JP4488194B2 - Resist composition - Google Patents

Description

  The present invention relates to a radiation-sensitive resist composition containing a resist compound represented by a specific chemical structural formula, an acid generator, and an acid crosslinking agent, which are useful as an acid amplification type non-polymeric resist material. The resist composition of the present invention is used as a radiation-sensitive material that is sensitive to radiation such as ultraviolet rays, far ultraviolet rays, electron beams, and X-rays, for masks used in the manufacture of LSIs and VLSIs in the electronics field.

  Conventional general resist materials are polymer materials capable of forming an amorphous thin film. For example, 0.1 μm is obtained by irradiating ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. to a resist thin film prepared by applying polymethyl methacrylate and a solution in which it is dissolved in a solvent for dissolving it onto a substrate. About a line pattern is formed.

  However, since the polymer resist has a large molecular weight of about 10,000 to 100,000 and the molecular weight distribution is wide, in lithography using the polymer resist, roughness is generated on the pattern surface in fine processing, and the pattern dimension is controlled. Becomes difficult and the yield decreases. Therefore, there is a limit to miniaturization in conventional lithography using a polymer resist material. In order to produce a finer pattern, various methods for reducing the molecular weight of a resist material have been disclosed.

  Examples of non-polymer resist materials are (1) positive and negative resists derived from fullerene, (2) positive and negative resists derived from calixarene, and (3) derived from starburst compounds. A positive resist, (4) a positive resist derived from a dendrimer, (5) a positive resist derived from a dendrimer / calixarene, and (6) a positive resist derived from a highly branched starburst compound, And (7) a positive resist derived from a starburst compound having an ester bond with trimesic acid as the central skeleton.

About (1), although etching resistance is good, applicability | paintability and a sensitivity have not reached the practical use level (refer patent documents 1-5). About (2), although it is excellent in etching tolerance, since a solubility with respect to a developing solution is bad, a satisfactory pattern is not obtained (refer patent documents 6-8). Regarding (3), the image may be distorted during heat treatment after exposure due to low heat resistance (see Patent Documents 9 to 11). Regarding (4), the manufacturing process is complicated and the heat resistance is low, so the image may be distorted during the heat treatment after exposure, and it cannot be said that it is practical (see Non-Patent Document 1). . Regarding (5), the manufacturing process is complicated and the raw material is expensive, so it cannot be said that it is practical. (See Patent Documents 12 and 13.) About (6), since a manufacturing process is complicated and a raw material is expensive, it cannot be said that it is practical. Regarding (7), since the heat resistance is low, the image may be distorted during the heat treatment after exposure, and the substrate adhesion is insufficient, so it cannot be said that it is practical (see Patent Document 14). .
On the other hand, it is disclosed that a compound having a spirobiindane or spirobichroman skeleton can be used as an antioxidant (see Patent Document 15), an acid generator (see Patent Document 16) or an additive (see Patent Document 17) in a resist composition. Has been. However, it is not known that a chemically amplified resist can be used as a base material that is crosslinked by a crosslinking agent using an acid generated from an acid generator during exposure as a catalyst.
JP-A-7-134413 JP 9-211182 A JP-A-10-282649 Japanese Patent Application Laid-Open No. 11-143074 Japanese Patent Laid-Open No. 11-258996 JP-A-11-72916 JP-A-11-322656 JP-A-9-236919 JP 2000-305270 A JP 2002-99088 A JP 2002-99089 A JP 2002-49152 A JP 2003-183227 A Japanese Patent Laid-Open No. 2002-328466 JP 2002-241348 A JP-A-9-143146 Japanese Patent No. 2589803 Proceedings of SPIE vol. 3999 (2000) P1202-1206.

  An object of the present invention is to provide a radiation-sensitive resist composition that can be used not only for ultraviolet rays such as i-rays and g-rays but also for excimer laser light such as visible rays and KrF, electron rays, X-rays, and ion beams. It is to provide. Still another object of the present invention is to provide a non-polymeric radiation-sensitive resist composition having high sensitivity, high resolution, high heat resistance and solvent solubility by a simple production process.

As a result of intensive studies, the present inventors have found that a resist composition containing a compound having a specific chemical structure and an acid generator that directly or indirectly generates an acid upon irradiation with radiation and an acid crosslinking agent are the above-mentioned problems. It was found to be useful for solving the problem.
That is, the present invention can be applied directly or directly by irradiation with any radiation selected from the group consisting of the compound (A) represented by the formula (1), visible light, ultraviolet light, excimer laser, electron beam, X-ray, and ion beam. The present invention relates to a resist composition comprising an acid generator (B) that indirectly generates an acid, and an acid crosslinking agent (C).

In formula (1), R1 to R8 are independently a hydrogen atom or a hydroxy group, and at least two are hydroxy groups. R9 to R12 are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Z is an oxygen atom or a single bond.
Furthermore, the present invention provides a resist substrate in which a resist film made of the resist composition is formed on the substrate, and a pattern-formed substrate in which the resist film made of the resist composition is patterned.
Furthermore, the present invention provides a step of forming a resist film by applying the resist composition on a substrate, and the resist film is any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, X-ray and ion beam. And a step of developing the exposed resist film using a developing solution after performing a heat treatment if necessary, and a resist pattern forming method.
Further, the present invention provides a step of coating the resist composition on a substrate to form a resist film, a step of heat-treating the resist film, and applying the heat-treated resist film to visible light, ultraviolet light, excimer laser, electron beam, X A step of irradiating and exposing any radiation selected from the group consisting of a line and an ion beam, and a step of developing the exposed resist film with an alkali developer after heat treatment as necessary. A resist pattern forming method is provided.
Furthermore, the present invention provides a patterned wiring board obtained by performing etching after performing the pattern forming method.

