 55.3 g of Compound Example 43 (all of which are THP groups).

Examples 1-15, Comparative Example

The components shown in the following Table 1 were dissolved in 8.2 g of propylene glycol monomethyl ether acetate, and this was filtered through a 0.1 µm Teflon filter to prepare a resist solution.

With respect to the composition thus prepared, the development defect and the image performance of the resist were evaluated by the following method. Table 2 shows the evaluation results of sensitivity, resolution, development defect, and PEB temperature dependency.

(Evaluation method of phenomenon defect function)

(1) Development defect-I

The photosensitive resin composition was uniformly applied onto the silicon substrate subjected to the hexamethyldisilazane treatment by a spin coater, heated and dried on a hot plate at 120 ° C. for 60 seconds to form a resist film of 0.8 μm. This resist film was exposed by the electron beam modeling device (acceleration voltage 50 keV, beam diameter 0.12 micrometer), and it heated on the hotplate for 90 second at 110 degreeC immediately after exposure. The solution was further developed at 23 ° C. for 60 seconds in an aqueous solution of tetramethylammonium hydroxide at a concentration of 2.38 wt%, washed with pure water for 30 seconds, and then dried. The formed sample of the contact hole pattern thus obtained was measured with a KLA2112 group (manufactured by KLA Tencol Co., Ltd.) (Threshould 12, Pixcel Size = 0.39).

(2) Development defect-II

In (1) development defect function -I, the development defect function was measured with the same method with respect to the heating, image development, washing | cleaning, and a dry sample except not exposing.

(Image evaluation method)

In the same manner as in the development defect function (I) above, a 0.8 탆 resist film was formed, and the film was exposed, heated, developed, washed and dried.

Then, the film thickness was measured by the film thickness meter, and the residual film rate was calculated. Moreover, the formed 0.2 micrometer contact hole pattern was observed with the scanning electron microscope, and the profile was investigated.

(Sensitivity evaluation method)

Sensitivity was evaluated by the exposure amount (microC / cm <2>) which reproduces a mask pattern of 0.40 micrometer.

(Resolution evaluation method)

The resolution indicates the limit resolution (mu m) at the exposure amount which reproduces the mask pattern of 0.40 mu m.

(PEB temperature dependence)

In the case where the PEB temperature was raised by 10 ° C., the fact that the marginal resolution did not decrease was set to 0, that the decrease in the marginal resolution was 0.01 µm, and that the decrease in the marginal resolution was 0.02 µm or more.                     

Acid generators PAG-1 and PAG-2 are as follows.

Surfactants (W-1), (W-2), (W-3), (W-4), and (W-5) are as follows.

W-1: Megafac F176 (made by Dainippon Ink Corporation)

W-2: Megafac R08 (made by Dainippon Ink Corporation)

W-3: polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.)

W-4: Polyoxyethylene Nonylphenyl Ether

W-5: TOROYSOL S-366 (made by Troy Chemical Company)

The composition, physical properties, etc. of the binder resin used are as follows.

(b-3): p-hydroxy styrene / p-t-butoxycarboxy styrene copolymer (molar ratio: 80/20), weight average molecular weight 13000, molecular weight distribution (Mw / Mn) 1.4

(b-4): p-hydroxystyrene / p- (1-ethoxyethoxy) styrene copolymer (molar ratio: 70/30), weight average molecular weight 12000, molecular weight distribution (Mw / Mn) 1.3

(b-21): p-hydroxy styrene / t-butyl methacrylate copolymer (molar ratio: 70/30), weight average molecular weight 16000, molecular weight distribution (Mw / Mn) 2.0

(b-22): p-hydroxystyrene / p- (1-t-butoxyethoxy) styrene copolymer (molar ratio: 85/15), weight average molecular weight 12000, molecular weight distribution (Mw / Mn) 1.1

(b-28): p-hydroxystyrene / p- (1-phenethyloxyethoxy) styrene copolymer (molar ratio: 85/1 5), weight average molecular weight 12000, molecular weight distribution (Mw / Mn) 1.2

(b-29): p-hydroxystyrene / p- (1-phenoxyethoxyethoxy) styrene copolymer (molar ratio: 85/15), weight average molecular weight 13000, molecular weight distribution (Mw / Mn) 1.2

(PHS): Poly-p-hydroxystyrene (product made in Japan procurement company, brand name VP-15000)                     

(PHS / St: synthesized in Synthesis Example 1): p-hydroxystyrene / styrene (molar ratio: 80/20), weight average molecular weight 26000, molecular weight distribution (Mw / Mn) 1.9

As can be clearly seen from the results shown in Table 2, the positive electron beam or X-ray resist composition of the present invention has high resolution, provides a rectangular pattern profile, has less development defects, and has a low PEB temperature dependency. In addition, the same excellent effect was observed also when the irradiation source was X-rays.

