Resist composition for electron beam, euv or x-ray

专利摘要:
(A1) A resist composition for electron beams, EUV or X-rays, which has a higher reduction potential than diphenyl iodonium salt and contains a compound which generates an acid by irradiation with actinic rays or radiation.
公开号:KR20030080195A
申请号:KR10-2003-0008691
申请日:2003-02-12
公开日:2003-10-11
发明作者:미즈타니가즈요시；다카하시효우
申请人:후지 샤신 필름 가부시기가이샤；
IPC主号:

专利说明:

RESIST COMPOSITION FOR ELECTRON BEAM, EUV OR X-RAY}
[1] The present invention relates to a resist composition suitable for use in ultra-microlithography processes such as the manufacture of VLSI and high-capacity microchips or other photofabrication processes. More specifically, it relates to a positive resist composition and a negative resist composition capable of forming a high precision pattern using electron beams, EUV (extreme ultraviolet rays) or X-rays.
[2] In recent years, integrated circuits have been increasingly integrated, and processing of ultra-fine patterns having a line width of 1/2 micron or less is required in the manufacture of semiconductor substrates such as VLSI. In order to meet these demands, the wavelength of use of the exposure apparatus used for photolithography has become shorter, and it is currently considered to use ultraviolet rays and excimer laser light (for example, XeCl, KrF or ArF). Moreover, formation of a finer pattern by electron beam or X-rays is examined.
[3] Electron beam lithography is regarded as the next generation or the next generation of pattern forming technology, and there has been a strong demand for the development of positive and negative resists having high sensitivity, high resolution, and rectangular profile forming ability.
[4] According to electron beam lithography, the accelerated electron beam collides and scatters with atoms constituting the resist material to supply energy to the compound, causing the resist material to react to form an image. The use of highly accelerated electron beams increases the straight forward propagation of the electron beams and reduces the effects of electron scattering, making it possible to form patterns with high resolution, rectangular profiles and good edge roughness. However, on the other hand, the transmittance of the electron beam is increased, and the sensitivity is decreased. Thus, in electron beam lithography, there is a tradeoff between sensitivity and resolution, resist profile and edge roughness, which is a problem to be solved to meet the needs of both sensitivity and resolution, resist profile and edge roughness. EUV lithography and X-ray lithography also have the same problem.
[5] The positive resists for electron beams or X-rays have been mainly studied exclusively for resist technology for KrF excimer laser. For example, Japanese Patent Application Laid-Open No. 2000-181065 describes the combination of an acid-generating compound with electron beam irradiation and an amine compound having a boiling point of 250 ° C. or lower, and European Patent No. 919,867 describes a polymer having an acid-decomposable group, an acid generator, and an electron beam. The use of a sensitizer is described, and Japanese Patent Application Laid-open No. Hei 7-508840 describes a combination of an amide compound and a polymer having an acid-decomposable group. Furthermore, Japanese Patent Laid-Open No. 3-200968 describes the use of maleimide compounds, Japanese Patent Laid-Open No. 7-92680 describes the use of sulfonamide compounds, and Japanese Patent Laid-Open No. 11-44950- The use of sulfonimide compounds containing SO ₂ -NH-SO ₂ -substructures is described. However, even these attempts could not solve the problem of satisfying all the needs of high sensitivity, high resolution, good rectangular resist profile and good edge roughness.
[6] On the other hand, various alkali-soluble resins have been proposed regarding chemically amplified negative resists. Japanese Patent Application Laid-open No. Hei 8-152717 describes the use of partially alkyletherized polyvinylphenols. Japanese Patent Laid-Open No. Hei 6-67431 and Japanese Patent Laid-Open No. Hei 10-10733 describe the use of copolymers of vinylphenol and styrene. Japanese Patent No. 2505033 describes the use of novolak resins. Japanese Patent Laid-Open Nos. 7-311463 and 8-292559 describe the use of monodisperse polyvinylphenol. However, using such alkali-soluble resin, all characteristics of sensitivity, resolution, resist profile and edge roughness could not be satisfied by irradiation with electron beams or X-rays.
[7] Moreover, regarding chemical amplification negative resists, various compounds which generate | occur | produce an acid by irradiation of an electron beam or X-rays have been proposed. Japanese Patent Publication Hei 8-3635 describes the use of organic halogen compounds. JP-A 2-150848 and JP-A 6-199770 describe the use of iodonium salts and sulfonium salts. JP-A 2-52348, JP-A-4-367864 and JP-A-4-367865 describe the use of acid generators containing Cl or Br. Japanese Patent Laid-Open No. Hei 4-210960 and Japanese Patent Laid-Open No. Hei 4-217249 describe the use of diazodisulfones or diazosulfone compounds. Japanese Patent Application Laid-open No. Hei 4-226454 describes the use of triazine compounds, Japanese Patent Application Laid-Open No. Hei 3-87746, Japanese Patent Application Laid-open No. Hei 4-291259, Japanese Patent Application Laid-open No. Hei 6-236024 and US Pat. No. 5,344,742 The use of nate compounds is described. However, even with such an acid generator, the trade-off relationship between sensitivity and resolution, resist profile and edge roughness could not be solved by irradiation of electron beams or X-rays.
[8] Furthermore, as for the crosslinking agent, for example, metyrolmelamine, resol resin, epoxidized novolak resin or urea resin and the like are used. However, these crosslinking agents are unstable to heat, and there is a problem of storage stability of the resist solution.
[9] The resist compositions described in Japanese Patent Nos. 3,000,740, 9-166870 and 2-15270 also satisfy the requirements for high sensitivity, high resolution, good rectangular resist profile and excellent edge roughness by irradiation with electron beams or X-rays. Insufficient to make
[10] Therefore, it has been difficult to meet all the requirements of sufficient high sensitivity, sufficient high resolution, good rectangular resist profile and good edge roughness in the techniques known to date, and there has been a strong desire to solve this problem.
[11] SUMMARY OF THE INVENTION An object of the present invention is to provide a resist composition which solves the problem of technology for improving performance in the microfabrication of semiconductor devices using electron beams, EUV or X-rays.
[12] Another object of the present invention is to provide a positive resist composition having excellent sensitivity and resolution when using electron beams, EUV or X-rays.
[13] It is another object of the present invention to provide a positive resist composition that satisfies the sensitivity and resolution as well as the characteristics of rectangular pattern profile and edge roughness when using electron beam, EUV or X-ray.
[14] It is yet another object of the present invention to provide a chemically amplified negative resist composition which satisfies all properties of sensitivity, resolution, resist profile and edge roughness when using electron beam, EUV or X-ray.
[15] Other objects of the present invention will become apparent from the following description.
[16] The present inventors have discovered that the objects of the present invention can be achieved by a resist composition containing a specific acid generator as a result of diligence, and completed the present invention.
[17] Specifically, the present invention includes the following resist compositions:
[18] (1) A resist composition for electron beams, EUV or X-rays, which has a higher reduction potential than the (A1) diphenyl iodonium salt and contains a compound which generates an acid by irradiation with actinic rays or radiation.
[19] (2) Compounds having a higher reduction potential than (A1) diphenyl iodonium salt and generating an acid by irradiation of actinic radiation or radiation and insoluble or poorly soluble in aqueous solutions of (BP) alkali, A positive resist composition for electron beam, EUV or X-ray containing a polymer that is soluble in aqueous solution.
[20] (3) The compound according to (2), which has a higher reduction potential than the (A1) diphenyl iodonium salt and generates an acid by irradiation with actinic rays or radiation, is represented by the following general formulas (1), (2) or ( Positive resist composition for electron beam, EUV or X-ray which is a compound represented by 3).
[21]
[22] (In General Formula (1), Y represents the aryl group which may have a substituent or the alkyl group which may have a substituent.
[23] R _1a to R _8a each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a carboxyl group, an alkyl group which may have a substituent, or a cycloalkyl group which may have a substituent.)
[24]
[25] (In General Formula (2), R ₁ to R ₁₅ each independently represent a hydrogen atom, a nitro group, a cyano group, or a trifluoromethyl group, provided that two or more of R ₁ to R ₁₅ are a nitro group, a cyano group, and Trifluoromethyl group.
[26] In General Formula (3), R ₁₆ to R ₂₇ each independently represent a hydrogen atom, a nitro group, a cyano group, a trifluoromethyl group, or a halogen atom.
[27] y represents 0 or 1.
[28] X ⁻ is a fluorine atom, an alkyl group substituted with one or more fluorine atoms, an alkoxy group substituted with one or more fluorine atoms, an acyl group substituted with one or more fluorine atoms, an acyloxy group substituted with one or more fluorine atoms, one or more fluorine atoms A sulfonyl group substituted with an atom, a sulfonyloxy group substituted with one or more fluorine atoms, a sulfonylamino group substituted with one or more fluorine atoms, an aryl group substituted with one or more fluorine atoms, an aralkyl group substituted with one or more fluorine atoms, and one Or an anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least one selected from the alkoxycarbonyl groups substituted with the above fluorine atoms.)
[29] (4) The compound of (2) or (3) WHEREIN: The acid generate | occur | produces by irradiation of (A2) actinic light or a radiation, and further has a compound which has a structure represented by either of following general formula (I)-(III) A positive resist composition for electron beam, EUV or X-ray containing.
[30]
[31] (In General Formulas (I) to (III), R ₁ to R ₃₇ may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, or a -SR ₃₈ group. R ₃₈ represents an alkyl group or an aryl Group.
[32] X ⁻ is a fluorine atom, an alkyl group substituted with one or more fluorine atoms, an alkoxy group substituted with one or more fluorine atoms, an acyl group substituted with one or more fluorine atoms, an acyloxy group substituted with one or more fluorine atoms, one or more fluorine atoms A sulfonyl group substituted with an atom, a sulfonyloxy group substituted with one or more fluorine atoms, a sulfonylamino group substituted with one or more fluorine atoms, an aryl group substituted with one or more fluorine atoms, an aralkyl group substituted with one or more fluorine atoms, and one Anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least one selected from alkoxycarbonyl groups substituted with the above fluorine atoms)
[33] (5) The compound according to any one of (2) to (4), wherein the compound (A3) generates a fluorine atom-containing carboxylic acid by irradiation with actinic rays or radiation and (A4) fluorine by irradiation with actinic rays or radiation A positive resist composition for electron beam, EUV or X-ray further containing at least one compound selected from compounds which generate an atom-free carboxylic acid.
[34] (6) The polymer according to any one of (2) to (5), wherein the polymer is insoluble or poorly soluble in the aqueous alkali solution (BP), but becomes soluble in the aqueous alkali solution by the action of an acid. Or a positive resist composition for electron beam, EUV or X-ray, which is a polymer having a structural unit containing a group represented by (X2).
[35]
[36] (In formula (X1), R <_1b> and R <_2b> may be same or different, and each represents a hydrogen atom or an alkyl group.
[37] R _3b and R _4b may be the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, or a cycloalkyl group which may have a substituent.
[38] R <_5b> represents the alkyl group which may have a substituent, the cycloalkyl group which may have a substituent, the aryl group which may have a substituent, or the aralkyl group which may have a substituent.
[39] m represents the integer of 0-20, n represents the integer of 0-5.)
[40]
[41] (In formula (X2), R <_6b> and R <_7b> may be same or different, and each represents a hydrogen atom or an alkyl group.
[42] W represents a divalent organic group.
[43] R _8b represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.)
[44] (7) The polymer according to any one of (2) to (6), wherein the polymer which is insoluble or poorly soluble in the aqueous alkali solution (BP) but becomes soluble in the aqueous alkali solution by the action of acid is decomposed by the action of acid. A positive resist composition for electron beam, EUV or X-ray, which is a polymer having a structural unit containing a tertiary ester group.
[45] (8) The polymer according to any one of (2) to (6), wherein the polymer is insoluble or poorly soluble in the aqueous alkali solution (BP), but becomes soluble in the aqueous alkali solution by the action of acid. A positive resist composition for electron beam, EUV or X-ray, which is a polymer having a structural unit containing a tert-butoxycarbonyl group.
[46] (9) A crosslinking agent which has a higher reduction potential than (A1) diphenyl iodonium salt and generates an acid by irradiation of actinic light or radiation, a crosslinking agent crosslinked by the action of (BN) alkali-soluble resin and (C) acid. Negative resist composition for electron beam, EUV or X-ray containing.
[47] (10) The compound of (9), wherein the compound having a higher reduction potential than the (A1) diphenyl iodonium salt and generates an acid by irradiation with actinic rays or radiation is represented by the following general formulas (1), (2) or (3): Negative resist composition for electron beam, EUV or X-ray which is a compound represented by).
[48]
[49] (In General Formula (1), Y represents the aryl group which may have a substituent or the alkyl group which may have a substituent.
[50] R _1a to R _8a each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a carboxyl group, an alkyl group which may have a substituent, or a cycloalkyl group which may have a substituent.)
[51]
[52] (In General Formula (2), R ₁ to R ₁₅ each independently represent a hydrogen atom, a nitro group, a cyano group, or a trifluoromethyl group, provided that two or more of R ₁ to R ₁₅ are a nitro group, a cyano group, and Trifluoromethyl group.
[53] In General Formula (3), R ₁₆ to R ₂₇ each independently represent a hydrogen atom, a nitro group, a cyano group, a trifluoromethyl group, or a halogen atom.
[54] y represents 0 or 1.
[55] X ⁻ is a fluorine atom, an alkyl group substituted with one or more fluorine atoms, an alkoxy group substituted with one or more fluorine atoms, an acyl group substituted with one or more fluorine atoms, an acyloxy group substituted with one or more fluorine atoms, one or more fluorine atoms A sulfonyl group substituted with an atom, a sulfonyloxy group substituted with one or more fluorine atoms, a sulfonylamino group substituted with one or more fluorine atoms, an aryl group substituted with one or more fluorine atoms, an aralkyl group substituted with one or more fluorine atoms, and one Or an anion of alkyl sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid or anthracene sulfonic acid having at least one selected from alkoxycarbonyl groups substituted with the above fluorine atoms.)
[56] (11) The compound of (9) or (10) which produces | generates an acid by irradiation of (A2) actinic light or radiation, and further has a compound which has a structure represented by either of following general formula (I)-(III). Negative resist composition for electron beam, EUV or X-ray containing.
[57]
[58] (In general formula (I)-(III), R <_1> -R <_37> may be same or different, and each is a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, and a halogen. represents an atom or -SR _38. R ₃₈ represents a straight-chain, branched or cyclic alkyl group or an aryl group.
[59] X ⁻ is a fluorine atom, a straight, branched or cyclic alkyl group substituted with one or more fluorine atoms, a straight, branched or cyclic alkoxy group substituted with one or more fluorine atoms, an acyl group substituted with one or more fluorine atoms, 1 An acyloxy group substituted with one or more fluorine atoms, a sulfonyl group substituted with one or more fluorine atoms, a sulfonyloxy group substituted with one or more fluorine atoms, a sulfonylamino group substituted with one or more fluorine atoms, an aryl substituted with one or more fluorine atoms Anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least one selected from the group, an aralkyl group substituted with one or more fluorine atoms, and an alkoxycarbonyl group substituted with one or more fluorine atoms)
[60] (12) The compound according to any one of (9) to (11), wherein the compound (A3) generates a fluorine atom-containing carboxylic acid by irradiation with actinic rays or radiation and (A4) fluorine by irradiation with actinic rays or radiation A negative resist composition for electron beam, EUV or X-ray further containing at least one compound selected from compounds which generate an atom-free carboxylic acid.
[61] (13) The crosslinking agent which crosslinks by the action of the said (C) acid in any one of (9)-(12) is chosen from the compound represented by following General formula (2)-(4) and an alkoxy methylation melamine compound. Negative resist composition for electron beam, EUV or X-ray which is at least one compound.
[62]
[63] (In General Formula (2)-(4), R <_5b> represents a hydrogen atom, an alkyl group, or an acyl group each independently.
[64] In General Formula (2), R _6b to R _9b each independently represent a hydrogen atom, a hydroxy group, an alkyl group, or an alkoxy group.
[65] X represents a single bond, methylene group or oxygen atom.)
[66] (14) The crosslinking agent which crosslinks by any action of the said (C) acid in any one of (9)-(12) has 1-6 benzene rings per molecule, and two or more in either of these benzene rings A negative resist composition for electron beam, EUV or X-ray, which is a compound selected from phenol derivatives having a hydroxymethyl group and / or an alkoxymethyl group bonded thereto.
[67] Hereinafter, the composition which comprises the resist composition which concerns on this invention is demonstrated in detail.
[68] << Compound which has higher reduction potential than (A1) diphenyl iodonium salt and generates an acid by irradiation of actinic light or radiation (hereinafter, also referred to as "(A1) component" or "compound of (A1)") >
[69] The compound of (A1) is used as an acid generator in the present invention. The reduction potential of the compound of (A1) can be measured by cyclic voltammetry. As a compound of (A1), the diphenyl iodonium salt which has an electron-withdrawing group like a bis (chlorophenyl) iodonium salt, for example in a phenyl group, and the compound represented by following General formula (1)-(3) are mentioned. Preferably, the compounds represented by General Formulas (1) to (3) are used.
[70] In General formula (1), Y represents the aryl group which may have a substituent, or the alkyl group which may have a substituent. R _1a to R _8a each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a carboxyl group, or an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent.
[71] The alkyl group represented by Y may be either a linear or branched alkyl group, and preferably has 1 to 8 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group and octyl group. The alkyl group may further have a substituent.
[72] The aryl group represented by Y is preferably one having 6 to 16 carbon atoms. Specific examples of the aryl group include phenyl group, naphthyl group, anthryl group, phenanthryl group and pyrenyl group.
[73] As a substituent of the alkyl group or aryl group represented by Y, for example, an aryl group, an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, a hydroxyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, Nitro group, arylcarbonyl group, alkylcarbonyl group and the like. Among the substituents of the alkyl or aryl group represented by Y, electron-withdrawing substituents such as halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms or iodine atoms), cyano groups, nitro groups, arylcarbonyl groups or alkylcarbonyl groups have a reduction potential. It is preferable at the point of view.
[74] The alkyl group represented by any one of R _1a to R _8a may be either a linear or branched alkyl group, and preferably 1 to 8 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group and octyl group. The alkyl group may further have a substituent.
[75] The cycloalkyl group represented by any one of R _1a to R _8a is preferably 3 to 8 carbon atoms. Specific examples of the cycloalkyl group include cyclopropyl group, cyclopentyl group, cyclohexyl group and the like. The cycloalkyl group may further have a substituent.
[76] Examples of the halogen atom represented by any one of R _1a to R _8a include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
[77] As a substituent of the alkyl group or cycloalkyl group represented by any one of R <_1a> -R <_8a> , For example, an alkyl group (for example, methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, tert- butyl group, n-a) And a cycloalkyl group, a phenyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group and a nitro group. Among substituents of an alkyl group or a cycloalkyl group represented by any one of R _1a to R _8a , an alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group) from the viewpoint of improving solvent solubility. , n-amyl group or tert-amyl group) are preferable, and electron-withdrawing substituents such as halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group or nitro group This is preferred.
[78] When the compound of general formula (A1) has a monoanion, it is preferable to generate an organic sulfonic acid as the monoanion, and it is more preferable to generate an alkyl sulfonic acid, an aromatic sulfonic acid, a fluorinated alkyl sulfonic acid or a fluorinated aromatic sulfonic acid. Among the organic sulfonic acids, carbon atoms are preferable because they appropriately control the diffusion of the generated acid to improve resolution. Specifically, an aromatic sulfonic acid containing an alkyl group having 4 to 20 carbon atoms, a benzene ring or a naphthalene ring, a fluorinated alkyl sulfonic acid having 4 to 12 carbon atoms in an alkyl group, and a fluorinated aromatic sulfonic acid containing a benzene ring or a naphthalene ring It is preferably used.
[79] In formula (2), R ₁ to R ₁₅ each independently represent a hydrogen atom, a nitro group, a cyano group, or a trifluoromethyl group, provided that at least two of R ₁ to R ₁₅ represent a nitro group, a cyano group, and Trifluoromethyl group.
[80] In General formula (3), R <_16> -R <_27> represents a hydrogen atom, a nitro group, a cyano group, a trifluoromethyl group, or a halogen atom each independently.
[81] y represents 0 or 1.
[82] X ⁻ is a fluorine atom, an alkyl group substituted with one or more fluorine atoms, an alkoxy group substituted with one or more fluorine atoms, an acyl group substituted with one or more fluorine atoms, an acyloxy group substituted with one or more fluorine atoms, one or more fluorine atoms A sulfonyl group substituted with an atom, a sulfonyloxy group substituted with one or more fluorine atoms, a sulfonylamino group substituted with one or more fluorine atoms, an aryl group substituted with one or more fluorine atoms, an aralkyl group substituted with one or more fluorine atoms, and one An anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least one selected from the alkoxycarbonyl group substituted with the above fluorine atoms is shown.
[83] Halogen atoms represented by any one of R ₁₆ to R ₂₇ include fluorine, chlorine, bromine and iodine atoms.
[84] The alkyl group substituted with one or more fluorine atoms may be any of linear, branched and cyclic alkyl groups, and preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms.
[85] Specifically, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, heptafluoroisopropyl group, perfluorobutyl group, perfluorooctyl group, purple Luorododecyl group, perfluorocyclohexyl group, etc. can be mentioned. Especially, the C1-C4 perfluoroalkyl group substituted with all the fluorine atoms is preferable. Especially preferred is a perfluorobutyl group.
[86] The alkoxy group substituted with the at least one fluorine atom may be a linear, branched or cyclic alkoxy group, preferably having 1 to 12 carbon atoms and substituted with 1 to 25 fluorine atoms.
[87] Specifically, trifluoromethoxy group, pentafluoroethoxy group, heptafluoroisopropyloxy group, perfluorobutoxy group, perfluorooctyloxy group, perfluorododecyloxy group, and perfluorocyclohexyl jade You can list when. Especially, the C1-C4 perfluoroalkoxy group substituted with all the fluorine is preferable.
[88] The acyl group substituted with the at least one fluorine atom is preferably 2 to 12 carbon atoms and substituted with 1 to 23 fluorine atoms. Specifically, trifluoroacetyl group, fluoroacetyl group, pentafluoropropionyl group, pentafluorobenzoyl group, etc. can be mentioned.
[89] The acyloxy group substituted with the at least one fluorine atom is preferably 2 to 12 carbon atoms and substituted with 1 to 23 fluorine atoms. Specifically, trifluoroacetoxy group, fluoroacetoxy group, pentafluoropropionyloxy group, pentafluorobenzoyloxy group, etc. can be mentioned.
[90] The sulfonyl group substituted with the at least one fluorine atom is preferably 1 to 12 carbon atoms and substituted with 1 to 25 fluorine atoms. Specifically, trifluoromethanesulfonyl group, pentafluoroethanesulfonyl group, perfluorobutanesulfonyl group, perfluorooctanesulfonyl group, pentafluorobenzenesulfonyl group, and 4-trifluoromethylbenzenesulfonyl group are listed. can do.
[91] The sulfonyloxy group substituted with at least one fluorine atom described above is preferably that having 1 to 12 carbon atoms and substituted with 1 to 25 fluorine atoms. Specifically, a trifluoromethanesulfonyloxy group, a perfluorobutanesulfonyloxy group, 4-trifluoromethylbenzenesulfonyloxy group, etc. are mentioned.
[92] The sulfonylamino group substituted with at least one fluorine atom described above is preferably that having 1 to 12 carbon atoms and substituted with 1 to 25 fluorine atoms. Specific examples thereof include a trifluoromethanesulfonylamino group, a perfluorobutanesulfonylamino group, a perfluorooctanesulfonylamino group, a pentafluorobenzenesulfonylamino group, and the like.
[93] The aryl group substituted with one or more fluorine atoms preferably has 6 to 14 carbon atoms and is substituted with 1 to 9 fluorine atoms. Specifically, pentafluorophenyl group, 4-trifluoromethylphenyl group, heptafluoronaphthyl group, nonafluoroanthryl group, 4-fluorophenyl group, 2,4-difluorophenyl group, etc. are mentioned.
[94] The aralkyl group substituted with one or more fluorine atoms preferably has 7 to 10 carbon atoms and is substituted with 1 to 15 fluorine atoms. Specifically, pentafluorophenylmethyl group, pentafluorophenylethyl group, perfluorobenzyl group, perfluorophenethyl group, etc. can be mentioned.
[95] The alkoxycarbonyl group substituted with the at least one fluorine atom is preferably 2 to 13 carbon atoms and substituted with 1 to 25 fluorine atoms. Specifically, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, pentafluorophenoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorooctyloxycarbonyl group, etc. are mentioned.
[96] X ⁻ preferably represents a benzenesulfonate anion substituted with fluorine, more preferably a pentafluorobenzenesulfonate anion.
[97] Alkyl sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid or anthracene sulfonic acid having the fluorine-containing substituent is, for example, linear, branched or cyclic alkoxy group, acyl group, acyloxy group, sulfonyl group, sulfonyloxy group, sulfonylamino group, aryl group , An aralkyl group or an alkoxycarbonyl group (the carbon number range of these groups is the same as defined above), and may be further substituted with a substituent such as a halogen atom, a hydroxy group or a nitro group except for a fluorine atom.
[98] In the present invention, a compound of (A1) having a reduction potential higher than -0.78 V, which is a reduction potential of diphenyl iodonium salt, can be used as the acid generator. In view of stability, a compound of (A1) having a reduction potential of -0.5 V or less is preferably used.
[99] Although the specific example of the compound of (A1) is shown below, this invention is not limited to these.
[100]
[101]
[102]
[103]
[104] As for content of the compound of (A1) in the resist composition of this invention, 0.01-40 weight% is suitable with respect to the total solid of a resist composition, Preferably it is 0.5-30 weight%, More preferably, it is 1.0-25 weight%.
[105] << (A2) Compound which generate | occur | produces an acid by irradiation of actinic light or a radiation, and has a structure represented by either of general formula (I)-(III) (Hereinafter, "(A2) component" or "(A2) Also referred to as ") >>
[106] The resist composition which concerns on this invention may further contain the compound of (A2) as an acid generator.
[107] In General Formulas (I) to (III), R ₁ to R ₃₇ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a halogen atom or a -SR ₃₈ group. R ₃₈ represents an alkyl group or an aryl group.
[108] The alkyl group represented by any one of R ₁ to R ₃₇ may be either a linear, branched or cyclic alkyl group. The linear or branched alkyl group may have a substituent, and examples thereof include those having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group or tert-butyl group. The cyclic alkyl group may have a substituent and can mention C3-C8 things, such as a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group, for example.
[109] The alkoxy group represented by any one of R ₁ to R ₃₇ may be any of linear, branched and cyclic alkoxy groups. The linear or branched alkoxy group may have a substituent, for example, a methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group or jade C1-C8 things, such as a yloxy group, can be mentioned. Examples of the cyclic alkoxy group include a cyclopentyloxy group and a cyclohexyloxy group which may have a substituent.
[110] Examples of the halogen atom represented by any one of R ₁ to R ₃₇ include fluorine, chlorine, bromine and iodine atoms.