  Since the resist composition of the present invention has high sensitivity, a high-resolution resist pattern can be produced, and a highly integrated semiconductor device can be produced with high productivity.

Hereinafter, the present invention will be described in detail.
The resist composition of the present invention contains a compound (A) represented by the formula (1), an acid generator (B), and an acid crosslinking agent (C). In formula (1), R1 to R8 are independently a hydrogen atom or a hydroxy group, and at least two are hydroxy groups. R9 to R12 are independently a hydrogen atom or an alkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. Of these, a hydrogen atom, a methyl group, and an ethyl group are preferable.
In the formula (1), Z is an oxygen atom or a single bond. The single bond referred to here means that other structural units are directly connected to each other.

  In the compound (A) used in the present invention, among the compounds represented by the formula (1), R1 to R4 in the formula (1) are hydrogen atoms, R9 to R12 are methyl groups, and R5 to R8 are hydroxy. The compound which is group is more preferable. For example, it has physical properties preferable for resist material forming applications such as high sensitivity, high heat resistance, and sufficient resistance to heat treatment in the pattern formation step.

  There is no restriction | limiting in particular in the method of manufacturing the compound (A) used by this invention, A conventionally well-known method is applicable. For example, it can be obtained by reacting phenols such as catechol, resorcin, 1,2,4-trihydroxybenzene, pyrogallol and acetone in the presence of acetic acid and hydrochloric acid or in the presence of acetic acid and sulfuric acid.