The positive electron beam or X-ray resist composition of the present invention has high resolution, can provide excellent rectangular profile patterns, has less development defects, and has low PEB temperature dependency.

Claims (6)

Onium salt (a) which produces | generates an acid by irradiation of an electron beam or X-ray, and has one or more electron withdrawing groups on the substituent of a cation site | part, and A resin (b) which increases in solubility in an alkaline developer by the action of an acid; The electron withdrawing group is a positive electron beam, characterized in that selected from the group consisting of fluorine atom, chlorine atom, cyano group, trifluoromethyl group, nitro group, sulfonyl group, acyl group, alkoxycarbonyl group, acyloxy group and sulfonyloxy group Or X-ray resist composition. Onium salt (a) which generates an acid by irradiation of an electron beam or X-ray, and has at least one electron-withdrawing group on the substituent of the cation site, Resin (b) whose solubility in alkaline developing solution increases by the action of an acid, and It has a group that can be decomposed by an acid, the solubility in an alkaline developer is increased by the action of an acid, and contains a low molecular weight dissolution inhibiting compound (c) having a molecular weight of 3000 or less, The electron withdrawing group is a positive electron beam, characterized in that selected from the group consisting of fluorine atom, chlorine atom, cyano group, trifluoromethyl group, nitro group, sulfonyl group, acyl group, alkoxycarbonyl group, acyloxy group and sulfonyloxy group Or X-ray resist composition. Onium salt (a) which generates an acid by irradiation of an electron beam or X-ray, and has at least one electron-withdrawing group on the substituent of the cation site, Low molecular dissolution inhibiting compound (c) having a group capable of being decomposed by an acid, increasing solubility in an alkaline developer by the action of an acid, and having a molecular weight of 3000 or less; and It contains resin (d) which is insoluble in water and soluble in alkaline developer. The electron withdrawing group is a positive electron beam, characterized in that selected from the group consisting of fluorine atom, chlorine atom, cyano group, trifluoromethyl group, nitro group, sulfonyl group, acyl group, alkoxycarbonyl group, acyloxy group and sulfonyloxy group Or X-ray resist composition. The positive electron beam according to any one of claims 1 to 3, wherein the onium salt (a) is at least one compound selected from the group consisting of compounds represented by the following general formulas (I) to (III). Or X-ray resist composition.

Wherein at least one of R ₁ to R ₁₅ , at least one of R ₁₆ to R ₄₃ , and at least one of R ₄₄ to R ₅₃ represent an electron withdrawing group, and the electron withdrawing group has a fluorine atom and a chlorine atom , Cyano group, trifluoromethyl group, nitro group, sulfonyl group, acyl group, alkoxycarbonyl group, acyloxy group and sulfonyloxy group, and the remaining R ₁ to R ₅₃ are the same or different, and are hydrogen atom, minute An alkyl group which may be gaseous or cyclic, an alkoxy group which may be branched or cyclic, a hydroxy group, a halogen atom or a -SR ₅₄ group is represented, R ₅₄ represents an alkyl group or an aryl group which may be branched or cyclic. Two or more of R ₁ to R ₁₅ , R _{16 to} R ₄₃ , and R ₄₄ to R ₅₃ combine to include one or two or more selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom You may form a ring. X ⁻ represents an anion of alkanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid having 1 to 12 carbon atoms which may be substituted. The compound of claim 4, wherein in the general formulas (I) to (III), X ⁻ One or more fluorine atoms Branched or cyclic alkyl groups substituted with one or more fluorine atoms, Branched or cyclic alkoxy groups substituted with one or more fluorine atoms, Acyl groups substituted with one or more fluorine atoms, An acyloxy group substituted with one or more fluorine atoms, Sulfonyl groups substituted with one or more fluorine atoms, Sulfonyloxy groups substituted with one or more fluorine atoms, Sulfonylamino groups substituted with one or more fluorine atoms, Aryl groups substituted with one or more fluorine atoms, An aralkyl group substituted with one or more fluorine atoms, and A positive electron beam or X-ray resist composition, characterized in that it is an anion of benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid having at least one selected from alkoxycarbonyl groups substituted with at least one fluorine atom. The positive electron beam or X-ray resist composition according to any one of claims 1 to 3, which contains a fluorine-based and / or silicon-based surfactant (e).