[111] Examples of the aryl group represented by R ₃₈ include those having 6 to 14 carbon atoms such as a phenyl group, tolyl group, methoxyphenyl group or naphthyl group, which may have a substituent.
[112] Substituents of the groups are preferably an alkyl group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (for example, a fluorine atom, a chlorine atom or an iodine atom), a 6 to 10 aryl group, a 2 to 6 alkenyl group, Cyano group, hydroxyl group, carboxyl group, alkoxycarbonyl group, nitro group, etc. are mentioned.
[113] In formulas (I) to (III), X ⁻ is a fluorine atom, an alkyl group substituted with one or more fluorine atoms, an alkoxy group substituted with one or more fluorine atoms, an acyl group substituted with one or more fluorine atoms, one or more An acyloxy group substituted with a fluorine atom, a sulfonyl group substituted with one or more fluorine atoms, a sulfonyloxy group substituted with one or more fluorine atoms, a sulfonylamino group substituted with one or more fluorine atoms, an aryl group substituted with one or more fluorine atoms, An anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least one selected from an aralkyl group substituted with one or more fluorine atoms and an alkoxycarbonyl group substituted with one or more fluorine atoms.
[114] The alkyl group substituted with one or more fluorine atoms may be any of linear, branched and cyclic alkyl groups, and preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms.
[115] Specifically, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, heptafluoroisopropyl group, perfluorobutyl group, perfluorooctyl group, purple Luorododecyl group, perfluorocyclohexyl group, etc. can be mentioned. Especially, the C1-C4 perfluoroalkyl group substituted with all the fluorine atoms is preferable. Especially preferred is a perfluorobutyl group.
[116] The alkoxy group substituted with the at least one fluorine atom may be a linear, branched or cyclic alkoxy group, preferably having 1 to 12 carbon atoms and substituted with 1 to 25 fluorine atoms.
[117] Specifically, trifluoromethoxy group, pentafluoroethoxy group, heptafluoroisopropyloxy group, perfluorobutoxy group, perfluorooctyloxy group, perfluorododecyloxy group, and perfluorocyclohexyl jade You can list when. Especially, the C1-C4 perfluoroalkoxy group substituted with all the fluorine is preferable.
[118] The acyl group substituted with the at least one fluorine atom is preferably 2 to 12 carbon atoms and substituted with 1 to 23 fluorine atoms. Specifically, trifluoroacetyl group, fluoroacetyl group, pentafluoropropionyl group, pentafluorobenzoyl group, etc. can be mentioned.
[119] The acyloxy group substituted with the at least one fluorine atom is preferably 2 to 12 carbon atoms and substituted with 1 to 23 fluorine atoms. Specifically, trifluoroacetoxy group, fluoroacetoxy group, pentafluoropropionyloxy group, pentafluorobenzoyloxy group, etc. can be mentioned.
[120] The sulfonyl group substituted with the at least one fluorine atom is preferably 1 to 12 carbon atoms and substituted with 1 to 25 fluorine atoms. Specifically, trifluoromethanesulfonyl group, pentafluoroethanesulfonyl group, perfluorobutanesulfonyl group, perfluorooctanesulfonyl group, pentafluorobenzenesulfonyl group, 4-trifluoromethylbenzenesulfonyl group, etc. are mentioned. can do.
[121] The sulfonyloxy group substituted with at least one fluorine atom described above is preferably that having 1 to 12 carbon atoms and substituted with 1 to 25 fluorine atoms. Specifically, a trifluoromethanesulfonyloxy group, a perfluorobutanesulfonyloxy group, 4-trifluoromethylbenzenesulfonyloxy group, etc. are mentioned.
[122] The sulfonylamino group substituted with at least one fluorine atom described above is preferably that having 1 to 12 carbon atoms and substituted with 1 to 25 fluorine atoms. Specific examples thereof include a trifluoromethanesulfonylamino group, a perfluorobutanesulfonylamino group, a perfluorooctanesulfonylamino group, a pentafluorobenzenesulfonylamino group, and the like.
[123] The aryl group substituted with one or more fluorine atoms preferably has 6 to 14 carbon atoms and is substituted with 1 to 9 fluorine atoms. Specifically, pentafluorophenyl group, 4-trifluoromethylphenyl group, heptafluoronaphthyl group, nonafluoroanthryl group, 4-fluorophenyl group, 2,4-difluorophenyl group, etc. are mentioned.
[124] The aralkyl group substituted with one or more fluorine atoms preferably has 7 to 10 carbon atoms and is substituted with 1 to 15 fluorine atoms. Specifically, pentafluorophenylmethyl group, pentafluorophenylethyl group, perfluorobenzyl group, perfluorophenethyl group, etc. can be mentioned.
[125] The alkoxycarbonyl group substituted with the at least one fluorine atom is preferably 2 to 13 carbon atoms and substituted with 1 to 25 fluorine atoms. Specifically, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, pentafluorophenoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorooctyloxycarbonyl group, etc. are mentioned.
[126] X ⁻ preferably represents a benzenesulfonate anion substituted with fluorine, more preferably a pentafluorobenzenesulfonate anion.
[127] Alkyl sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid or anthracene sulfonic acid having the fluorine-containing substituent is, for example, linear, branched or cyclic alkoxy group, acyl group, acyloxy group, sulfonyl group, sulfonyloxy group, sulfonylamino group, aryl group , An aralkyl group or an alkoxycarbonyl group (the carbon number range of these groups is the same as defined above), and may be further substituted with a substituent such as a halogen atom, a hydroxy group or a nitro group except for a fluorine atom.
[128] Although the specific example of a compound represented by either of general formula (I)-(III) below is shown, this invention is not limited to these.
[129]
[130]
[131]
[132]
[133]
[134]
[135]
[136]
[137] The compound represented by any one of the general formulas (I) and (II) is, for example, reacted with an aryl Grignard reagent such as aryl magnesium bromide and substituted or unsubstituted phenyl sulfoxide, and then the obtained triarylsulfonium halide is reacted. A method comprising the step of salt exchange with a sulfonic acid, a substituted or unsubstituted phenylsulfoxide and the corresponding aromatic compound are condensed in the presence of an acid catalyst such as methanesulfonic acid / diphosphorous pentaoxide or aluminum chloride, It may be synthesized by a method comprising the step of salt exchange with water, or a method comprising the step of condensing the diarylionium salt and the diaryl sulfide in the presence of a catalyst such as copper acetate and then salt exchange the resulting condensate. .
[138] The compound represented by the general formula (III) can be synthesized by reacting the periodate with an aromatic compound and salt-exchanging the obtained iodonium salt with the corresponding sulfonic acid.
[139] In this invention, the compound of (A1) and the compound of (A2) are used together by the ratio shown below. Specifically, the compounds are usually 100/0 to 10/90, preferably 90/10 to 30/70, more preferably 80/20 to 40 in molar ratio of the compound of (A1) / the compound of (A2) / 60 is used.
[140] << (A3) Compound which produces | generates fluorine atom containing carboxylic acid by irradiation of actinic light or radiation (henceforth "a compound of (A3)") >>
[141] The resist composition which concerns on this invention may contain the compound of (A3) further as an acid generator.
[142] Examples of the fluorine atom-containing carboxylic acid include fluorine-substituted aliphatic carboxylic acid and fluorine-substituted aromatic carboxylic acid.
[143] Examples of the fluorine-substituted aliphatic carboxylic acid include acetic acid, propionic acid, n-butyric acid, isobutyric acid, valeric acid, trimethylacetic acid, capronic acid, heptanoic acid, caprylic acid, pelagonic acid, capric acid, lauric acid and myristic And fluorine-substituted compounds of aliphatic carboxylic acids such as acid, palmitic acid, threaric acid, undecanoic acid or tridecanoic acid. Aliphatic carboxylic acid may further have a halogen atom except a hydroxy group, an alkoxy group, or a fluorine atom as a substituent. The aliphatic carboxylic acid may contain a linking group such as an oxygen atom, a sulfur atom, a carbonyl group, an ester group or a sulfonyl group in its alicyclic chain.
[144] Preferred fluorine-substituted aliphatic carboxylic acids include those represented by the following general formula:
[145] L- (CH ₂ ) _p (CF ₂ ) _q (CH ₂ ) _r -COOH
[146] In the formula, L represents a hydrogen atom or a fluorine atom, p and r each independently represent an integer of 0 to 15, and q represents an integer of 1 to 15. In the formula, the hydrogen or fluorine atom contained in the alkyl chain may be substituted with a fluorine atom (preferably having 1 to 5 carbon atoms), an alkoxy group (preferably having 1 to 5 carbon atoms) or a hydroxy group which may be substituted with a fluorine atom. May be substituted.
[147] As a fluorine-substituted aliphatic carboxylic acid, the fluorine-substituted compound of C2-C20 saturated aliphatic carboxylic acid is preferable, and the fluorine-substituted compound of C4-C20 saturated aliphatic carboxylic acid is more preferable. By adjusting the carbon number of the aliphatic carboxylic acid to 4 or more, the diffusion of the generated acid can be reduced to further suppress the line width fluctuation with time from exposure to post-heating. Among them, fluorine-substituted compounds of linear or branched saturated aliphatic carboxylic acids having 4 to 18 carbon atoms are preferably used.
[148] As a fluorine-substituted aromatic carboxylic acid, the fluorine substituted compound of C7-C20 aromatic carboxylic acid is preferable, The fluorine substituted compound of C7-C15 aromatic carboxylic acid is more preferable, The aromatic C7-C11 aromatic carboxylic acid Acids are more preferred. Specific examples of the fluorine-substituted aromatic carboxylic acid include, for example, benzoic acid, substituted benzoic acid, naphthoic acid, substituted naphthoic acid, anthracenecarboxylic acid or substituted anthracenecarboxylic acid (wherein the substituent is an alkyl group, an alkoxy group, And fluorine-substituted compounds of aromatic carboxylic acids such as hydroxy, halogen, aryl, acyl, acyloxy, nitro, alkylthio and arylthio groups. Among these, the fluorine-substituted compound or substituted benzoic acid of benzoic acid is used preferably.
[149] Examples of aliphatic or aromatic carboxylic acids substituted with fluorine atoms include aliphatic or aromatic carboxylic acids in which one or more hydrogen atoms present in a skeleton other than a carboxyl group are substituted with fluorine atoms. In particular, an aliphatic or aromatic carboxylic acid (perfluoro saturated aliphatic carboxylic acid or perfluoro aromatic carboxylic acid) in which all hydrogen atoms present in the skeleton other than the carboxyl group are substituted with fluorine atoms is preferable. By using such perfluoro aliphatic or aromatic carboxylic acid, the sensitivity is further improved.
[150] Among the aliphatic carboxylic acid anions, anions having a fluorine atom on the α-carbon atom of the carboxylic acid have a high acid strength and tend to easily salt exchange with a carboxylic acid anion having no fluorine atom. Perfluoro aliphatic carboxylic acid anions have higher acid strength.
[151] In the compound of (A3), an onium salt compound (eg, sulfonium salt or iodonium salt) having an anion of an aliphatic or aromatic carboxylic acid substituted with the fluorine atom as a monoanion, an imidocarboxylate compound each having a carboxylic ester group And nitrobenzyl ester compounds.
[152] As an example of a more preferable compound of (A3), the compound represented by the following general formula (IF)-(IIIF) is mentioned.
[153] By using such a compound, sensitivity, resolution and exposure margin are further improved. When this compound is irradiated with actinic light or radiation, a saturated aliphatic or aromatic carboxylic acid substituted with one or more fluorine atoms corresponding to an anion represented by X ⁻ in any one of general formulas (IF) to (IIIF) is generated. It functions as an acid generator.
[154]
[155] In formulas (IF) to (IIIF), R ₁ to R ₃₇ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxy group, a halogen atom or -SR ₃₈ groups are represented. R ₃₈ represents a straight chain, branched or cyclic alkyl group or an aryl group. X ⁻ represents an anion of an aliphatic or aromatic carboxylic acid substituted with one or more fluorine atoms.
[156] In any of General Formulas (IF) to (IIIF), X ⁻ preferably represents an anion of a perfluoro aliphatic carboxylic acid or a perfluoro aromatic carboxylic acid, more preferably fluorine having 4 or more carbon atoms. An anion of substituted alkylcarboxylic acid is shown.
[157] The linear or branched alkyl group represented by any one of R ₁ to R ₃₈ may have a substituent, and for example, has 1 to C carbon such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group or t-butyl group. You can list four things. The cyclic alkyl group represented by any one of R ₁ to R ₃₈ may have a substituent, and examples thereof include 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group or cyclohexyl group.
[158] The alkoxy group represented by any one of R ₁ to R ₃₇ may have a substituent, for example, a methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group or tert -C1-C4 things, such as a butoxy group, are mentioned.
[159] Examples of the halogen atom represented by any one of R ₁ to R ₃₇ include fluorine, chlorine, bromine and iodine atoms.
[160] The aryl group represented by R ₃₈ may have a substituent, and examples thereof include 6 to 14 carbon atoms such as a phenyl group, tolyl group, methoxyphenyl group or naphthyl group.
[161] Substituents for the above groups are preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (for example, a fluorine atom, a chlorine atom or an iodine atom), a 6 to 10 carbon atoms aryl group, an alkenyl group having 2 to 6 carbon atoms, a cyano group, Hydroxy groups, carboxyl groups, alkoxycarbonyl groups, nitro groups and the like.
[162] The iodonium compound or sulfonium compound represented by any one of General Formulas (IF) to (IIIF) used in the present invention is a monoanion represented by X ^−, and a saturated aliphatic or aromatic carboxylic acid substituted with one or more fluorine atoms. Has an anion. The anion is an anion (-COO ^-) formed by departure of the hydrogen atoms of the saturated aliphatic or aromatic carboxylic acid (-COOH) is.
[163] Although the specific example of the compound of (A3) is shown below, this invention is not limited to these.
[164] Specific examples (I-1f) to (I-36f) of acid generators represented by general formula (IF):
[165]
[166]
[167]
[168]
[169]
[170] Specific examples (II-1f) to (II-67f) of acid generators represented by general formula (IIF):
[171]
[172]
[173]
[174]
[175]
[176]
[177]
[178]
[179]
[180] Specific examples (III-1f) to (III-4f) of the acid generator represented by general formula (IIIF):
[181]
[182] Specific examples of other acid generators (IV-1f) to (V-4f):
[183]
[184] The compound represented by the general formula (IF) can be synthesized by reacting an aromatic compound with a periodonium salt, and salt-exchanging the obtained iodonium salt with a corresponding carboxylic acid.
[185] The compound represented by any one of the general formulas (IIF) and (IIIF), for example, by reacting an aryl Grignard reagent such as aryl magnesium bromide with a substituted or unsubstituted phenyl sulfoxide, and then the obtained triarylsulfonium halide corresponds to A method comprising the step of salt exchange with a carboxylic acid, a substituted or unsubstituted phenylsulfoxide and the corresponding aromatic compound are condensed in the presence of an acid catalyst such as methanesulfonic acid / diphosphorous pentaoxide or aluminum chloride, and then Or a method comprising the step of salt exchange of the condensate, or a method comprising the step of condensing the diarylionium salt and the diaryl sulfide in the presence of a catalyst such as copper acetate and then salt exchange the resulting condensate. have.
[186] Salt exchange can be carried out by introducing a halide at one time and then converting it to a carboxylate using a silver chemical such as silver oxide or by using an ion exchange resin. In the salt exchange, a commercially available thing can be used as carboxylic acid or a carboxylate, or what was obtained by hydrolyzing a commercially available carboxylic acid halide can be used.
[187] The fluorine-substituted carboxylic acid as the anion moiety is preferably derived from a fluorine-aliphatic compound prepared by telomerization (also called telomer method) or oligomerization (also called oligomer method). Methods for producing fluorine-aliphatic compounds include, for example, Nobuo Ishikawa Supervision, CMC Publishing Co., Ltd. Pp. 117-118 of "Synthesis and Function of Fluorine Compounds" of the publication (1997) and Hughlikky, Milos and Pablaz, Attila. Supervision, published in American Chemistry (1995) Monograph 187, Organofluorine Compound Chemistry II, pp. 747-752. The telomerization method includes a step of radical polymerization of a fluorine-containing vinyl compound, such as tetrafluoroethylene, by synthesis of a telomer with an alkyl halide having a large chain transfer constant such as iodide as a telogen. In the synthesis according to the telomer method, a mixture of a plurality of compounds having different carbon chain lengths is obtained, and the mixture may be used as it is or may be used after purification.
[188] In the present invention, the compound of (A1) and the compound of (A3) are used in combination at the following ratio. Specifically, the compound is usually 100/0 to 10/90, preferably 90/10 to 30/70, more preferably 80/20 to 40 / in a molar ratio of the compound of (A1) / the compound of (A3). 60 is used.
[189] << (A4) Compound which generates fluorine atom-free carboxylic acid by irradiation with actinic light or radiation (hereinafter also referred to as "compound of (A4)" >>
[190] The resist composition which concerns on this invention may contain the compound of (A4) further as an acid generator.
[191] Examples of the compound of (A4) include compounds represented by the following general formulas (AI) to (AV):
[192]
[193] In the above general formula, R ₃₀₁ to R ₃₀₇ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxy group, a halogen atom or -SR ₀ . R ₀ represents a linear, branched or cyclic alkyl group or an aryl group.
[194] R _a and R _b each independently represent a hydrogen atom, a nitro group, a halogen atom, or an alkyl group which may have a substituent or an alkoxy group which may have a substituent. R _c and R _d each independently represent a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Alternatively, R _c and R _d may be bonded to each other to form an aromatic ring, a monocyclic or polycyclic aliphatic hydrocarbon ring (the ring may contain an oxygen atom or a nitrogen atom). Y ₁ and Y ₂ each represent a carbon atom, and the Y ₁ -Y ₂ bond may be a single bond or a double bond. X ⁻ represents an anion of at least one carboxylic acid compound represented by the following general formula. X ₁ and X ₂ each independently represent an ester group formed on a carboxyl group of at least one carboxylic acid compound represented by the following general formula.
[195]
[196]
[197] In the above general formula, R ₃₃₈ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms (wherein the alkyl group may contain an oxygen atom or a nitrogen atom in the chain of the alkyl group), and a straight carbon group having 2 to 20 carbon atoms. A chain, branched or cyclic alkenyl group, a straight or branched alkynyl group having 2 to 20 carbon atoms, a straight, branched or cyclic alkoxy group having 1 to 20 carbon atoms, at least a part of the hydrogen atoms of the alkyl group is a halogen atom And / or a group substituted with a hydroxy group, at least a part of a hydrogen atom of the alkenyl group is substituted with a halogen atom and / or a hydroxy group, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Substituents for the aryl group include alkyl, nitro, hydroxy, alkoxy, acyl, alkoxycarbonyl and halogen atoms.
[198] R ₃₃₉ is a single bond, a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, where the alkylene group may contain an oxygen atom or a nitrogen atom in the chain of the alkylene group, A chain, branched or cyclic alkenylene group, a group in which at least a part of the hydrogen atoms of the alkylene group is substituted with a halogen atom and / or a hydroxy group, and at least a part of the hydrogen atoms of the alkenylene group is substituted with a halogen atom and / or a hydroxy group Group or the alkoxyalkylene group having 2 to 20 carbon atoms. The plurality of R ₃₃₈ and R ₃₃₉ may be the same or different from each other.
[199] R ₃₄₀ represents a hydroxy group or a halogen atom. The plurality of R ₃₄₀ may be the same or different from each other. m, n, p and q each independently represent an integer of 0 to 3, except that m + n ≦ 5 and p + q ≦ 5. z represents 0 or 1.
[200] In General Formulas (AI) to (AV), _a linear or branched alkyl group represented by any one of R ₃₀₁ to R ₃₃₇ , R _a , R _b , R _c , R _d, and R ₀ may have a substituent. The C1-C4 thing, such as a methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, or tert- butyl group, is mentioned. Examples of the cycloalkyl group include those having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group which may have a substituent.
[201] As the alkoxy group represented by any one of R ₃₀₁ to R ₃₃₇ , R _a and R _b , a methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, which may have a substituent, The C1-C4 thing, such as a sec-butoxy group or tert-butoxy group, is mentioned.
[202] Examples of the halogen atom represented by any one of R ₃₀₁ to R ₃₃₇ , R _a , R _b , R _c and R _d include fluorine, chlorine, bromine and iodine atoms.
[203] Examples of the aryl group represented by any one of R ₀ , R _c and R _d include those having 6 to 14 carbon atoms, such as a phenyl group, tolyl group, methoxyphenyl group or naphthyl group, which may have a substituent.
[204] As the substituent of the group, preferably, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (for example, a fluorine atom, a chlorine atom or an iodine atom), a 6 to 10 carbon atoms aryl group, an alkenyl group having 2 to 6 carbon atoms, and a cyano group , Hydroxy group, carboxyl group, alkoxycarbonyl group and nitro group.
[205] Examples of the aromatic ring, monocyclic or polycyclic aliphatic hydrocarbon ring formed by combining R _c and R _d (the ring may contain a hydrogen atom or a nitrogen atom) include benzene, naphthalene, cyclohexane, norbornene and oxabicyclo Structures and the like.
[206] The sulfonium or iodonium compound represented by any one of the general formulas (AI) to (AIII) used in the present invention is represented by any one of the general formulas (C1) to (C10) as the dianion represented by X ⁻ . anion (-COO ^-) of the carboxyl group (-COOH) of at least one carboxylic acid compound is exemplified.
[207] Examples of the compound represented by any one of the general formulas (AIV) to (AV) used in the present invention include one or more carboxyl compounds represented by any one of the above general formulas (C1) to (C10) as substituent X ₁ or X ₂ . Ester group (-COO-) formed from carboxyl group (-COOH) is mentioned.
[208] Examples of the linear, branched or cyclic alkyl group having 1 to 30 carbon atoms represented by R ₃₃₈ (wherein an alkyl group may contain an oxygen atom or a nitrogen atom) include methyl, ethyl, propyl, butyl, pentyl and hex. The actual group, cyclohexyl group, dodecyl group, 1-ethoxyethyl group, adamantyl group, etc. are mentioned.
[209] Examples of the linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms include ethenyl group, propenyl group, isopropenyl group, cyclohexenyl group and the like.
[210] Examples of the linear, branched or cyclic alkynyl group having 2 to 20 carbon atoms include an ethynyl group and a propynyl group.
[211] Examples of the linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, propyloxy group, butoxy group, cyclohexyloxy group, isobutoxy group and dodecyloxy group.
[212] Examples of the substituted or unsubstituted aryl group having 6 to 20 carbon atoms include phenyl group, natryl group and anthryl group.
[213] Examples of the aryl group substituent include an alkyl group, a nitro group, a hydroxy group, an alkoxy group, an acyl group, an alkoxycarbonyl group and a halogen atom.
[214] Examples of the linear, branched or cyclic alkylene group having 1 to 20 carbon atoms represented by R ₃₃₉ (wherein the alkylene group may contain an oxygen atom or a nitrogen atom) may include a methylene group, an ethylene group, a propylene group, a butylene group, An isobutylene group, an ethoxyethylene group, a cyclohexylene group, etc. are mentioned.
[215] Examples of the linear, branched or cyclic alkenylene group having 2 to 20 carbon atoms include vinylene group and allylene group.
[216] Although the specific example of the compound of (A4) is shown below, this invention is not limited to these.
[217]
[218]
[219] In the present invention, the compound of (A1) and the compound of (A4) are used in combination at the following ratio. Specifically, the compound is usually 100/0 to 10/90, preferably 90/10 to 30/70, more preferably 80/20 to 40 / in a molar ratio of the compound of (A1) to the compound of (A4). 60 is used.
[220] << other compounds which generate acid by irradiation of actinic light or radiation >>
[221] In the present invention, in addition to the compound of (A1), the compound of (A2), the compound of (A3) and the compound of (A4), a compound which generates an acid by actinic light or radiation irradiation may be further used.
[222] The molar ratio of the compound of (A1), the compound of (A2), the compound of (A3) and the other compound that generates an acid by irradiation of actinic radiation or radiation in combination with the total amount of the compound of (A4) according to the present invention is usually 100 / 0-10 / 90, Preferably it is 98 / 2-40 / 60, More preferably, it is 95 / 5-50 / 50.
[223] The compound which generates an acid by irradiation of actinic light or radiation in combination with such an acid generator according to the present invention may be used for photoinitiators of cationic polymerization, photoinitiators of photoradical polymerization, photobleachers of pigments, photochromic agents, or microresists. It can select suitably from the compound which generate | occur | produces an acid by the well-known light used, and mixtures thereof.
[224] Specific examples of such compounds include SI Schlesinger, Photogr. Sci. Eng. Diazonium salts described in, 18, 387 (1974) and TS Bal et al., Polymer , 21, 423 (1980) and the like; Ammonium salts described in US Pat. Nos. 4,069,055, 4,069,056 and Re27,992, Japanese Patent Application Laid-Open No. 3-140140, DC Necker et al., Macromolecules , 17,2468 (1984), CS Wen et al. Teh, Proc. Conf. Rad. Curing ASIA , p.478, Tokyo. Phosphonium salts described in Oct (1988), US Pat. No. 4,069,055, US Pat. No. 4,069,056, et al., JV Crivello et al. Macromolecules , 10 (6) 1307 (1977), Chem. & Eng. News , Nov. 28, p. 31 (1988), European Patent Nos. 104,143, 339,049 and 410,201, and the iodonium salts described in Japanese Patent Laid-Open Nos. 2-150848 and 2-296514, 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. 17, 2877 (1979), European Patents 370,693, 161,811, 410,201, 339,049, 233,567, 297,443 and 297,442, and U.S. Patents 3,902,114, 4,933,377, Sulfonium salts described in US Pat. Nos. 4,760,013, 4,734,444 and 2,883,827, German Patents 2,904,626, 3,604,580, 3,604,581, JV Crivello et al., Macromolecules , 10 (6), 1307 (1977), JV Crivello et al. , J. Polymer Sci., Polymer Chem. Selenium, as described in Ed., 17, 1047 (1979), and CS Wen et al., Teh. Proc. Conf. Rad. Curing ASIA , p.478, Tokyo. Onium salts such as arsonium salts described in (Oct., 1988) and the like; U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Patent Publication No. 48-36281, Patent Publication No. 55-32070, Patent Publication No. 60-239736, Patent Publication No. 61-169835, Patent Publication Organic halogen compounds described in 61-169837, Patent Publication No. 62-58241, Patent Publication No. 62-212401, Patent Publication No. 63-70243, Patent Publication No. 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 / organohalogen compounds described in JP, 19 (12), 377 (1986) and JP-A 2-161445; 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), DHR 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. , Chem. Commun., 532 (1972), S. Hayase et al., Macromolecules , 18, 1799 (1985), E. Reichamanis et al., J. Electrochem. Soc. , Solid State Sci. Technol. , 130 (6), FM Houlihan et al., Macromolecules , 21, 2001 (1998), European Patents 290,750, 046,083, 156,535, 271,851 and 0,388,343, US 3,901,710 and 4,181,531 Photoacid generators having o-nitrobenzyl-type protecting groups described in Japanese Patent Application Laid-Open No. 60-198538 and Japanese Patent Laid-Open No. 53-133022; 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., PolymerPreprints, Japan , 37 (3), European Patents 199,672, 084,515, 044,115, 618,564 and 101,122, Compounds that generate sulfonic acid by photolysis represented by iminosulfonates described in US Pat. ; And disulfone compounds described in Japanese Patent Application Laid-Open No. 61-166544 and the like.
[225] In addition, polymer compounds, such as 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 Publication No. 63-26653, Japanese Patent Publication No. 55-164824, Japanese Patent Publication No. 62-69263, Japanese Patent Publication No. 63- The compounds described in 146038, Patent Publication No. 63-163452, Patent Publication No. 62-153853, Patent Publication No. 63-146029 and the like can be used.
[226] See also 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 also be used a compound which generates an acid by exposure.
[227] << A polymer which is insoluble or poorly soluble in an aqueous alkali solution, but soluble in an aqueous alkali solution by the action of an acid (hereinafter also referred to as "(BP) component") >>
[228] Examples of the (BP) component used in the positive resist composition of the present invention include resins having a group capable of being decomposed by an acid in the main chain or the side chain, or both the main chain and the side chain. More preferred are resins having groups degradable with acid in their side chains.
[229] Preferred examples of the group decomposable to an acid include groups represented by -COOA ^O and groups represented by -OB ^O.
[230] Wherein A ^O represents -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), -Si (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -C (R ⁰⁴ ) (R ⁰⁵ ) -OR ⁰⁶ Indicates. B ^O represents A ^O or —CO—OA ^O. R ^O1 to R ^O6 may be the same or different, and each may have a substituent, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl which may have a substituent Group.