  Examples of the compound (A) include, but are not limited to, the following compounds. 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, 6,6′-dihydroxy-1,1′-spirobiindane, 6,6′-dihydroxy-3, 3,3 ′, 3 ′, 5,5′-hexamethyl-1,1′-spirobiindane, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-5,5′-diethyl-1 , 1′-spirobiindane, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-7,7′-diisopropyl-1,1′-spirobiindane, 6,6′-dihydroxy-3,3 , 3 ′, 3′-tetramethyl-5,5′-dimethoxy-1,1′-spirobiindane, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-7,7′-diethoxy -1,1'-spirobiindane, 6,6'-dihydroxy-3,3,3 ', 3' Tetramethyl-5,5′-dichloro-1,1′-spirobiindane, 6,6′-dihydroxy-3,3,3 ′, 3 ′, 4,4′-hexamethyl-1,1′-spirobiindane, 6, 6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-7,7′-di-n-propyl-1,1′-spirobiindane, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-4,4′-di-tert-butyl-1,1′-spirobiindane, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-4,4′-dimethoxy -1,1'-spirobiindane, 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-5,5'-diethoxy-1,1'-spirobiindane, 6,6'-dihydroxy-3 , 3,3 ′, 3′-tetramethyl-5,5′-di-n-propoxy-1,1′-spi Robinindane, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-4,4′-dichloro-1,1′-spirobiindane, 6,6′-dihydroxy-3,3,3 ′, 3 ′, 7,7′-hexamethyl-1,1 ′, spirobiindane, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-7,7′-di-n-butoxy-1 , 1′-spirobiidan, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-5,5′-di-n-propyl-1,1′-spirobiindane, 6,6′-dihydroxy -3,3,3 ', 3'-tetramethyl-7,7'-di-n-butyl-1,1'-spirobiindane, 6,6'-dihydroxy-3,3,3', 3'-tetra Methyl-5,5′-diisopropoxy-1,1′-spirobiindane, 6,6′-dihydroxy-3,3,3 ′, 3′- Tramethyl-7,7′-diethyl-1,1′-spirobiindane, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-5,5′-diisobutyl-1,1′-spirobiindane, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-4,4′-diethoxy-1,1′-spirobiindane, 6,6′-dihydroxy-3,3,3 ′, 3 ′ -Tetramethyl-7,7'-di-n-butoxy-1,1'-spirobiindane, 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane, 6 , 6′-dihydroxy-3,3,3 ′, 3 ′, 5,5′-hexamethyl-1,1′-spirobiindane, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl- 5,5′-di-tert-butyl-1,1′-spirobiindane, 6,6′-dihydro -3,3,3 ', 3'-tetramethyl-7,7'-dimethoxy-1,1'-spirobiindane, 6,6'-dihydroxy-3,3,3', 3'-tetramethyl-7 , 7'-dichloro-1,1'-spirobiindane, 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane, 6,6'-dihydroxy-3,3 , 3 ′, 3 ′, 5,5′-hexamethyl-1,1′-spirobiindane, 6,6′-dihydroxy-3,3,3 ′, 3′-tetramethyl-5,5′-diisopropyl-1, 1′-spirobiindane, 5,5 ′, 6,6′-tetrahydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, 4,4 ′, 6,6′-tetrahydroxy -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane, 6,6', 7,7'-tetrahi Roxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, 4,6,7,4 ′, 6 ′, 7′-hexahydroxy-3,3,3 ′, 3′- Tetramethyl-1,1′-spirobiindane, 4,5,6,7,4 ′, 5 ′, 6′-hexahydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, 5,6,7,5 ′, 6 ′, 7′-hexahydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, 4,5,6,7,4 ′, 5 ', 6'-Hexahydroxy-1,1'-spirobiindane, 5,6,7,5', 6 ', 7'-hexahydroxy-1,1'-spirobiindane, 7,7'-dihydroxy-4,4 , 4 ′, 4′-tetramethyl-2,2′-spirobichroman, 7,7′-dihydroxy-2,2′-spirobichroman, 7,7′-dihydro Xi-4,4,4 ′, 4 ′, 6,6′-hexamethyl-2,2′-spirobichroman, 7,7′-dihydroxy-4,4,4 ′, 4′-tetramethyl-6 6′-diethyl-2,2′-spirobichroman, 7,7′-dihydroxy-4,4,4 ′, 4′-tetramethyl-8,8′-diisopropyl-2,2′-spirobichroman, 7,7′-dihydroxy-4,4,4 ′, 4′-tetramethyl-6,6′-dimethoxy-2,2′-spirobichroman, 7,7′-dihydroxy-4,4,4 ′, 4'-tetramethyl-8,8'-diethoxy-2,2'-spirobichroman, 7,7'-dihydroxy-4,4,4 ', 4'-tetramethyl-6,6'-dichloro-2 , 2'-spirobichroman, 7,7'-dihydroxy-4,4,4 ', 4', 4,4'-hexamethyl-2,2'-spiro Chroman, 7,7'-dihydroxy-4,4,4 ', 4'-tetramethyl-8,8'-di-n-propyl-2,2'-spirobichroman, 7,7'-dihydroxy-4 , 4,4 ′, 4′-tetramethyl-4,4′-di-tert-butyl-2,2′-spirobichroman, 7,7′-dihydroxy-4,4,4 ′, 4′-tetra Methyl-4,4′-dimethoxy-2,2′-spirobichroman, 7,7′-dihydroxy-4,4,4 ′, 4′-tetramethyl-6,6′-diethoxy-2,2′- Spirobichroman, 7,7′-dihydroxy-4,4,4 ′, 4′-tetramethyl-6,6′-di-n-propoxy-2,2′-spirobichroman, 7,7′-dihydroxy -4,4,4 ', 4'-tetramethyl-4,4'-dichloro-2,2'-spirobichroman, 7,7'-dihydro -4,4,4 ', 4', 8,8'-hexamethyl-2,2 ', -spirobichroman, 7,7'-dihydroxy-4,4,4', 4'-tetramethyl-8 , 8'-di-n-butoxy-2,2'-spirobiidan, 7,7'-dihydroxy-4,4,4 ', 4'-tetramethyl-6,6'-di-n-propyl-2, 2′-spirobichroman, 7,7′-dihydroxy-4,4,4 ′, 4′-tetramethyl-8,8′-di-n-butyl-2,2′-spirobichroman, 7,7 '-Dihydroxy-4,4,4', 4'-tetramethyl-6,6'-diisopropoxy-2,2'-spirobichroman, 7,7'-dihydroxy-4,4,4 ', 4 '-Tetramethyl-8,8'-diethyl-2,2'-spirobichroman, 7,7'-dihydroxy-4,4,4', 4'-tetramethyl-6,6 '-Diisobutyl-2,2'-spirobichroman, 7,7'-dihydroxy-4,4,4', 4'-tetramethyl-4,4'-diethoxy-2,2'-spirobichroman, 7 , 7'-dihydroxy-4,4,4 ', 4'-tetramethyl-8,8'-di-n-butoxy-2,2'-spirobichroman, 7,7'-dihydroxy-4,4 4 ′, 4′-tetramethyl-2,2′-spirobichroman, 7,7′-dihydroxy-4,4,4 ′, 4 ′, 6,6′-hexamethyl-2,2′-spirobichroman 7,7′-dihydroxy-4,4,4 ′, 4′-tetramethyl-6,6′-di-tert-butyl-2,2′-spirobichroman, 7,7′-dihydroxy-4, 4,4 ′, 4′-tetramethyl-8,8′-dimethoxy-2,2′-spirobichroman, 7,7′-dihydroxy- 4,4,4 ′, 4′-tetramethyl-8,8′-dichloro-2,2′-spirobichroman, 7,7′-dihydroxy-4,4,4 ′, 4′-tetramethyl-2 , 2′-spirobichroman, 7,7′-dihydroxy-4,4,4 ′, 4 ′, 6,6′-hexamethyl-2,2′-spirobichroman, 7,7′-dihydroxy-4, 4,4 ′, 4′-tetramethyl-6,6′-diisopropyl-2,2′-spirobichroman, 6,6 ′, 7,7′-tetrahydroxy-4,4,4 ′, 4′- Tetramethyl-2,2′-spirobichroman, 4,4 ′, 7,7′-tetrahydroxy-4,4,4 ′, 4′-tetramethyl-2,2′-spirobichroman, 7,7 ', 8,8'-tetrahydroxy-4,4,4', 4'-tetramethyl-2,2'-spirobichroman, 4,7,8,4 ', 7', 8 ' -Hexahydroxy-4,4,4 ', 4'-tetramethyl-2,2'-spirobichroman, 4,6,7,8,4', 6 ', 7'-hexahydroxy-4,4 4 ′, 4′-tetramethyl-2,2′-spirobichroman, 6,7,8,6 ′, 7 ′, 8′-hexahydroxy-4,4,4 ′, 4′-tetramethyl-2 , 2′-spirobichroman, 4,6,7,8,4 ′, 6 ′, 7′-hexahydroxy-2,2′-spirobichroman, 6,7,8,6 ′, 7 ′, 8 '-Hexahydroxy-2,2'-spirobichroman. Among them, 5,5 ′, 6,6′-tetrahydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, 7,7 ′, 8,8′-tetrahydroxy-4 4,4 ′, 4′-tetramethyl-2,2′-spirobichroman is preferred. For example, it is possible to obtain a compound having physical properties preferable for use in forming a resist material having high sensitivity and excellent solubility and substrate adhesion.