[231] Preferable examples of the acid decomposable group include 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 agent Tertiary alkyl carbonate groups and the like. Further preferred examples include tertiary alkyl ester groups, tertiary alkyl carbonate groups, cumyl ester groups, acetal groups, tetrahydropyranyl ether groups and the like. In particular, tert-butoxycarbonyl group is preferable.
[232] In the case where an acid decomposable group is bonded as a side chain, the mother resin is an alkali-soluble resin having an -OH group or a -COOH group in the side chain. As a base resin, alkali-soluble resin mentioned later can be mentioned.
[233] The alkali dissolution rate of the alkali-soluble resin is preferably 170 angstroms / sec or more, more preferably 330 A / sec or more, as measured by 0.261 N tetramethylammonium hydroxide (TMAH) at 23 ° C.
[234] In view of the alkali dissolution rate, preferred alkali-soluble resins include copolymers of poly (o-, m- or p-hydroxystyrene) and o-, m- or p-hydroxystyrene, hydrogenated poly (hydroxystyrene) , Halogen- or alkyl-substituted poly (hydroxystyrene), some O-alkylates or O-acylates of poly (hydroxystyrene), styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers And hydrogenated novolac resins.
[235] Resin which has a structural unit containing group represented by said general formula (X1) or (X2) is also called (BP) component.
[236] In general formula (XI), R <_1b> and R <_2b> may be same or different, and each represents a hydrogen atom or an alkyl group. R _3b and R _4b may be the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, or a cycloalkyl group which may have a substituent. R <_5b> represents the alkyl group which may have a substituent, the cycloalkyl group which may have a substituent, the aryl group which may have a substituent, or the aralkyl group which may have a substituent. m represents the integer of 0-20, n represents the integer of 0-5.
[237] In general formula (X2), R <_6b> and R <_7b> may be same or different, and each represents a hydrogen atom or an alkyl group. W represents a divalent organic group. R <_8b> represents the alkyl group which may have a substituent, the cycloalkyl group which may have a substituent, the aryl group which may have a substituent, or the aralkyl group which may have a substituent.
[238] The alkyl group represented by any one of R ⁰¹ to R ⁰⁶ and R _1b , R _5b and R _8b may be a linear or branched alkyl group, preferably a methyl group, an ethyl group, a propyl group or an n-butyl group which may have a substituent. The C1-C4 thing, such as a sec-butyl group or a tert- butyl group, is mentioned.
[239] The cycloalkyl group represented by any one of R ⁰¹ to R ⁰⁶ and R _3b to R _8b preferably includes 3 to 8 carbon atoms such as a cyclopropyl, cyclopentyl group or cyclohexyl group which may have a substituent.
[240] The alkenyl group represented by any one of R ⁰¹ to R ⁰⁶ preferably includes 2 to 8 carbon atoms such as vinyl group, allyl group, butenyl group or cyclohexenyl group which may have a substituent.
[241] Aralkyl groups represented by any one of R ⁰¹ to R ⁰⁶ and R _5b , R _5b and R _8b are preferably those having 7 to 12 carbon atoms such as a benzyl group, phenethyl group or naphthylmethyl group which may have a substituent. do.
[242] As the aryl group represented by any one of R ⁰¹ to R ⁰⁶ and R _5b and R _8b , those having 6 to 15 carbon atoms, such as a phenyl group, tolyl group, naphthyl group or atryl group, which may preferably have a substituent are listed.
[243] Substituents of the alkyl group, cycloalkyl group, alkenyl group, aralkyl group or aryl group include carboxyl, acyloxy group, cyano group, aryl group, alkyl group, cycloalkyl group, halogen atom, hydroxy group, alkoxy group, acetylamido group and alkoxy Carbonyl group, acyl group, etc. are mentioned.
[244] The divalent organic group represented by W is preferably a linear, branched or cyclic alkylene group which may have a substituent, an arylene group which may have a substituent, a heteroarylene group which may have a substituent, or an aral which may have a substituent. Killene groups, -S-, -C (= 0)-, -N (R _4c )-, -SO-, -SO _2- , -CO _2- , -N (R _4c ) SO ₂ -and of these groups The divalent groups formed by combining two or more are listed. R _4c represents a hydrogen atom or an alkyl group (which means the same as the alkyl group represented by R ⁰¹ ).
[245] The (BP) component used in the present invention is an alkali-soluble resin and an acid, as described in European Patent 254,853, Japanese Patent Application Laid-Open No. 2-25850, Japanese Patent Application Laid-Open No. 3-223860 and Japanese Patent Application Laid-Open No. 4-251259. It can be obtained by reacting a precursor of a decomposable group or copolymerizing various monomers with a monomer forming an alkali-soluble resin having a group decomposable with an acid.
[246] Although the specific example of component (BP) used for this invention is shown below, this invention is not limited to these.
[247]
[248]
[249]
[250]
[251]
[252]
[253]
[254] The content of acid decomposable groups in the resin is represented by the formula B / (B + S), where B represents the number of decomposable groups with acid, and S is an alkali-soluble group that is not protected by an acid decomposable group. Indicates the number of. The content rate is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40. When the content rate exceeds 0.7, it is disadvantageous from the viewpoint of film shrinkage after PEB, poor adhesion to the substrate, or scum generation. On the other hand, when the content rate is less than 0.01, a remarkable standing wave effect may appear on the pattern side wall, which is not preferable.
[255] The weight average molecular weight (Mw) of the component (BP) is preferably in the range of 2,000 to 200,000. If it is less than 2,000, the film thickness of the unexposed part after development is large, whereas if it exceeds 200,000, the dissolution rate with respect to alkali of alkali-soluble resin itself will fall, and sensitivity will fall. The weight average molecular weight is more preferably in the range of 5,000 to 100,000, still more preferably in the range of 8,000 to 50,000.
[256] The molecular weight distribution (Mw / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 2.0, particularly preferably 1.0 to 1.6.
[257] The weight average molecular weight is measured by gel permeation chromatography and expressed using polystyrene conversion value.
[258] You may use the polymer of 2 or more types of component (BP) for the positive resist composition of this invention.
[259] The amount of the polymer of the component (BP) is usually 70 to 98% by weight, preferably 80 to 96% by weight based on the solids of the positive resist composition of the present invention.
[260] << (BN) alkali-soluble resin (Hereinafter, it is also called "(BN) component" or "resin of (BN).") >>
[261] Alkali-soluble resins used in the negative resist compositions of the present invention include polyvinylphenols and copolymers having structural units derived from, for example, phenol novolak resins, polyvinylphenol resins, vinylphenols, and the like, described so far in negative chemically amplified resists. The polymer which has a phenol skeleton, such as resin obtained by protecting or modifying a part of resin, is mentioned.
[262] As resin of (BN) component, resin containing the repeating unit represented by the following general formula (a) is mentioned preferably:
[263]
[264] In formula (a), R <_1> represents a hydrogen atom, a halogen atom, a cyano group, the alkyl group which may have a substituent, or the haloalkyl group which may have a substituent. R <_2> represents a hydrogen atom, the alkyl group which may have a substituent, the cycloalkyl group which may have a substituent, the aryl group which may have a substituent, the aralkyl group which may have a substituent, or the acyl group which may have a substituent. R ₃ and R ₄ may be the same or different and each may have a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. The aryl group which may have an aralkyl group or a substituent is shown.
[265] A represents a single bond, which may have a substituent which may have a good alkylene group, the substituent may have a good alkenylene group, the substituent may have a good cycloalkylene group, an optionally substituted aryl group, -O-, -SO ₂ -, -O -CO-R _5- , -CO-OR ₆ -or -CO-N (R ₇ ) -R _8- .
[266] R <_5> , R <_6> and R <_8> may be same or different, and each may have a single bond, the alkylene group which may have a substituent, the alkenylene group which may have a substituent, the cycloalkylene group which may have a substituent, and the substituent may have The arylene group, the alkylene group, the alkenylene group, the cycloalkylene group, or the arylene group represents a divalent group formed by bonding one or more selected from ether structure, ester structure, amido structure, urethane structure or ureido structure.
[267] R <_7> represents a hydrogen atom, the alkyl group which may have a substituent, the cycloalkyl group which may have a substituent, the aralkyl group which may have a substituent, or the aryl group which may have a substituent.
[268] n represents the integer of 1-3. Alternatively, a plurality of R ₂ , R ₂ and R ₃ , or R ₂ and R ₄ may be bonded to each other to form a ring.
[269] The phenol resin containing the repeating structural unit represented by the said general formula (a) is used more preferable.
[270] The alkyl group represented by any one of R ₁ to R ₄ and R ₇ is preferably an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group and octyl group can be enumerated. The cycloalkyl group represented by any one of R ₂ to R ₄ and R ₇ may be monocyclic or polycyclic. Examples of the monocyclic cycloalkyl group include those having 3 to 8 carbon atoms, specifically cyclopropyl group, cyclopentyl group and cyclohexyl group. As a polycyclic cycloalkyl group, an adamantyl group, norbornyl group, isobornyl group, dicyclopentyl group, (alpha)-pineneyl group, a tricyclo decanyl group, etc. are mentioned preferably, for example.
[271] As an alkenyl group represented by either of R <_3> and R <_4> , a C2-C8 alkenyl group specifically, vinyl, allyl group, butenyl group, and cyclohexenyl group are mentioned preferably.
[272] The aryl group represented by any one of R ₂ to R ₄ and R ₇ is an aryl group having 6 to 15 carbon atoms, specifically, a phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group and anthryl Group etc. can be mentioned preferably.
[273] As the aralkyl group represented by any one of R ₂ to R ₄ and R ₇ , examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, and the like.
[274] As the haloalkyl group represented by R ₁ , specifically, a haloalkyl group having 1 to 4 carbon atoms may specifically include chloromethyl group, chloroethyl group, chloropropyl group, chlorobutyl group, bromomethyl group, bromoethyl group, and the like. .
[275] As an acyl group represented by R <_2> , a C1-C10 acyl group specifically, a formyl group, an acetyl group, a propanoyl group, butanoyl group, pivaloyl group, a benzoyl group, etc. can be mentioned preferably.
[276] The alkylene group represented by any one of A, R ₅ , R ₆ and R ₈ may have a substituent, for example, having 1 to 8 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group Alkylene groups may be preferably listed.
[277] Alkenylene groups represented by any one of A, R ₅ , R ₆ and R ₈ may preferably include alkenylene groups having 2 to 6 carbon atoms, such as an ethenylene group, a propenylene group and a butenylene group, which may have a substituent. Can be.
[278] The cycloalkylene group represented by any one of A, R ₅ , R ₆ and R ₈ may preferably include a cycloalkylene group having 5 to 8 carbon atoms, such as a cyclopentylene group and a cyclohexylene group, which may have a substituent. have.
[279] As the arylene group represented by any one of A, R ₅ , R _6, and R ₈ , arylene groups having 6 to 12 carbon atoms, such as a phenylene group, tolylene group, and naphthylene group, which may have a substituent, are preferably listed. .
[280] Examples of the substituent of the group include an active hydrogen such as an amino group, an amido group, a ureido group, a urethane group, a hydroxy group or a carboxyl group, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an alkoxy group (e.g. , Methoxy group, ethoxy group, propoxy group or butoxy group), thioether group, acyl group (e.g., acetyl group, propanoyl group or benzoyl group), acyloxy group (e.g. acetoxy group, propanoyloxy group or Benzoyloxy group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group or propoxycarbonyl group), cyano group, nitro group, etc. are mentioned. In particular, the group which has active hydrogen, such as an amino group, a hydroxyl group, or a carboxyl group, is preferable.
[281] As a ring formed by combining a plurality of R ₂ , R ₂ and R ₃ , or R ₂ and R ₄ with each other, a 4 to 7 membered ring containing an oxygen atom such as a benzofuran ring, a benzodioxolol ring or a benzopyran ring is used. Listed.
[282] The resin of (BN) used in the present invention may be a resin composed of a repeating structural unit represented by the general formula (a) alone. For the purpose of further improving the performance of the negative resist composition of the present invention, the resin of (BN) may be a copolymer containing a repeating structural unit represented by the general formula (a) and a repeating unit derived from at least one other polymerizable monomer. good.
[283] Copolymerizable monomers that can be used in the present invention include acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and crotonic acid esters. Listed are compounds having one addition polymerizable unsaturated bond selected.
[284] Among the monomers, monomers which improve solubility in alkali, such as monomers having a carboxyl group such as carboxystyrene, N- (carboxyphenyl) acrylamide or N- (carboxyphenyl) methacrylamide, or maleimide are used as copolymerizable components. desirable.
[285] The content of other monomers in the resin is preferably 50 mol% or less, more preferably 30 mol% or less, based on the total repeating units of the resin.
[286] Although the specific example of resin which has a repeating structural unit represented by general formula (a) below is shown, this invention is not limited to these.
[287]
[288]
[289]
[290]
[291]
[292]
[293]
[294]
[295]
[296]
[297]
[298] In the above embodiment, n represents a positive integer. Each of x, y and z represents the molar ratio of each repeating unit. In the resin composed of two components, x and y are used in the range of x = 10 to 95, y = 5 to 90, preferably x = 40 to 90 and y = 10 to 60. In the resin consisting of three components, x, y and z are x = 10 to 90, y = 5 to 85, z = 5 to 85, preferably x = 40 to 80, y = 10 to 50, z = 10 Used in the range of ~ 50.
[299] As for the molecular weight of resin of (BN), Preferably resin which has a repeating structural unit represented by General formula (a), 1,000-200,000 are preferable at a weight average molecular weight, and 3,000-50,000 are more preferable. The molecular weight distribution of the resin is 1 to 10, preferably 1 to 3, more preferably 1 to 1.5. The smaller the molecular weight distribution, the higher the resolution, the better the resist profile, the smoother the sidewalls of the resist pattern, and the better the edge roughness of the resist pattern.
[300] Content of the repeating unit represented by general formula (a) is 5-100 mol% with respect to alkali-soluble resin, Preferably it is 10-90 mol%.
[301] Alkali-soluble resins containing the structural unit represented by the general formula (a) used in the present invention are described in Macromolecules , 28 (11), 3787-3789 (1995), Polym. Bull. (Berlin) , 24 (4), 385-389 (1990) and Unexamined-Japanese-Patent No. 8-286375 can be synthesize | combined. Specifically, desired alkali-soluble resin can be obtained by radical polymerization method or living anion polymerization method.
[302] The said resin may be used independently and may be used as a mixture of 2 or more types.
[303] The polymerization average molecular weight is expressed as a polystyrene value of a value obtained by gel permeation chromatography.
[304] As for the alkali dissolution rate of alkali-soluble resin, when measured by 0.261N tetramethylammonium hydroxide (TMAH) at 23 degreeC, it is preferable that it is 20 angstroms / sec or more, Preferably it is 200 angstroms / sec or more.
[305] In this invention, alkali-soluble resin which has a repeating unit represented by general formula (a) may be used independently, or may be used together with other alkali-soluble resin. In the resin ratio, the usage-amount of other alkali-soluble resin can be used up to 100 weight part with respect to 100 weight part of alkali-soluble resin which has a repeating unit represented by General formula (a). Examples of other alkali-soluble resins used in combination include novolak resins, hydrogenated novolak resins, acetone-pyrogallol resins, styrene-maleic anhydride copolymers, carboxyl group-containing methacrylic resins and derivatives thereof, but the present invention includes these It is not limited to.
[306] The usage-amount of resin of (BN) is 30 to 95 weight% with respect to the total solid of a resist composition, Preferably it is 40 to 90 weight%, More preferably, it is used in the range of 50 to 80% weight%.
[307] << crosslinking agent which crosslinks by action of (C) acid (hereinafter also referred to as "(C) component" or "crosslinking agent of (C)" >>
[308] The crosslinking agent (hereinafter also referred to as “acid crosslinking agent” or simply “crosslinking agent”) which is crosslinked by the action of the acid used in the negative resist composition of the present invention is an alkali-soluble resin in the presence of an acid such as an acid generated by irradiation. It is a compound which can be crosslinked. As a crosslinking agent of (C), the compound containing one or more substituents (henceforth "crosslinkable substituent") which have crosslinking reactivity with alkali-soluble resin is mentioned, for example.
[309] As a specific example of a crosslinkable substituent,
[310] (i) hydroxyalkyl groups or derivatives thereof such as hydroxyalkyl groups, alkoxyalkyl groups or acetoxyalkyl groups;
[311] (ii) carbonyl groups or derivatives thereof such as formyl group or carboxyalkyl group;
[312] (iii) a substituent having a nitrogen-containing group such as dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, dietyrolaminomethyl group, or morpholinomethyl group;
[313] (iv) a substituent having a glycidyl group such as a glycidyl ether group, a glycidyl ester group or a glycidylamino group;
[314] (v) aromatic derivatives such as aralkyloxyalkyl groups such as benzyloxymethyl group or benzoyloxymethyl group or arylcarbonyloxyalkyl groups;
[315] (vi) Substituents which have a polymerizable multiple bond, such as a vinyl group or an isopropenyl group, are mentioned.
[316] As a crosslinkable substituent in the crosslinking agent of (C) which concerns on this invention, a hydroxyalkyl group and an alkoxyalkyl group are preferable, for example, and an alkoxymethyl group is more preferable.
[317] As a crosslinking agent containing a crosslinkable substituent, for example
[318] (i) Methirol group-containing compounds such as metharol group-containing melamine compounds, methirol group-containing benzoguanamine compounds, methirol group-containing urea compounds, methirol group-containing glycoluril compounds or methirol group-containing phenol compounds ;
[319] (ii) alkoxyalkyl group-containing compounds such as alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycoluril compounds or alkoxyalkyl group-containing phenol compounds;
[320] (iii) carboxymethyl group-containing compounds such as a carboxymethyl group-containing melamine compound, a carboxymethyl group-containing benzoguanamine compound, a carboxymethyl group-containing urea compound, a carboxymethyl group-containing glycoluril compound, or a carboxymethyl group-containing phenol compound; And
[321] (iv) epoxy compounds such as bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolac resin epoxy compounds, resol resin epoxy compounds or poly (hydroxystyrene) epoxy compounds.
[322] Moreover, resin which introduce | transduced the said crosslinkable substituent into the acidic functional group of alkali-soluble resin, and provided the property of a crosslinking agent can be used as a crosslinking agent. In such a case, the introduction ratio of the crosslinkable substituent is controlled in the range of usually 5 to 60 mol%, preferably 10 to 50 mol%, more preferably 15 to 40 mol%, based on the total acidic functional groups in the alkali-soluble resin. . When the introduction ratio of the crosslinkable substituent is less than 5 mol%, sufficient crosslinking reaction hardly occurs, and as a result, problems such as a decrease in film thickness, swelling of the pattern, and meandering are likely to occur. On the other hand, when ratio exceeds 60 mol%, alkali solubility of alkali-soluble resin falls and there exists a tendency for developability to deteriorate.
[323] As a crosslinking agent of (C) used for the negative resist composition of this invention, an alkoxy methylated urea compound or its polymer, and an alkoxy methylated glycoluril compound or its polymer are preferable.
[324] As a particularly preferable crosslinking agent (C1), the compound and the alkoxy methylation melamine compound represented by either of the following general formula (2)-(4) can be mentioned.
[325] R _5b in General Formulas (2) to (4) is each independently a hydrogen atom, an alkyl group (preferably one having 1 to 5 carbon atoms, more preferably one having 1 to 3 carbon atoms, such as a methyl group, an ethyl group or a propyl). Group) or an acyl group (preferably a C2-C6 thing, More preferably, a C2-C4 thing, such as an acetyl group or a propionyl group).
[326] R _6b to R _9b in Formula (2) each independently represent a hydrogen atom, a hydroxy group, an alkyl group (preferably one having 1 to 5 carbon atoms, more preferably one having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, or Propyl group) or an alkoxy group (preferably a C1-C5 thing, more preferably a C1-C3 thing, such as a methoxy group, an ethoxy group, or a propoxy group).
[327] X in General formula (2) represents a single bond, a methylene group, or an oxygen atom. X is preferably a single bond or a methylene group.
[328] The groups may further have a substituent such as an alkyl group such as methyl group or ethyl group, alkoxy group such as methoxy group or ethoxy group, hydroxy group or halogen atom.
[329] Although the specific example of the compound and alkoxy methylation melamine compound represented by General formula (2)-(4) below is shown, this invention is not limited to these.
[330]
[331]
[332] The crosslinking agent condensates a urea compound or a glycoluril compound with formalin to introduce a metyrol group, etherifies the methirol group with a lower alcohol such as methyl alcohol, ethyl alcohol, propyl alcohol or butyl alcohol, and cools the reaction solution. And then recover the precipitated compound or resin. In addition, the said crosslinking agent can use a commercial item, such as Cymel (made by Mitsui Cyanamide) or Nikarad (made by Sanwa Chemical).
[333] Particularly preferred (C2) crosslinking agents include compounds selected from phenol derivatives having 1 to 6 benzene rings per molecule and having at least two hydroxymethyl groups and / or alkoxymethyl groups bonded to any one of the benzene rings. .
[334] It has a molecular weight of 1,500 or less, has 1 to 6 benzene rings per molecule, and two or more groups selected from hydroxymethyl group and alkoxymethyl group are intensively bound to one benzene ring or are dispersed and bound to a benzene ring. Phenol derivatives are preferably used.
[335] As the alkoxy methyl group bonded to the benzene ring, an alkoxy methyl group having 6 or less carbon atoms is preferable. Specifically, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, sec-butoxymethyl group, and tert-butoxymethyl group are mentioned. Moreover, the alkoxy substituted alkoxy group, such as 2-methoxyethoxy group or 2-methoxy-1-propoxy group, is preferable.
[336] Among the phenol derivatives, particularly preferred ones are shown below.
[337]
[338]
[339]
[340]
[341]
[342]
[343] In the formula, L ¹ to L ⁸ may be the same or different and each represents a hydroxymethyl group, methoxymethyl group or ethoxymethyl group.
[344] Phenol derivatives having a hydroxymethyl group include a base phenol containing a corresponding phenolic compound (all L ¹ to L ⁸ in the compound represented by the above general formula represents a hydrogen atom) containing no hydroxymethyl group and formaldehyde. It can obtain by making it react under. At this time, in order to prevent the occurrence of resination or gelation, it is preferable to perform the reaction at a temperature of 60 ° C or lower. Specifically, it can synthesize | combine by the method described in Unexamined-Japanese-Patent No. 6-282067, Unexamined-Japanese-Patent No. 7-64285, etc.
[345] Phenol derivatives having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, in order to prevent resination or gelation, it is preferable to perform reaction at the temperature of 100 degrees C or less. Specifically, the phenol derivative can be synthesized by the method described in European Patent No. 632,003.
[346] Phenol derivatives having a hydroxymethyl group or an alkoxymethyl group are preferred from the viewpoint of storage stability, and phenol derivatives having an alkoxymethyl group are particularly preferred from the viewpoint of storage stability. The phenol derivative which has two or more groups of hydroxymethyl group and an alkoxymethyl group in the whole, and these groups are intensively couple | bonded with one benzene ring, or dispersely couple | bonded with the benzene ring may be used independently, or 2 or more types You may use in combination.
[347] The crosslinking agent is used in the range of 3 to 70% by weight, preferably 5 to 50% by weight, based on the total solids of the negative resist composition. If the addition amount of the crosslinking agent is less than 3% by weight, the residual film ratio will be lowered. On the other hand, if the amount of the crosslinking agent is more than 70% by weight, the resolution will be lowered and it is more disadvantageous in terms of storage stability of the resist solution.
[348] You may use combining the compound which has said N-hydroxymethyl group, N-alkoxymethyl group, or N-acyloxymethyl group, and the phenol derivative which has a hydroxymethyl group or an alkoxymethyl group.
[349] << other components used for the resist composition of this invention >>
[350] The resist composition of this invention may further contain other components, such as an organic basic compound, dye, and surfactant as needed.
[351] <Organic basic compound>
[352] Preferred organobasic compounds that can be used in the present invention are compounds which are more basic than phenol. Among these compounds, nitrogen-containing basic compounds are preferably used.
[353] As a preferable chemical environment of a nitrogen-containing basic compound, the structure represented by the following general formula (A), (B), (C), (C) or (E) can be mentioned.
[354]
[355] In the formula, R²⁵⁰, R²⁵¹And R²⁵²May be the same or different and each represents a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an aminoalkyl group of 1 to 6 carbon atoms, a hydroxyalkyl group of 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, Or R²⁵¹And R²⁵²These may combine with each other and form a ring.
[356] R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms.
[357] More preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments per molecule. Particularly preferred compounds are compounds containing both cyclic structures containing substituted or unsubstituted amino groups and nitrogen atoms, and compounds containing alkylamino groups.
[358] Preferred embodiments of the nitrogen-containing basic compound are substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted Sol, substituted or unsubstituted imidazole, substituted or 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 piperazine, substituted or unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, and the like. Preferred substituents include amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxy group and cyano group. .
[359] Particularly preferred compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 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) piperi Dine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole , 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (amino Methyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine and N- (2 -Aminoethyl) morpholine, etc. can be mentioned. However, the present invention is not limited to these.
[360] The said organic basic compound may be used independently, or may be used in combination of 2 or more type.
[361] In the usage ratio of the acid generator and the organic basic compound used in the positive resist composition, the molar ratio of (acid generator) / (organic basic compound) is preferably 2.5 to 300. If the molar ratio is less than 2.5, the sensitivity may decrease, and the resolution may decrease. On the other hand, when the molar ratio exceeds 300, the size of the resist pattern may change with the passage of time from exposure to heat treatment, and resolution may also decrease. The molar ratio of (acid generator) / (organic basic compound) is preferably 5.0 to 200, and more preferably 7.0 to 150.
[362] The amount of the organic basic compound used in the negative resist composition is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight based on the total solids of the resist composition. If the amount of the organic basic compound is less than 0.001% by weight, the effect of adding the organic basic compound is not obtained. On the other hand, when it exceeds 10 weight%, there exists a tendency for the fall of a sensitivity and the deterioration of the developability of an unexposed part to appear.
[363] <Dye>
[364] Suitable dyes include oily dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (These dyes are Orient Chemical) Manufactured by Industiris Co.), crystal violet (CI 42555), methyl violet (CI 42535), rhodamine B (CI 45170B), malachite green (CI 42000) and methylene blue (CI 52015).
[365] <Solvent>
[366] The resist composition of this invention is melt | dissolved in the solvent which can melt | dissolve the said component, and is apply | coated to a support body. Preferred solvents to be used include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy Ethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxy propionate, ethyl ethoxy propionate, Methylpyruvate, ethylpyruvate, propylpyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like. This solvent may be used independently, or may be used in combination of 2 or more type.
[367] Particularly preferred solvents include propylene glycol monomethyl ether acetate and mixed solvents of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether.
[368] <Surfactant>
[369] In the resist composition of the present invention, fluorine-based and / or silicon-based surfactants may be preferably combined.
[370] The resist composition of the present invention preferably contains at least one of a fluorine-based surfactant, a silicone-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom.
[371] Combining the surfactant with the above components in the resist composition of the present invention is particularly effective in forming finer linewidth patterns, and further improves development defects.
[372] As said surfactant, For example, Unexamined-Japanese-Patent No. 62-36663, 61-226746, 61-226745, 62-170950, 63-34540, Unexamined-Japanese-Patent No. 7-230165, patent publication And those described in Japanese Patent Application Laid-Open No. Hei 8-62834, Hei 9-54432 and Hei 9-5988. Moreover, you may use the following commercially available surfactant.
[373] Commercially available surfactants to be used include, for example, F-Top EF301, EF303 (manufactured by Shin Akita Kasei Co., Ltd.), Florad FC430, FC431 (manufactured by Sumimoto 3M Co., Ltd.), Mecfac F171, F173, F176, F189, R08 (Dinipon Ink & Chemical) Products), and fluorine-based surfactants or silicone-based surfactants such as Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass) and Troysol S-366 (manufactured by Troy Chemical) Can be. In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Industries Co., Ltd.) can also be used as the silicone-based surfactant.
[374] The usage-amount of surfactant is 0.001-2 weight% normally with respect to the total solid of a resist composition, Preferably it is 0.01-1 weight%.
[375] Surfactant may be used independently, or may be used in combination of 2 or more type.
[376] As surfactant other than the above, specifically, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, or polyoxyethylene oleyl ether, polyoxyethylene octyl Polyoxyethylene alkylaryl ethers such as phenol ether or polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymer, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan mono Sorbitan fatty acid esters such as oleate, sorbitan trioleate or sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxy Ethylene sorbitan trioleate or poly ox And nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as cyethylene sorbitan tristearate.
[377] The compounding quantity of such other surfactant is 2 weight part or less normally, Preferably it is 1 weight part or less with respect to 100 weight part of total solids of the resist composition which concerns on this invention.
[378] The pattern formation process onto the resist film in the manufacture of the precision integrated circuit device may be carried out by the appropriate method of applying the resist composition of the present invention onto a substrate (for example, a silicon / silicon dioxide film or a transparent substrate such as a glass substrate or an ITO substrate) For example, a spinner, a coater, or the like is applied in a suitable method, and the coating layer is exposed through a predetermined mask, followed by heating, developing, rinsing, and drying to form a good resist pattern.
[379] Examples of the exposure light used include electron beams, EUV (extreme ultraviolet rays), and X-rays.
[380] In this invention, you may use a well-known inorganic or organic antireflection film as needed. In addition, an antireflection film may be coated on the resist layer.
[381] Suitable examples of the antireflection film used as the lower layer of the resist layer include inorganic film types such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon or amorphous silicon, and organic film types made of light absorbers and polymer materials. The former requires a device such as a vacuum deposition apparatus, a CVD apparatus or a sputtering apparatus to form an antireflection film. Examples of the organic antireflection film include a film containing a condensate of a diphenylamine derivative described in JP-A-7-69611 and a formaldehyde-modified melamine resin, an alkali-soluble resin and a light absorber, and maleic anhydride described in US Patent No. 5,294,680. Membrane containing reaction product of copolymer and diamine light absorber, Membrane containing resin binder as described in Japanese Patent Application Laid-Open No. 6-118631 and methirolmelamine-based thermal crosslinking agent, Carboxylic as described in Japanese Patent Application Laid-Open No. 6-118656 A film containing an acrylic resin having an acid group, an epoxy group and a light absorber in the same molecule, a film containing methirolmelamine and a benzophenone light absorber described in JP-A-8-87115, and JP-A-8-179509 The film | membrane containing the polyvinyl alcohol resin to which the low molecular weight absorber of Claim was added can be mentioned.
[382] Commercially available organic antireflective coatings include DUV-30 series and DUV-40 series (manufactured by Brewer Science, Inc.), and AR-2, AR-3, and AR-5 (manufactured by Shipley, Inc.) as organic antireflective layers. Can be.
[383] As a developing solution of the resist composition of this invention, For example, Inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, or ammonia water; Primary amines such as ethylamine or n-propylamine; Secondary amines such as diethylamine or di-n-butylamine; Tertiary amines such as triethylamine or methyldiethylamine; Alcohol amines such as dimethylethanolamine or triethanolamine; Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline; And alkaline aqueous solutions such as cyclic amines such as pyrrole or piperidine.
[384] Of the above developing solutions, a developing solution containing a quaternary ammonium salt is preferable, and a developing solution containing tetramethylammonium hydroxide or choline is more preferable.
[385] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
[386] Experimental Example: Measurement of Reduction Potential
[387] The reduction potential of the acid generator was measured by cyclic voltammetry. Specifically, each acid generator shown in Table 1 was dissolved in acetonitrile distilled under an argon atmosphere to prepare 1 mM of the acid generator solution for measurement. 0.1 mM of tetrabutylammonium perchlorate solution was used as a supporting electrolyte. As the electrode, MP-2 (manufactured by Yanako LID), C-2U (manufactured by Yanako LID) and Ag / AgCl were used as the working electrode, the counter electrode and the reference electrode, respectively. The measurement was performed at 23.5 degreeC. The scanning speed was 50 mV / cm 2. Since the acid generator was decomposed by reduction and the reaction was irreversible, only a reducing peak was observed.
[388]
[389] (1) Synthesis of Compound of (A1)
[390] 10 g of dibenzothiophene was dissolved in 200 ml of benzene, and the obtained solution was cooled at 5 ° C, and 40 ml of concentrated sulfuric acid was added dropwise thereto while stirring. The solution was raised to room temperature and stirred for 48 hours. The reaction mixture was poured onto ice, and the aqueous layers were extracted three times with 1 L of ether. The aqueous layer was cooled at 0 ° C, and an aqueous solution containing 16.95 g of trimethylammonium 3,5-ditrifluoromethylbenzenesulfonate was added dropwise to 1 L of water, followed by stirring at 0 ° C for 2 hours. The reaction mixture was extracted three times with 1 L of chloroform. The organic layer was washed with water and concentrated to obtain 2.5 g of an oil of Compound A1-1.
[391] Compounds A1-2 to A1-15 can also be synthesized in the same manner.
[392] (2) Synthesis of Compound of (A2)
[393] (2-1) Synthesis of Tetramethylammonium Pentafluorobenzenesulfonate
[394] 25 g of pentafluorobenzenesulfonyl chloride was dissolved in 100 ml of methanol under ice cooling, and 100 g of 25% tetramethylammonium hydroxide aqueous solution was slowly added thereto. This mixture was stirred at room temperature for 3 hours to obtain a tetramethylammonium pentafluorobenzenesulfonate solution. This solution was used for salt exchange with sulfonium salts or iodonium salts.
[395] (2-2) Synthesis of Triphenylsulfonium Pentafluorobenzenesulfonate
[396] 50 g of diphenyl sulfoxide was dissolved in 800 ml of benzene, and 200 g of aluminum chloride was added, and the mixture was refluxed for 24 hours. The reaction solution was slowly poured into 2 L of ice water, 400 ml of concentrated hydrochloric acid was added, and the mixture was heated at 70 ° C. for 10 minutes. The aqueous solution was washed with 500 ml of ethyl acetate and filtered, and then thereto was added a solution containing 200 g of ammonium iodide dissolved in 400 ml of water. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate and dried to obtain 70 g of triphenylsulfonium iodide.
[397] After dissolving 30.5 g of triphenylsulfonium iodide in 1,000 ml of methanol, 19.1 g of silver oxide was added to this solution, and the mixture was stirred at room temperature for 4 hours. The reaction solution was filtered, and an excess of the tetramethylammonium pentafluorobenzenesulfonate solution was added to the filtrate. The reaction solution was concentrated, the resulting residue was dissolved in 500 ml of dichloromethane, washed with 5% aqueous tetramethylammonium hydroxide solution, and washed with water. The organic layer was dried over anhydrous sodium sulfate and concentrated to give triphenylsulfonium pentafluorobenzenesulfonate of compound (I-1).
[398] (2-3) Synthesis of di (4-tert-amylphenyl) iodonium pentafluorobenzenesulfonate
[399] To a mixture of 60 g tert-amylbenzene, 39.5 g of potassium iodide, 81 g of acetic anhydride, and 170 ml of dichloromethane, 66.8 g of concentrated sulfuric acid was slowly added dropwise under ice-cooling. After 2 hours of stirring under ice cooling, the mixture was further stirred at room temperature for 10 hours. 500 ml of water was added to this reaction liquid under ice cooling, and the obtained liquid mixture was extracted with dichloromethane. The organic layer was washed with an aqueous sodium hydrogen carbonate solution, washed with water, and concentrated to give di (4-tert-amylphenyl) iodium sulfate. The obtained sulfate was added to the said tetramethylammonium pentafluorobenzenesulfonate aqueous solution in excess. 500 ml of water was added to the solution, followed by extraction with dichloromethane. The organic layer was washed with 5% aqueous tetramethylammonium hydroxide solution, washed with water, and concentrated to give di (4-tert-amylphenyl) iodonium pentafluorobenzenesulfonate of compound (III-1).
[400] (3) Synthesis of Acid Degradable Resin of (BP)
[401] (3-1) Synthesis of Resin (B-21)
[402] 32.4 g (0.2 mol) of p-acetoxystyrene and 7.01 g (0.07 mol) of tert-butyl methacrylate were dissolved in 120 ml of butyl acetate. 0.033 g of azobisisobutyronitrile (AIBN) was added to this solution at 80 ° C three times at 2.5 hour intervals, and the mixture was further stirred for 5 hours to carry out a polymerization reaction. The obtained reaction solution was poured into 1,200 ml of hexane to precipitate white resin. The obtained resin was dried and then dissolved in 200 ml of methanol.
[403] An aqueous solution prepared by dissolving 7.7 g (0.19 mol) of sodium hydroxide in 50 ml of water was added to the solution, and the mixed solution was heated to reflux for 1 hour to hydrolyze the resin. Then, the reaction mixture was diluted with 200 ml of water, neutralized with hydrochloric acid to precipitate a white resin. The resin was collected by filtration, washed with water and dried, and then dissolved in 200 ml tetrahydrofuran to prepare a solution. The solution was dropped into 5 L of ultrapure water with vigorous stirring and reprecipitated. The reprecipitation operation was repeated three times. The resin thus obtained was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain copoly (p-hydroxystyrene / tert-butyl methacrylate).
[404] (3-2) Synthesis of Resin (B-3)
[405] 10 g of poly (p-hydroxystyrene) (VP-8000, manufactured by Nippon Soda Co., Ltd.) was dissolved in 50 ml of pyridine. 3.63 g of di-tert-butyldicarbonates were dripped at this solution, stirring at room temperature. After stirring for 3 hours at room temperature, the reaction mixture was added dropwise to a solution containing 20 g of concentrated hydrochloric acid in 1 L of ion-exchanged water. The powder thus deposited was collected by filtration, washed with water and dried to obtain Resin (B-3).
[406] (3-3) Synthesis of Resin (B-32)
[407] 83.1 g (0.5 mol) of p-cyclohexylphenol was dissolved in 300 ml of toluene, and 150 g of 2-chloroethyl vinyl ether, 25 g of sodium hydroxide, 5 g of tetrabutylammonium bromide, and 60 g of triethylamine were added to the solution, followed by 120 ° C. The reaction was carried out for 5 hours. The reaction solution was washed with water, and excess 2-chloroethyl vinyl ether and toluene were distilled off. The oil thus obtained was purified by distillation under reduced pressure to obtain 4-cyclohexylphenoxyethyl vinyl ether.
[408] In 80 ml of tetrahydrofuran, 20 g of poly (p-hydroxystyrene) (VP-8000, manufactured by Nippon Soda Co., Ltd.) and 6.5 g of 4-cyclohexylphenoxyethyl vinyl ether were dissolved. After adding 0.01 g of p-toluenesulfonic acid to this solution, it reacted at room temperature for 18 hours. The reaction solution was added dropwise to 5 L of distilled water with vigorous stirring. The powder thus deposited was collected by filtration and dried to obtain a polymer (B-32).
[409] The resin of the other (BP) component was also synthesized in the same manner. The weight average molecular weight and molar ratio of a repeating unit in the polymer used for an Example below are shown.
[410] Suzy Weight average molecular weight Molar ratio of repeating units ^*)
[411] (B-3) 8,500 25/75
[412] (B-4) 8,500 25/75
[413] (B-21) 12,000 65/35
[414] (B-26) 11,500 15/60/25
[415] (B-28) 15,000 78/22
[416] (B-30) 8,000 80/20
[417] (B-31) 15,000 65/10/25
[418] (B-32) 12,000 82/18
[419] ^*) The molar ratio of a repeating unit is shown using the repeating unit of resin described in the specific example of resin of (BP) component previously, and the number in each polymer shows the molar ratio of a repeating unit in order from left to right.
[420] (4) Synthesis of Alkali-Soluble Resin of (BN)
[421] (4-1) Synthesis of Resin a- (29)
[422] 2,2'- while dissolving 3.9 g (0.024 mol) of 4-acetoxy styrene and 0.8 g (0.006 mol) of 4-methoxy styrene in 30 ml of 1-methoxy- 2-propanol, stirring the solution under nitrogen stream. 50 mg of polymerization initiators such as azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Waco Pure Chemical Industries, Ltd.), 9.1 g (0.056 mol) of 4-acetoxystyrene and 1.9 g of 4-methoxystyrene 70 ml of 1-methoxy-2-propanol liquid containing 0.014 mol) was dripped over 2 hours at 70 degreeC. After 2 hours, an additional 50 mg of the initiator was added and the reaction continued for another 2 hours. Then, temperature was heated up to 90 degreeC and the reaction liquid was stirred for 1 hour. After cooling the reaction solution, the mixture was poured into 1 L of ion-exchanged water with vigorous stirring to precipitate a white resin. The obtained resin was dried and then dissolved in 100 ml of methanol. 25% tetramethylammonium hydroxide aqueous solution was added to this solution, and the acetoxy group in resin was hydrolyzed. The solution was then neutralized with aqueous hydrochloric acid solution to precipitate a white resin. The resin was washed with ionized water and then dried under reduced pressure to obtain 11.6 g of resin a- (29) according to the present invention.
[423] When the weight average molecular weight (Mw) of the said resin was measured by GPC, it was 9,200 in polystyrene conversion, and dispersion degree (Mw / Mn) was 2.2. As a result of calculating the composition ratio of the said resin, the molar ratio of x / y was 80/20.
[424] (4-2) Synthesis of Resin a- (39)
[425] 12.0 g of poly (4-hydroxystyrene) (Mw: 10,500; Mw / Mn: 1.2) was dissolved in 100 ml of acetone, 2.0 g of pyridine was added to this solution, and then 1.3 g of acetic anhydride was added thereto, followed by stirring at 50 ° C. Reaction was carried out for 3 hours. The reaction solution was poured into 1 L of ion-exchanged water with vigorous stirring to precipitate a white resin. The obtained resin was dried under reduced pressure, and 12.2 g of resin a- (39) according to the present invention was obtained.
[426] When the weight average molecular weight (Mw) of the said resin was measured by GPC, it was 11,400 in polystyrene conversion, and dispersion degree (Mw / Mn) was 1.2. When the composition ratio of the resin was calculated, the molar ratio of x / y (4-hydroxystyrene / 4-acetoxy styrene) was 88/12.
[427] (4-3) Synthesis of Resin a- (91)
[428] 3.8 g (0.015 mol) of 2-[(4'-hydroxyphenyl) carbonyloxy] ethyl methacrylate, 1.0 g (0.009 mol) of 2-hydroxyethyl acrylate in 30 ml of 1-methoxy-2-propanol and 2,2'-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 0.3 g (0.006 mol) of acrylonitrile and the solution was stirred under a stream of nitrogen. Polymerization initiators such as 50 mg, 2-[(4'-hydroxyphenyl) carbonyloxy] ethyl methacrylate 8.8 g (0.035 mol), 2-hydroxyethyl acrylate 2.4 g (0.021 mol) and acrylonitrile 0.7 70 ml of 1-methoxy-2-propanol liquid containing g (0.014 mol) was dripped at 70 degreeC over 2 hours. After 2 hours, an additional 50 mg of the initiator was added and the reaction continued for another 2 hours. Then, temperature was heated up to 90 degreeC and the reaction liquid was stirred for 1 hour. After cooling the reaction solution, the mixture was poured into 1 L of ion-exchanged water with vigorous stirring to precipitate a white resin. The obtained resin was dried under reduced pressure to obtain 15.8 g of Resin a- (91) according to the present invention.
[429] When the weight average molecular weight (Mw) of the said resin was measured by GPC, it was 11,000 in polystyrene conversion, and dispersion degree (Mw / Mn) was 1.5. When the composition ratio of the resin was calculated, the molar ratio of x / y / z was 60/30/10.
[430] The resin of the other (BN) component according to the present invention was also synthesized in the same manner.
[431] (5) Synthesis of Crosslinking Agent
[432] 1 mol of p-aminophenol, 1 mol of sodium acetate, and 1 L of acetone were added to the flask, and 1 mol of isobutyric chloride was added dropwise to the mixture under ice-cooling. After 5 hours, the reaction mixture was poured into ice water to precipitate crystals. The crystals were collected by filtration to obtain 80% yield of HM-0-X.
[433] 0.8 ml of HM-0-X, 0.8 mol of potassium hydroxide, 500 ml of water, and 4.8 mol of 37% formalin aqueous solution were added to the flask, and the mixture was heated at 50 ° C. for 5 hours, and then neutralized with acetic acid. The mixture was concentrated under reduced pressure, the resulting oily product was dissolved in a mixture of ethyl acetate and methanol (1/1), separated by SiO ₂ column chromatography, and the desired crosslinking agent [HM-0] (L ₁ = L ₂ = CH). ₂ OH) was obtained as a colorless crystal in a yield of 50%.
[434]
[435] (5-2) Synthesis of Crosslinking Agent [HM-1]
[436] 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl] benzene (Trisp-PA, 20 g of Honshu Chemical Industries, Ltd. was added and dissolved. While stirring the solution, 60 ml of 37% aqueous formalin aqueous solution was slowly added thereto over 1 hour at room temperature. After stirring for another 6 hours at room temperature, the solution was poured into dilute sulfuric acid solution. The precipitate thus formed was collected by filtration and washed with water sufficiently and then recrystallized from 30 ml of methanol to obtain 20 g of a phenol derivative (crosslinking agent [HM-1]) of a white powder containing a hydroxymethyl group having the following structure. Its purity was 92% (calculated by liquid chromatography).
[437]
[438] (5-3) Synthesis of Crosslinking Agent [MM-1]
[439] 20 g of the phenol derivative (crosslinking agent [HM-1]) having the hydroxymethyl group obtained above was added to and dissolved in 1 L of methanol. 1 ml of concentrated sulfuric acid was added to this solution, and the mixture was heated to reflux for 12 hours. After the reaction was completed, the reaction solution was cooled, and 2 g of potassium carbonate was added thereto. The mixture was fully concentrated, and then 300 ml of ethyl acetate was added thereto. The solution was washed with water, concentrated to dryness, and 22g of a phenol derivative (crosslinking agent [MM-1]) containing a methoxymethyl group having the following structure was obtained as a white solid. Its purity was 90% (calculated by liquid chromatography).
[440]
[441] Examples 101-118 and Comparative Examples 101-105
[442] (1) Application of the resist composition
[443] Each component shown in Table 2 was dissolved in 26.0 g (total amount) of solvent in the following amount to prepare a resist composition solution. In Table 2, when a some compound is used in each component, the ratio is shown by weight ratio.
[444] Acid Degradable Resin (BP) 2.0g
[445] 0.20 g of acid generator
[446] Basic compound (if necessary) 0.0040 g
[447] Surfactant (if required) 0.0020 g
[448] The resist composition solution was microfiltered using a membrane filtration filter having a pore size of 0.1 μm to prepare a resist solution.
[449] This resist solution was applied onto a 6-inch silicon wafer using a spin coater (Mark 8, manufactured by Tokyo Electron Co., Ltd.), and baked at 110 ° C. for 90 seconds to obtain a uniform film having a thickness of 0.30 μm.
[450]
[451] The symbol of the component used in Table 2 is demonstrated below.
[452] Acid generators:
[453]
[454] Basic compound:
[455] (1): 1,8- diazabicyclo [4.3.0] non-5-ene
[456] (2): 2,6-diisopropylaniline
[457] (3): 4-dimethylaminopyridine
[458] (4): 2,4,5-triphenylimidazole
[459] (5): piperazine
[460] (6): 1, 5- diazabicyclo [4.3.0] non-5-ene
[461] (7): 1,5-diazabicyclo [2.2.2] octane
[462] (8): hexamethylenetetramine
[463] (9): 1-cyclohexyl-3- (2-morpholinomethyl) -2-thiourea (CHMETU)
[464] (10): phenylguanidine
[465] Surfactants:
[466] W-1: Megafac F176 (Dainippon Ink & Chemical Co., Ltd. product) (fluorine-based)
[467] W-2: Megafac R08 (made by Dainippon Ink & Chemicals Co., Ltd.) (fluorine-based and silicon-based)
[468] W-3: Polysiloxane Polymer KP-341 (Shin-Etsu Chemical Industries Co., Ltd.)
[469] W-4: polyoxyethylene phenyl ether
[470] W-5: Troysol S-366 (Troy Chemicals)
[471] solvent:
[472] S1: Propylene Glycol Monomethyl Ether Acetate
[473] S2: Propylene Glycol Monomethyl Ether Propionate
[474] S3: ethyl lactate
[475] S4: Butyl Acetate
[476] S5: 2-heptanone
[477] S6: Propylene Glycol Monomethyl Ether
[478] S7: ethoxyethyl propionate
[479] S8: γ-butyrolactone
[480] S9: ethylene carbonate
[481] S10: Propylene Carbonate
[482] S11: cyclohexanone
[483] (2) Preparation and Evaluation of Resist Patterns
[484] The electron beam irradiation was performed to the resist film using the electron beam drawing apparatus (HL750, Hitachi company; acceleration voltage 50KeV). After irradiation, the resist film was baked at 110 ° C. for 90 seconds, immersed in a 2.38% by weight aqueous tetramethylammonium hydroxide (TMAH) solution for 60 seconds to develop, washed with water for 30 seconds, and dried. The pattern thus obtained was evaluated by the following method.
[485] (2-1) sensitivity
[486] The minimum irradiation energy necessary for resolving the 0.15 micrometer line (line: space = 1: 1) was made into the sensitivity.
[487] (2-2) resolution
[488] The limit resolution (irradiated lines and spaces separately) in the irradiation energy for obtaining the sensitivity was taken as the resolution.
[489] (2-3) Pattern Profile
[490] The cross-sectional shape of the 0.14 µm-line pattern at the irradiation energy for obtaining the sensitivity was observed using a scanning electron microscope.
[491] Table 3 shows the obtained evaluation results.
[492]
[493] Examples 116-130 and Comparative Examples 106-110
[494] A resist solution was prepared in the same manner as in Example 101 using the components shown in Table 2 above. This resist solution was applied onto a 6-inch silicon wafer using a spin coater (Mark 8, manufactured by Tokyo Electron Co., Ltd.), and baked at 110 ° C. for 90 seconds to obtain a uniform film having a thickness of 0.30 μm.
[495] Electron beam irradiation was performed to this resist film using the electron beam drawing apparatus (HL750, Hitachi; acceleration voltage 100 KeV). Post-irradiation treatment and evaluation were carried out in the same manner as in Example 101.
[496] The obtained evaluation results are shown in Table 4 below.
[497]
[498] From the results shown in Tables 3 and 4, it can be seen that the positive resist composition of the present invention exhibits high sensitivity, high resolution and rectangular profile, and is excellent in performance.
[499] Examples 137-138 and Comparative Example 111
[500] Using the resist solutions of Examples 101 and 102 and Comparative Example 101, a resist film was prepared in the same manner as in Example 101 except that the thickness of the resist film was changed to 0.25 µm. The resist film was subjected to open-frame-exposure using EUV rays (wavelength: 13 nm) while varying the exposure energy amount of 0.5 mJ from 0 to 5.0 mJ, respectively, and baked at 110 ° C. for 90 seconds. Then, using a 2.38% by weight tetramethylammonium hydroxide (TMAH) aqueous solution, the dissolution rate at each exposure amount was measured to obtain a sensitivity curve. In the sensitivity curve, the exposure amount when the dissolution rate was the highest was regarded as sensitivity. In addition, the dissolution contrast (γ value) was calculated from the slope of the sensitivity curve. The larger the gamma value, the better the dissolution contrast. The obtained results are shown in Table 5 below.
[501] EUV rating ExampleCompositionSensitivity (mJ / ㎠)γ value 137Example 1013.09.5 138Example 1022.010.5 Comparative Example 111Comparative Example 101> 5.06.5
[502] From the results shown in Table 5, it can be seen that the positive resist composition of the present invention exhibits high sensitivity and high resolution compared with the resist composition of the comparative example in EUV evaluation, and has excellent performance.
[503] Examples 201 to 214 and Comparative Examples 201 to 205
[504] (1) Application of the resist composition
[505] Each component shown in Table 6 was dissolved in 18.0 g (total amount) of solvent in the following amounts to prepare a negative resist composition solution.
[506] Alkali-soluble resin (BN) 2.0 g
[507] Total amount of acid generator 0.20 g
[508] Total amount of crosslinking agent (C) 0.35 g
[509] Basic compound (if necessary) 0.0080 g
[510] Surfactant (if required) 0.0040 g
[511] The negative resist composition solution was filtered using a Teflon filter having a pore size of 0.1 μm, and then treated with hexamethyldisilazane using a spin coater (Mark 8, manufactured by Tokyo Electron Co., Ltd.) at 110 ° C. on a vacuum hot plate Heat-drying was carried out for 90 second, and the resist film of thickness 0.30micrometer was produced.
[512]
[513] Resin a- (1), a- (2), a- (3), a- (25), a- (27), a- (29) and a- (30) shown in Table 6 below , the composition (molar ratio) and molecular weight of a- (31), a- (32), a- (35), a- (39), a- (57), a- (91) and a- (93) Represents:
[514] a- (1): Mw = 15,000 Mw / Mn = 1.1
[515] a- (2): Mw = 9,000 Mw / Mn = 1.2
[516] a- (3): Mw = 8,000 Mw / Mn = 1.3
[517] a- (25): x / y = 70/30 Mw = 16,000 Mw / Mn = 1.5
[518] a- (27): x / y = 80/20 Mw = 9,500 Mw / Mn = 1.5
[519] a- (29): x / y = 80/20 Mw = 9,200 Mw / Mn = 2.2
[520] a- (30): x / y = 80/20 Mw = 12,000 Mw / Mn = 1.2
[521] a- (31): x / y = 90/10 Mw = 8,500 Mw / Mn = 1.3
[522] a- (32): x / y = 75/25 Mw = 9,000 Mw / Mn = 1.2
[523] a- (35): x / y = 75/25 Mw = 20,000 Mw / Mn = 2.1
[524] a- (39): x / y = 88/12 Mw = 11,400 Mw / Mn = 1.2
[525] a- (57): x / y = 95/5 Mw = 5,000 Mw / Mn = 1.2
[526] a- (91): x / y / z = 60/30/10 Mw = 11,000 Mw / Mn = 1.5
[527] a- (93): x / y = 85/15 Mw = 9,300 Mw / Mn = 1.1
[528] The symbol of the component used in Table 6 is demonstrated below.
[529] Acid generators:
[530] BCFY:
[531]
[532] PAG-1:
[533]
[534] PAG-2:
[535]
[536] Basic compound:
[537] (1): 1,8- diazabicyclo [4.3.0] non-5-ene
[538] (2): 2,6-diisopropylaniline
[539] (3): 4-dimethylaminopyridine
[540] (4): 2,4,5-triphenylimidazole
[541] (5): piperazine
[542] (6): 1, 5- diazabicyclo [4.3.0] non-5-ene
[543] (7): phenylguanidine
[544] (8): hexamethylenetetramine
[545] (9): CHMETU
[546] Surfactants:
[547] W-1: Megafac F176 (Dainippon Ink & Chemical Co., Ltd. product) (fluorine-based)
[548] W-2: Megafac R08 (made by Dainippon Ink & Chemicals Co., Ltd.) (fluorine-based and silicon-based)
[549] W-3: Polysiloxane Polymer KP-341 (Shin-Etsu Chemical Industries Co., Ltd.)
[550] W-4: polyoxyethylene phenyl ether
[551] W-5: Troysol S-366 (Troy Chemicals)
[552] solvent:
[553] S1: Propylene Glycol Monomethyl Ether Acetate
[554] S2: Propylene Glycol Monomethyl Ether Propionate
[555] S3: ethyl lactate
[556] S4: Butyl Acetate
[557] S5: 2-heptanone
[558] S6: Propylene Glycol Monomethyl Ether
[559] S7: ethoxyethyl propionate
[560] S8: γ-butyrolactone
[561] S9: ethylene carbonate
[562] S10: Propylene Carbonate
[563] S11: cyclohexanone
[564] (2) Preparation and Evaluation of Resist Patterns
[565] Electron beam irradiation was performed on the resist film using an electron beam drawing apparatus (HL 750, manufactured by Hitachi; acceleration voltage: 50 KeV). After irradiation, the resist film was heated at 110 ° C. by vacuum hot plate for 60 seconds, immersed in 2.38 wt% aqueous tetramethylammonium hydroxide (TMAH) solution for 60 seconds, developed, washed with water for 30 seconds and dried. The cross-sectional shape of the formed 0.15 μm-line (line: space = 1: 1) pattern was observed using a scanning microscope.
[566] The minimum irradiation energy required to resolve the 0.20 mu m-line (line: space = 1: 1) was taken as the sensitivity.
[567] The limit resolution (irradiated lines and spaces separately) in the irradiation energy for obtaining the sensitivity was taken as the resolution. When 0.20 micrometer-line (line: space = 1: 1) was not resolved, the limit resolution was made into resolution.
[568] The obtained evaluation results are shown in Table 7 below.
[569]
[570] The results shown in Table 7 show that the negative resist composition of the present invention exhibits high sensitivity, high resolution, and a rectangular pattern profile, and is excellent in performance.
[571] The same result was obtained when using an exposure X-ray drawing apparatus.
[572] According to the present invention, it is possible to provide a positive or negative resist composition for electron beam, EUV or X-ray, which is excellent in sensitivity and resolution and provides a rectangular profile.
[573] In the present application, each and every foreign patent application claiming the benefit of foreign priorities is presented as a reference for sufficient explanation.
[574] Although the present invention has been described in detail with reference to the detailed embodiments, various modifications and changes can be made by those skilled in the art without departing from the spirit and scope of the invention.