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

  The resist composition of the present invention comprises an acid generator (B) that generates an acid directly or indirectly by irradiation with radiation selected from visible light, ultraviolet light, excimer laser, electron beam, X-ray, and ion beam. ), And at least one acid crosslinking agent (C).

  The compound (A) is an acid amplification type compound, and when an acid coexists, the acid cross-linking agent (C) and the compound (A) are cross-linked between molecules or within the molecule to become an alkali-insoluble material. Since the portion where no acid coexists becomes an alkali-soluble material, it can be used as a negative resist capable of alkali development. The method for generating the acid is not particularly limited, but for example, an acid is generated in a radiation exposure part such as ultraviolet rays and high energy by coexisting an acid generator.

  That is, in the present invention, as long as an acid is generated in the system, the method for generating the acid is not limited. If excimer laser is used instead of ultraviolet rays such as g-line and i-line, finer processing is possible, and if electron beam, X-ray and ion beam are used as high-energy rays, further fine processing is possible. is there.

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

In the formula (5), R ²³ may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, hydroxyl Or a halogen atom, and X ⁻ is a sulfonate ion or a halide ion having an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group.

  The compound represented by the formula (5) is triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate. Di-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl-4- Hydroxyphenylsulfonium trifluoromethanesulfonate, bis (4-fluorophenyl) -4-hydroxyphenylsulfoniu Trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, tri (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (4-fluoro Phenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium- 2-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium 4-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenylnaphthylsulfonium trifluoromethanesulfonate And at least one selected from the group consisting of diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, and diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate.

In the formula (6), R ²⁴ may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, hydroxyl Represents a group or a halogen atom.

  The compound represented by the formula (6) includes bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butyl). Phenyl) iodonium perfluoro-n-octanesulfonate, bis (4-tert-butylphenyl) iodonium p-toluenesulfonate, bis (4-tert-butylphenyl) iodoniumbenzenesulfonate, bis (4-tert-butylphenyl) iodonium- 2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluorobenzenesulfonate, bis (4- t-Butyl Nyl) iodonium hexafluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyl Iodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyliodonium-2,4-difluorobenzenesulfonate To diphenyliodonium Safluorobenzenesulfonate, di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, di (4-trifluoromethylphenyl) iodonium perfluoro- n-octanesulfonate, di (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, di (4-trifluoromethylphenyl) iodoniumbenzenesulfonate, and di (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate It is preferably at least one selected from the group.

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

  The compound represented by the formula (7) includes N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoro Methylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- (1 -Camphorsulfonyloxy) naphthylimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) naphthyl Imido, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2- (Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4- Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (per Fluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) naphthylimide N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (Perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene- It is preferably at least one selected from the group consisting of 2,3-dicarboximide and N- (perfluoro-n-octanesulfonyloxy) naphthylimide.

In formula (8), R ²⁶ may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, and optionally substituted. A heteroaryl group, or an optionally substituted aralkyl group.

  The compound represented by the formula (8) includes diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone, di It should be at least one selected from the group consisting of (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone, and di (4-tolufluoromethylphenyl) disulfone. Is preferred.

In formula (9), R ²⁷ may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, and optionally substituted. A heteroaryl group, or an optionally substituted aralkyl group.

  The compound represented by the formula (9) includes α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -phenyl. Acetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile, and It is preferably at least one selected from the group consisting of α- (methylsulfonyloxyimino) -4-bromophenylacetonitrile.

In formula (10), R ²⁸ may be the same or different and each independently represents a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms. The halogenated alkyl group preferably has 1 to 5 carbon atoms. The compound represented by the formula (10) is selected from the group consisting of monochloroisocyanuric acid, monobromoisocyanuric acid, dichloroisocyanuric acid, dibromoisocyanuric acid, trichloroisocyanuric acid, and tribromoisocyanuric acid It is preferable that there is at least one kind.

In formulas (11) and (12), R ²⁹ and R ³⁰ are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group or an isopropyl group; a cyclopentyl group or a cyclohexyl group. A cycloalkyl group such as methoxy group, ethoxy group, propoxy group or the like; an alkoxyl group having 1 to 3 carbon atoms; an aryl group such as phenyl group, toluyl group or naphthyl group, preferably 6 to 10 carbon atoms An aryl group. L ²⁹ and L ³⁰ are each independently an organic group having a 1,2-naphthoquinonediazide group. Specific examples of the organic group having a 1,2-naphthoquinonediazide group include a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, and a 1,2-naphthoquinonediazide- A 1,2-quinonediazidosulfonyl group such as a 6-sulfonyl group can be mentioned as a preferable one. In particular, 1,2-naphthoquinonediazido-4-sulfonyl group and 1,2-naphthoquinonediazide-5-sulfonyl group are preferable. p is an integer of 1 to 3, q is an integer of 0 to 4, and 1 ≦ p + q ≦ 5. J ²⁹ is a single bond, a polymethylene group having 2 to 4 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, a phenylene group having 6 to 10 carbon atoms, a substituent represented by the following formula (13), a carbon atom A carbonyl group having 1 to 4 carbon atoms, an ester group having 1 to 4 carbon atoms, an amide group having 1 to 4 carbon atoms, or an ether group having 0 to 4 carbon atoms, and Y ²⁹ is a hydrogen atom or the number of carbon atoms 1 to 3 alkyl groups or aryl groups having 6 to 10 carbon atoms, and X ²⁹ and X ³⁰ are each independently a group represented by the following formula (14).

In formula (14), Z ³² is each independently an alkyl group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R ³² is It is an alkyl group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms, and r is an integer of 0 to 3. )

  Other acid generators include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) ) Bissulfonyldiazomethanes such as diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, 2- (4-methoxyphenyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3 5-triazine, tris (2,3-dibromopropyl) Halogen-containing triazine derivatives, such as isocyanurate and the like.

  Moreover, an acid generator (B) can be used individually or in mixture of 2 or more types. In the composition of the present invention, the amount of the acid generator used is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, and still more preferably 1 to 100 parts by weight per 100 parts by weight of the compound (A). 15 parts by weight. If the amount is less than 0.1 part by weight, the sensitivity and resolution tend to decrease. On the other hand, if the amount exceeds 30 parts by weight, the cross-sectional shape of the resist pattern tends to decrease.

  The resist composition of the present invention contains one or more acid crosslinking agents (C). The acid cross-linking agent (C) is a compound that cross-links with the acid used, and is directly applied by irradiation with any radiation selected from acid, visible light, ultraviolet light, excimer laser, electron beam, X-ray, and ion beam. It is a compound that can crosslink the compound (A) in the presence of a generated acid or indirectly. Examples of such a crosslinking agent include compounds having one or more substituents (hereinafter referred to as “crosslinkable substituents”) having crosslinking reactivity with the compound (A).

  Specific examples of such a crosslinkable substituent include, for example, (i) a hydroxyalkyl group such as a hydroxyalkyl group, an alkoxyalkyl group, an acetoxyalkyl group or a substituent derived therefrom; (ii) a formyl group, a carboxyalkyl A carbonyl group such as a group or a substituent derived therefrom; (iii) a nitrogen-containing group-containing substituent such as a dimethylaminomethyl group, a diethylaminomethyl group, a dimethylolaminomethyl group, a diethylolaminomethyl group, a morpholinomethyl group; (Iv) Glycidyl group-containing substituents such as glycidyl ether group, glycidyl ester group and glycidylamino group; (v) Allyloxyalkyl groups such as benzyloxymethyl group and benzoyloxymethyl group, and aromatics such as aralkyloxyalkyl group A substituent derived from a group; (vi) Group, such as a polymerizable multiple bond-containing substituents such as isopropenyl group, and the like. As the crosslinkable substituent of the acid crosslinking agent (C) used in the present invention, a hydroxyalkyl group, an alkoxyalkyl group, and the like are preferable, and an alkoxymethyl group is particularly preferable.

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

  As the acid cross-linking agent (C), a compound having a phenolic hydroxyl group, and a compound and resin imparted with properties as a cross-linking agent by introducing the cross-linkable substituent into an acidic functional group in an alkali-soluble resin are used. can do. The introduction rate of the crosslinkable substituent in that case is usually 5 to 100 mol%, preferably 10 to 60 mol%, more preferably 10 to 60 mol%, based on the total acidic functional groups in the compound having a phenolic hydroxyl group and the alkali-soluble resin. Preferably, it is adjusted to 15 to 40 mol%. If the introduction ratio of the crosslinkable substituent is less than 5 mol%, it is difficult to cause a sufficient crosslinking reaction, and the remaining film ratio is lowered, the pattern swelling phenomenon, the meandering, and the like are likely to occur.

  In the resist composition of the present invention, the acid crosslinking agent (C) is preferably an alkoxyalkylated urea compound or a resin thereof, or an alkoxyalkylated glycoluril compound or a resin thereof. Examples of the acid crosslinking agent (C1) particularly preferable as the acid crosslinking agent (C) include compounds represented by the following formulas (2) to (4) and alkoxymethylated melamine compounds.

In formulas (2) to (4), R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acyl group having 2 to 6 carbon atoms. The alkyl group having 1 to 5 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The acyl group having 2 to 6 carbon atoms is preferably an acyl group having 2 to 4 carbon atoms, and examples thereof include an acetyl group and a propionyl group. R < ⁶ > -R < ⁹ > in Formula (2) represents a hydrogen atom, a hydroxyl group, a C1-C5 alkyl group, or a C1-C5 alkoxyl group each independently. The alkyl group having 1 to 5 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The alkoxy group having 1 to 5 carbon atoms is preferably an alkoxy group having 1 to 3 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group. X ² represents a single bond, a methylene group, or an oxygen atom. Furthermore, a single bond or a methylene group is preferable. R ^{5 to} R ⁹ and X ² each have a substituent such as an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, a hydroxyl group or a halogen atom in addition to the groups exemplified above. You may do it.

  Specific examples of the compound represented by the formula (2) include the compounds shown below.

  Specific examples of the compound represented by the formula (3) include N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) glycoluril, N , N, N, N-tetra (n-propoxymethyl) glycoluril, N, N, N, N-tetra (i-propoxymethyl) glycoluril, N, N, N, N-tetra (n-butoxymethyl) Examples thereof include glycoluril, N, N, N, N-tetra (t-butoxymethyl) glycoluril and the like. Among these, N, N, N, N-tetra (methoxymethyl) glycoluril is particularly preferable.

  Specifically as a compound represented by Formula (4), the compound shown below etc. can be mentioned, for example.