权利要求:
Claims (19)
[1" claim-type="Currently amended] (A1) A resist composition for electron beams, EUV or X-rays, which has a higher reduction potential than diphenyl iodonium salt and contains a compound which generates an acid by irradiation with actinic radiation or radiation.
[2" claim-type="Currently amended] Compounds having a higher reduction potential than (A1) diphenyl iodonium salt and generating an acid by irradiation of actinic radiation or radiation, and are insoluble or poorly soluble in aqueous alkali solution, but are insoluble in alkaline aqueous solution by the action of acid. A positive resist composition for electron beam, EUV or X-ray, characterized by containing a polymer that becomes soluble.
[3" claim-type="Currently amended] The compound according to claim 2, wherein the compound having a higher reduction potential than the (A1) diphenyl iodonium salt and generating an acid by irradiation with actinic rays or radiation is represented by the following general formulas (1), (2) or (3): A positive resist composition for electron beam, EUV or X-ray, characterized in that the compound is represented.


(Wherein Y represents an aryl group which may have a substituent or an alkyl group which may have a substituent; R _1a to R _8a may each independently have a hydrogen atom, a halogen atom, a nitro group, a cyano group, a carboxyl group or a substituent) An alkyl group or a cycloalkyl group which may have a substituent; R ₁ to R ₁₅ each independently represent a hydrogen atom, a nitro group, a cyano group, or a trifluoromethyl group, provided that at least two of R ₁ to R ₁₅ are nitro groups; A cyano group and a trifluoromethyl group, R ₁₆ to R ₂₇ each independently represent a hydrogen atom, a nitro group, a cyano group, a trifluoromethyl group or a halogen atom, and y represents 0 or 1; X ⁻ is a fluorine atom, an alkyl group substituted with one or more fluorine atoms, an alkoxy group substituted with one or more fluorine atoms, an acyl group substituted with one or more fluorine atoms, one or more An acyloxy group substituted with a fluorine atom, a sulfonyl group substituted with one or more fluorine atoms, a sulfonyloxy group substituted with one or more fluorine atoms, a sulfonylamino group substituted with one or more fluorine atoms, an aryl group substituted with one or more fluorine atoms, Anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least one selected from an aralkyl group substituted with at least one fluorine atom and an alkoxycarbonyl group substituted with at least one fluorine atom)
[4" claim-type="Currently amended] The electron beam according to claim 2, further comprising a compound having a structure represented by any one of the following general formulas (I) to (III) by generating an acid by irradiation with (A2) actinic light or radiation. , Positive resist composition for EUV or X-ray.

Wherein R ₁ to R ₃₇ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a halogen atom or a -SR ₃₈ group; R ₃₈ represents an alkyl group or an aryl group; X ^- represents a fluorine atom, An alkyl group substituted with one or more fluorine atoms, an alkoxy group substituted with one or more fluorine atoms, an acyl group substituted with one or more fluorine atoms, an acyloxy group substituted with one or more fluorine atoms, a sulfonyl group 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, aralkyl groups substituted with one or more fluorine atoms, and alkoxy substituted with one or more fluorine atoms Anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having one or more selected from carbonyl groups)
[5" claim-type="Currently amended] The compound according to claim 2, wherein the compound (A3) generates a fluorine atom-containing carboxylic acid by irradiation with actinic rays or radiation and (A4) the compound generates fluorine atom-free carboxylic acid by irradiation with actinic rays or radiation. The positive resist composition for electron beam, EUV or X-ray which further contains 1 or more types of compounds chosen from.
[6" claim-type="Currently amended] The polymer according to claim 2, wherein the polymer which is insoluble or poorly soluble in the aqueous alkali solution (BP) but becomes soluble in the aqueous alkali solution by the action of an acid contains a group represented by the following general formula (X1) or (X2). A positive resist composition for an electron beam, EUV or X-ray, characterized in that the polymer having a structural unit.