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

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

  Further, as a particularly preferred crosslinking agent (C2) as the acid crosslinking agent (C), it is a phenol derivative having 1 to 6 benzene rings in the molecule, and has 2 or more hydroxyalkyl groups and / or alkoxyalkyl groups in the whole molecule. And compounds having a hydroxyalkyl group and / or an alkoxyalkyl group bonded to any benzene ring. Preferably, the molecular weight is 1500 or less, the molecule has 1 to 6 benzene rings, and has 2 or more hydroxyalkyl groups and / or alkoxyalkyl groups, and the hydroxyalkyl groups and / or alkoxyalkyl groups are contained therein. A phenol derivative formed by concentrating or allocating to any one of the benzene rings can be exemplified.

  As a hydroxyalkyl group couple | bonded with a benzene ring, a hydroxymethyl group, 2-hydroxyethyl group, and 2-hydroxy-1-propyl group are preferable. As the alkoxyalkyl group bonded to the benzene ring, those having 6 or less carbon atoms are preferable. Specifically, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, sec-butoxymethyl group, t-butoxymethyl group, 2- A methoxyethyl group and a 2-methoxy-1-propyl group are preferred. Among these phenol derivatives, particularly preferable ones are listed below.

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

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

  A phenol derivative having a hydroxymethyl group or an alkoxymethyl group synthesized in this manner is preferable from the viewpoint of stability during storage, but a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage. Such a phenol derivative having two or more hydroxymethyl groups or alkoxymethyl groups in total and concentrated on any benzene ring or distributed and bonded may be used alone or in combination of two kinds. A combination of the above may also be used.

Moreover, as a particularly preferable crosslinking agent (C3) as the acid crosslinking agent (C), a compound having an α-hydroxyisopropyl group can be exemplified. The compound having an α-hydroxyisopropyl group is not particularly limited as long as it has an α-hydroxyisopropyl group. In addition, the α-hydroxyisopropyl group is obtained by replacing the hydrogen atom of the hydroxyl group in the α-hydroxyisopropyl group with one or more acid dissociable groups (R—COO— group, R—SO ₂ — group, etc.). Groups are also included. Examples of the compound having an α-hydroxyisopropyl group include one or two types such as a substituted or unsubstituted aromatic compound, diphenyl compound, naphthalene compound, and furan compound containing at least one α-hydroxyisopropyl group. The above is mentioned. Specifically, for example, a compound represented by the following formula (15) (hereinafter referred to as “benzene compound (15)”), a compound represented by the following formula (16) (hereinafter referred to as “diphenyl compound ( 16) "), a compound represented by the following formula (17) (hereinafter referred to as" naphthalene compound (17) "), and a compound represented by the following formula (18) (hereinafter referred to as" furan compound "). (18) ")).

In the above formulas (15) to (18), each A ² independently represents an α-hydroxyisopropyl group or a hydrogen atom, and at least one A ² is an α-hydroxyisopropyl group. In formula (15), R ₅₁ represents a hydrogen atom, a hydroxyl group, a linear or branched alkylcarbonyl group having 2 to 6 carbon atoms, or a linear or branched alkoxycarbonyl group having 2 to 6 carbon atoms. Indicates a group. Further, in the formula (16), R ₅₂ represents a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —CO—, or —COO—. In formula (18), R ₅₃ and R ₅₄ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

  Specific examples of the benzene compound (15) include α-hydroxyisopropylbenzene, 1,3-bis (α-hydroxyisopropyl) benzene, 1,4-bis (α-hydroxyisopropyl) benzene, 1,2 , 4-Tris (α-hydroxyisopropyl) benzene, α-hydroxyisopropylbenzenes such as 1,3,5-tris (α-hydroxyisopropyl) benzene; 3-α-hydroxyisopropylphenol, 4-α-hydroxyisopropylphenol , 3,5-bis (α-hydroxyisopropyl) phenol, α-hydroxyisopropylphenols such as 2,4,6-tris (α-hydroxyisopropyl) phenol; 3-α-hydroxyisopropylphenyl methyl ketone, 4-α -Hydroxyisopropyl Phenyl methyl ketone, 4-α-hydroxyisopropylphenyl ethyl ketone, 4-α-hydroxyisopropylphenyl n-propyl ketone, 4-α-hydroxyisopropylphenyl isopropyl ketone, 4-α-hydroxyisopropylphenyl n-butyl ketone, 4-α-hydroxyisopropylphenyl · t-butylketone, 4-α-hydroxyisopropylphenyl · n-pentylketone, 3,5-bis (α-hydroxyisopropyl) phenyl · methylketone, 3,5-bis (α-hydroxyisopropyl) ) Phenyl ethyl ketone, α-hydroxyisopropylphenyl alkyl ketones such as 2,4,6-tris (α-hydroxyisopropyl) phenyl methylketone; 3-α-hydroxyisopropylbenzoic acid , Methyl 4-α-hydroxyisopropyl benzoate, ethyl 4-α-hydroxyisopropyl benzoate, n-propyl 4-α-hydroxyisopropyl benzoate, isopropyl 4-α-hydroxyisopropyl benzoate, 4-α-hydroxyisopropyl N-butyl benzoate, t-butyl 4-α-hydroxyisopropylbenzoate, n-pentyl 4-α-hydroxyisopropylbenzoate, methyl 3,5-bis (α-hydroxyisopropyl) benzoate, 3,5-bis Examples include 4-α-hydroxyisopropyl benzoate alkyls such as ethyl (α-hydroxyisopropyl) benzoate and methyl 2,4,6-tris (α-hydroxyisopropyl) benzoate.