(Wherein R _1b and R _2b may be the same or different and each represents a hydrogen atom or an alkyl group; R _3b and R _4b may be the same or different, and each may have a hydrogen atom or a substituent or an alkyl group or substituent). Good cycloalkyl group; R _5b represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent or an aralkyl group which may have a substituent; m represents an integer of 0 to 20. N represents an integer of 0 to 5).

(Wherein R _6b and R _7b may be the same or different and each represents a hydrogen atom or an alkyl group; W represents a divalent organic group; R _8b represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent) An aryl group which may have or an aralkyl group which may have a substituent is shown.)
[7" claim-type="Currently amended] The polymer according to claim 2, wherein the polymer which is insoluble or poorly soluble in the aqueous alkali solution (BP) but becomes soluble in the aqueous alkali solution by the action of an acid contains a structural unit containing a tertiary ester group decomposed by the action of an acid. Positive resist composition for electron beam, EUV or X-ray, characterized in that the polymer having.
[8" claim-type="Currently amended] The polymer according to claim 2, wherein the polymer which is insoluble or poorly soluble in the aqueous alkali solution (BP), but becomes soluble in the aqueous alkali solution by the action of acid contains a tert-butoxycarbonyl group decomposed by the action of acid. A positive resist composition for an electron beam, EUV or X-ray, characterized in that the polymer having a unit.
[9" claim-type="Currently amended] (A1) A compound having a reduction potential higher than that of diphenyl iodonium salt, and containing a compound which generates an acid by irradiation of actinic light or radiation, a (BN) alkali-soluble resin and a crosslinking agent crosslinked by the action of (C) acid. A negative resist composition for electron beam, EUV or X-ray.
[10" claim-type="Currently amended] The compound according to claim 9, wherein the compound having a higher reduction potential than the (A1) diphenyl iodonium salt and generating an acid by irradiation with actinic rays or radiation is represented by the following general formulas (1), (2) or (3). A negative resist composition for electron beam, EUV or X-ray, characterized in that the compound.