  Specific examples of the diphenyl compound (16) include 3-α-hydroxyisopropylbiphenyl, 4-α-hydroxyisopropylbiphenyl, 3,5-bis (α-hydroxyisopropyl) biphenyl, 3,3 ′. -Bis (α-hydroxyisopropyl) biphenyl, 3,4'-bis (α-hydroxyisopropyl) biphenyl, 4,4'-bis (α-hydroxyisopropyl) biphenyl, 2,4,6-tris (α-hydroxyisopropyl ) Biphenyl, 3,3 ′, 5-tris (α-hydroxyisopropyl) biphenyl, 3,4 ′, 5-tris (α-hydroxyisopropyl) biphenyl, 2,3 ′, 4,6, -tetrakis (α-hydroxy) Isopropyl) biphenyl, 2,4,4 ′, 6, -tetrakis (α-hydroxyiso) Propyl) biphenyl, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) biphenyl, 2,3 ′, 4,5 ′, 6-pentakis (α-hydroxyisopropyl) biphenyl, 2,2 ′, 4 , 4 ′, 6,6′-hexakis (α-hydroxyisopropyl) biphenyl and the like α-hydroxyisopropylbiphenyls; 3-α-hydroxyisopropyldiphenylmethane, 4-α-hydroxyisopropyldiphenylmethane, 1- (4-α-hydroxy) Isopropylphenyl) -2-phenylethane, 1- (4-α-hydroxyisopropylphenyl) -2-phenylpropane, 2- (4-α-hydroxyisopropylphenyl) -2-phenylpropane, 1- (4-α- Hydroxyisopropylphenyl) -3-phenylpropane, 1- 4-α-hydroxyisopropylphenyl) -4-phenylbutane, 1- (4-α-hydroxyisopropylphenyl) -5-phenylpentane, 3,5-bis (α-hydroxyisopropyldiphenylmethane, 3,3′-bis ( α-hydroxyisopropyl) diphenylmethane, 3,4′-bis (α-hydroxyisopropyl) diphenylmethane, 4,4′-bis (α-hydroxyisopropyl) diphenylmethane, 1,2-bis (4-α-hydroxyisopropylphenyl) ethane 1,2-bis (4-α-hydroxypropylphenyl) propane, 2,2-bis (4-α-hydroxypropylphenyl) propane, 1,3-bis (4-α-hydroxypropylphenyl) propane, 2, , 4,6-Tris (α-hydroxyisopropyl) diphe Lumethane, 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenylmethane, 3,4 ′, 5-tris (α-hydroxyisopropyl) diphenylmethane, 2,3 ′, 4,6-tetrakis (α-hydroxyisopropyl) Diphenylmethane, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenylmethane, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) diphenylmethane, 2,3 ′, 4,5 ′, 6 Α-hydroxyisopropyldiphenylalkanes such as pentakis (α-hydroxyisopropyl) diphenylmethane, 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenylmethane; 3-α-hydroxyisopropyldiphenyl ether 4-α-hydroxyisopro Rudiphenyl ether, 3,5-bis (α-hydroxyisopropyl) diphenyl ether, 3,3′-bis (α-hydroxyisopropyl) diphenyl ether, 3,4′-bis (α-hydroxyisopropyl) diphenyl ether, 4,4′-bis (Α-hydroxyisopropyl) diphenyl ether, 2,4,6-tris (α-hydroxyisopropyl) diphenyl ether, 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenyl ether, 3,4 ′, 5-tris (α- Hydroxyisopropyl) diphenyl ether, 2,3 ′, 4,6-tetrakis (α-hydroxyisopropyl) diphenyl ether, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenyl ether, 3,3 ′, 5,5 ′ -Tetrakis α-hydroxyisopropyl) diphenyl ether, 2,3 ′, 4,5 ′, 6-pentakis (α-hydroxyisopropyl) diphenyl ether, 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) Α-hydroxyisopropyl diphenyl ethers such as diphenyl ether; 3-α-hydroxyisopropyl diphenyl ketone, 4-α-hydroxyisopropyl diphenyl ketone, 3,5-bis (α-hydroxyisopropyl) diphenyl ketone, 3,3′-bis (α -Hydroxyisopropyl) diphenylketone, 3,4'-bis (α-hydroxyisopropyl) diphenylketone, 4,4'-bis (α-hydroxyisopropyl) diphenylketone, 2,4,6-tris (α-hydroxyisopropyl) Diphenyl , 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenyl ketone, 3,4 ′, 5-tris (α-hydroxyisopropyl) diphenyl ketone, 2,3 ′, 4,6-tetrakis (α-hydroxy) Isopropyl) diphenyl ketone, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenyl ketone, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) diphenyl ketone, 2,3 ′, 4 , 5 ′, 6-pentakis (α-hydroxyisopropyl) diphenyl ketone, α-hydroxyisopropyl diphenyl ketones such as 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenyl ketone; Phenyl 3-α-hydroxyisopropyl benzoate, 4-α-hydroxyisopropyl benzoate Phenyl benzoate, 3-α-hydroxyisopropylphenyl benzoate, 4-α-hydroxyisopropylphenyl benzoate, phenyl 3,5-bis (α-hydroxyisopropyl) benzoate, 3-α-hydroxyisopropylbenzoate 3-α -Hydroxyisopropylphenyl, 3-α-hydroxyisopropylbenzoic acid 4-α-hydroxyisopropylphenyl, 4-α-hydroxyisopropylbenzoic acid 3-α-hydroxyisopropylphenyl, 4-α-hydroxyisopropylbenzoic acid 4-α-hydroxy Isopropyl phenyl, 3,5-bis (α-hydroxyisopropyl) phenyl benzoate, phenyl 2,4,6-tris (α-hydroxyisopropyl) benzoate, 3,5-bis (α-hydroxyisopropyl) benzoic acid 3- α-hydroxy Sopropylphenyl, 3,5-bis (α-hydroxyisopropyl) benzoate 4-α-hydroxyisopropylphenyl, 3-α-hydroxyisopropylbenzoate 3,5-bis (α-hydroxyisopropyl) phenyl, 4-α- 3,5-bis (α-hydroxyisopropyl) phenyl hydroxyisopropylbenzoate, 2,4,6-tris (α-hydroxyisopropyl) phenyl benzoate, 2,4,6-tris (α-hydroxyisopropyl) benzoic acid 3 -Α-hydroxyisopropylphenyl, 2,4,6-tris (α-hydroxyisopropyl) benzoic acid 4-α-hydroxyisopropylphenyl, 3,5-bis (α-hydroxyisopropyl) benzoic acid 3,5-bis (α -Hydroxyisopropyl) phenyl, 3-α-hydroxyisopropyl Pyrbenzoate 2,4,6-tris (α-hydroxyisopropyl) phenyl, 4-α-hydroxyisopropylbenzoate 2,4,6-tris (α-hydroxyisopropyl) phenyl, 2,4,6-tris (α -Hydroxyisopropyl) benzoic acid 3,5-bis (α-hydroxyisopropyl) phenyl, 3,5-bis (α-hydroxyisopropyl) benzoic acid 2,4,6-tris (α-hydroxyisopropyl) phenyl, 2,4 , 6-tris (α-hydroxyisopropyl) benzoic acid 2,4,6-tris (α-hydroxyisopropyl) phenyl and the like α-hydroxyisopropylbenzoic acid phenyls and the like.