(Wherein Y represents an aryl group which may have a substituent or an alkyl group which may have a substituent; R _1a to R _8a may each independently have a hydrogen atom, a halogen atom, a nitro group, a cyano group, a carboxyl group or a substituent) An alkyl group or a cycloalkyl group which may have a substituent; R ₁ to R ₁₅ each independently represent a hydrogen atom, a nitro group, a cyano group, or a trifluoromethyl group, provided that at least two of R ₁ to R ₁₅ are nitro groups; A cyano group and a trifluoromethyl group, R ₁₆ to R ₂₇ each independently represent a hydrogen atom, a nitro group, a cyano group, a trifluoromethyl group or a halogen atom, and y represents 0 or 1; X ⁻ is a fluorine atom, an alkyl group substituted with one or more fluorine atoms, an alkoxy group substituted with one or more fluorine atoms, an acyl group substituted with one or more fluorine atoms, one or more An acyloxy group substituted with a fluorine atom, a sulfonyl group substituted with one or more fluorine atoms, a sulfonyloxy group substituted with one or more fluorine atoms, a sulfonylamino group substituted with one or more fluorine atoms, an aryl group substituted with one or more fluorine atoms, Anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least one selected from an aralkyl group substituted with at least one fluorine atom and an alkoxycarbonyl group substituted with at least one fluorine atom)
[11" claim-type="Currently amended] 10. The electron beam according to claim 9, further comprising a compound having a structure represented by any one of the following general formulas (I) to (III) by generating an acid by irradiation with (A2) actinic light or radiation. , Negative resist composition for EUV or X-ray.

Wherein R ₁ to R ₃₇ may be the same or different and each represents a hydrogen atom, a straight chain, a branched or cyclic alkyl group, a straight chain, a branched or cyclic alkoxy group, a hydroxy group, a halogen atom or a -SR ₃₈ group; ₃₈ represents a straight-chain, branched or cyclic alkyl group or an aryl group; X ⁻ is a fluorine atom, a straight-chain, branched or cyclic alkyl group substituted with one or more fluorine atoms, a straight-chain, branched or substituted with one or more fluorine atoms Cyclic alkoxy groups, acyl groups substituted with one or more fluorine atoms, acyloxy groups 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, one or more fluorine A sulfonylamino group substituted with an atom, an aryl group substituted with one or more fluorine atoms, an aralkyl group substituted with one or more fluorine atoms, and an alkoxycarbonyl group substituted with one or more fluorine atoms Anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having one or more selected
[12" claim-type="Currently amended] The compound according to claim 9, wherein the compound (A3) generates a fluorine atom-containing carboxylic acid by irradiation with actinic rays or radiation and (A4) the compound generates fluorine atom-free carboxylic acid by irradiation with actinic rays or radiation. The negative resist composition for electron beam, EUV or X-ray which further contains 1 or more types of compounds chosen from.
[13" claim-type="Currently amended] The crosslinking agent crosslinked by the action of the acid (C) is at least one compound selected from the compounds represented by the following general formulas (2) to (4) and an alkoxymethylated melamine compound. Negative resist composition for electron beam, EUV or X-ray.

(Wherein R _5b each independently represents a hydrogen atom, an alkyl group or an acyl group; R _6b to R _9b each independently represents a hydrogen atom, a hydroxy group, an alkyl group or an alkoxy group; X represents a single bond, a methylene group or an oxygen atom) )
[14" claim-type="Currently amended] The crosslinking agent crosslinked by the action of the (C) acid has 1 to 6 benzene rings per molecule, and two or more hydroxymethyl groups and / or alkoxymethyl groups are bonded to any one of the benzene rings. A negative resist composition for electron beams, EUV or X-rays, characterized in that the compound is selected from phenol derivatives.
[15" claim-type="Currently amended] The compound for generating a fluorine atom-containing carboxylic acid by irradiation with actinic light or radiation (A3) is a compound represented by any one of the following general formulas (IF) to (IIIF). Positive resist composition for electron beam, EUV or X-ray.

Wherein R ₁ to R ₃₇ each independently represent a hydrogen atom, a straight chain, a branched or cyclic alkyl group, a straight chain, a branched or cyclic alkoxy group, a hydroxy group, a halogen atom or a -SR ₃₈ group; R ₃₈ is a straight chain Represents a branched or cyclic alkyl group or an aryl group; X ⁻ represents an anion of an aliphatic or aromatic carboxylic acid substituted with one or more fluorine atoms)
[16" claim-type="Currently amended] The compound according to claim 5, wherein the compound (A4) generates fluorine atom-free carboxylic acid by irradiation with actinic light or radiation is a compound represented by any one of the following general formulas (AI) to (AV). Positive resist composition for electron beams, EUV or X-rays.

Wherein R ₃₀₁ to R ₃₀₇ each independently represent a hydrogen atom, a straight chain, a branched or cyclic alkyl group, a straight chain, a branched or cyclic alkoxy group, a hydroxy group, a halogen atom or a -SR ₀ group; R ₀ represents a straight chain R _a and R _b each independently represent a hydrogen atom, a nitro group, a halogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent; R _c and R each _d independently represents a halogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, or R _c and R _d combine with each other to form an aromatic, monocyclic or polycyclic aliphatic hydrocarbon ring (the ring is an oxygen atom); or may be bonded to form a good may contain a nitrogen atom); Y ₁ and Y ₂ each represents characters carbon atoms, Y ₁ -Y ₂ represents a single bond or a double bond Results It may be good; X ^- is to represent an anion of at least one carboxylic acid compound represented by the formula; X ₁ and X ₂ is an ester group formed at the carboxyl group of one or more carboxylic acid compounds, each to independently represented by the general formula Indicates.


Wherein R ₃₃₈ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms (wherein the alkyl group may contain an oxygen atom or a nitrogen atom in the chain of the alkyl group), a linear or branched phase having 2 to 20 carbon atoms Or a cyclic alkenyl group, a linear, branched or cyclic alkynyl group having 2 to 20 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, and at least a part of the hydrogen atoms of the alkyl group is a halogen atom and / or a hydroxy group A group substituted with at least one hydrogen atom of the alkenyl group, a group substituted with a halogen atom and / or a hydroxy group, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; R ₃₃₉ is a single bond, a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, where the alkylene group may contain an oxygen atom or a nitrogen atom in the chain of the alkylene group, A chain, branched or cyclic alkenylene group, a group in which at least a part of the hydrogen atoms of the alkylene group is substituted with a halogen atom and / or a hydroxy group, and at least a part of the hydrogen atoms of the alkenylene group is substituted with a halogen atom and / or a hydroxy group A group or an alkoxyalkylene group having 2 to 20 carbon atoms; A plurality of R ₃₃₈ and R ₃₃₉ may be the same as or different from each other; R ₃₄₀ represents a hydroxy group or a halogen atom; A plurality of R _340s may be the same as or different from each other; m, n, p and q each independently represent an integer of 0 to 3, provided that m + n ≦ 5 and p + q ≦ 5; z represents 0 or 1)
[17" claim-type="Currently amended] The negative resist composition for electron beams, EUV or X-rays according to claim 9, wherein the alkali-soluble resin of (BN) is a resin containing a repeating unit represented by the following general formula (a).

(Wherein R ₁ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent or a haloalkyl group which may have a substituent; R ₂ may have a hydrogen atom, an alkyl group which may have a substituent or a substituent) A cycloalkyl group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or an acyl group which may have a substituent; R <_3> and R <_4> may be same or different, and each is a hydrogen atom, a halogen atom, a cyano group, An alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent; A may have a single bond or a substituent Alkenylene group which may have alkylene group and substituent, substituent Even better cycloalkylene group, an arylene group which may have a _{substituent, -O-, -SO 2 -, -O} -CO-R 5 -, -CO-OR 6 -, -CO-N (R 7) -R 8 R ₅ , R ₆ and R ₈ may be the same or different and each is a single bond, an alkylene group which may have a substituent, an alkenylene group which may have a substituent, a cycloalkylene group which may have a substituent, or a substituent An arylene group which may have an alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, and a divalent compound formed by combining at least one selected from an ether structure, an ester structure, an amido structure, a urethane structure and a ureido structure. R <_7> represents a hydrogen atom, the alkyl group which may have a substituent, the cycloalkyl group which may have a substituent, the aralkyl group which may have a substituent, or the aryl group which may have a substituent; n represents the integer of 1-3 Or a plurality of R ₂ , R ₂ and R ₃ , or R ₂ and R ₄ may be bonded to each other to form a ring)
[18" claim-type="Currently amended] The electron beam, EUV or the compound according to claim 1, further comprising an organic basic compound containing a structure represented by the following general formulas (A), (B), (C), (D) or (E). X-ray resist composition.

(Wherein R²⁵⁰, R²⁵¹And R²⁵²May be the same or different and each represents a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an aminoalkyl group of 1 to 6 carbon atoms, a hydroxyalkyl group of 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, Or R²⁵¹And R²⁵²These may combine with each other to form a ring; R²⁵³, R²⁵⁴, R²⁵⁵And R²⁵⁶May be the same or different and each represents an alkyl group having 1 to 6 carbon atoms)
[19" claim-type="Currently amended] The resist composition for electron beam, EUV or X-ray of claim 1, further comprising a fluorine-based and / or silicon-based surfactant.

类似技术:

---

公开号 | 公开日 | 专利标题

---

US6673512B1|2004-01-06|Negative-working resist composition

---

JP4187934B2|2008-11-26|Positive resist composition

---

JP3444821B2|2003-09-08|Positive photoresist composition

---

JP3912767B2|2007-05-09|Positive photosensitive composition

---

US6818377B2|2004-11-16|Positive photosensitive composition

---

KR100947853B1|2010-03-18|Positive-working resist composition and pattern forming method using thereof

---

JP4007570B2|2007-11-14|Positive resist composition

---

KR100950508B1|2010-03-31|Positive resist composition and pattern forming method using the same

---

US6962766B2|2005-11-08|Positive photoresist composition

---

US6605409B2|2003-08-12|Positive resist composition

---

KR100878499B1|2009-01-13|Positive resist composition

---

JP3613491B2|2005-01-26|Photosensitive composition

---

JP4150509B2|2008-09-17|Positive photosensitive composition

---

KR100900468B1|2009-06-03|POSITIVE RESIST COMPOSITION FOR ArF EXCIMER LASER EXPOSURE AND PATTERN FORMING METHOD USING THE COMPOSITION

---

KR100885691B1|2009-02-26|Positive photoresist composition and pattern forming method

---

JP4149194B2|2008-09-10|Positive radiation sensitive composition

---

KR100538968B1|2006-07-11|Positive Photosensitive Composition

---

KR100760245B1|2007-09-19|Positive-working resist composition

---

JP4262402B2|2009-05-13|Positive resist composition

---

JP4857138B2|2012-01-18|Resist composition and pattern forming method using the same

---

JP4102032B2|2008-06-18|Positive resist composition

---

JP3591672B2|2004-11-24|Positive photosensitive composition

---

JP4124978B2|2008-07-23|Positive resist composition

---

KR100797488B1|2008-01-23|Positive photosensitive composition

---

US6245485B1|2001-06-12|Positive resist composition

同族专利:

---

公开号 | 公开日

---

KR100890739B1|2009-03-26|

---

US20030198894A1|2003-10-23|

---

KR100931616B1|2009-12-14|

---

KR20080088563A|2008-10-02|

---

US7521168B2|2009-04-21|

---

EP1338921A3|2007-12-12|

---

EP2477073A1|2012-07-18|

---

EP1338921A2|2003-08-27|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

法律状态:
2002-02-13|Priority to JP2002035685

---

2002-02-13|Priority to JPJP-P-2002-00035685

---

2002-02-15|Priority to JP2002038494

---

2002-02-15|Priority to JPJP-P-2002-00038494

---

2003-02-12|Application filed by 후지 샤신 필름 가부시기가이샤

---

2003-10-11|Publication of KR20030080195A

---

2009-03-26|Application granted

---

2009-03-26|Publication of KR100890739B1

优先权:

---

申请号 | 申请日 | 专利标题

---

JP2002035685|2002-02-13|

---

JPJP-P-2002-00035685|2002-02-13|

---

JP2002038494|2002-02-15|

---

JPJP-P-2002-00038494|2002-02-15|