  Further, specific examples of the naphthalene compound (17) include 1- (α-hydroxyisopropyl) naphthalene, 2- (α-hydroxyisopropyl) naphthalene, 1,3-bis (α-hydroxyisopropyl) naphthalene, 1,4-bis (α-hydroxyisopropyl) naphthalene, 1,5-bis (α-hydroxyisopropyl) naphthalene, 1,6-bis (α-hydroxyisopropyl) naphthalene, 1,7-bis (α-hydroxyisopropyl) Naphthalene, 2,6-bis (α-hydroxyisopropyl) naphthalene, 2,7-bis (α-hydroxyisopropyl) naphthalene, 1,3,5-tris (α-hydroxyisopropyl) naphthalene, 1,3,6-tris (Α-hydroxyisopropyl) naphthalene, 1,3,7-tris (α Hydroxyisopropyl) naphthalene, 1,4,6-tris (α-hydroxyisopropyl) naphthalene, 1,4,7-tris (α-hydroxyisopropyl) naphthalene, 1,3,5,7-tetrakis (α-hydroxyisopropyl) And naphthalene.

  Specific examples of the furan compound (18) include 3- (α-hydroxyisopropyl) furan, 2-methyl-3- (α-hydroxyisopropyl) furan, 2-methyl-4- (α- Hydroxyisopropyl) furan, 2-ethyl-4- (α-hydroxyisopropyl) furan, 2-n-propyl-4- (α-hydroxyisopropyl) furan, 2-isopropyl-4- (α-hydroxyisopropyl) furan, 2 -N-butyl-4- (α-hydroxyisopropyl) furan, 2-t-butyl-4- (α-hydroxyisopropyl) furan, 2-n-pentyl-4- (α-hydroxyisopropyl) furan, 2,5 -Dimethyl-3- (α-hydroxyisopropyl) furan, 2,5-diethyl-3- (α-hydroxyisopropyl) fura 3,4-bis (α-hydroxyisopropyl) furan, 2,5-dimethyl-3,4-bis (α-hydroxyisopropyl) furan, 2,5-diethyl-3,4-bis (α-hydroxyisopropyl) ) Furan etc. can be mentioned.

  The acid crosslinking agent (C3) is preferably a compound having two or more free α-hydroxyisopropyl groups, a benzene compound (15) having two or more α-hydroxyisopropyl groups, and two or more α-hydroxyisopropyl groups. More preferred are diphenyl compounds (16), naphthalene compounds (17) having two or more α-hydroxyisopropyl groups, α-hydroxyisopropylbiphenyls having two or more α-hydroxyisopropyl groups, and α-hydroxyisopropyl groups. A naphthalene compound (17) having two or more is particularly preferred.

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

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

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

  In the total acid crosslinking agent, the alkoxymethylated melamine compound and / or the compound represented by the formula (4) is 50 to 99% by weight, preferably 60 to 99% by weight, more preferably 70 to 98% by weight, still more preferably. It is preferably 80 to 97% by weight. Since the resolution can be improved by setting the alkoxymethylated melamine compound and / or the compound represented by the formula (4) to 50% by weight or more of the total acid crosslinking agent component, it is preferable that the compound be 99% by weight or less. The pattern cross-sectional shape is preferable because it is easy to obtain a rectangular cross-sectional shape.

  In the resist composition of the present invention, an acid diffusion control agent, a dissolution control agent, a dissolution accelerator, a sensitizer, and other components (D) as necessary, as long as the object of the present invention is not impaired. One or more kinds of various additives such as a surfactant can be added.

[1] Acid Diffusion Control Agent In the present invention, an action of controlling an undesired chemical reaction in an unexposed area by controlling a diffusion phenomenon in a resist film of an acid generated from a photoacid generator by irradiation. You may mix | blend the acid diffusion control agent which has. By using such an acid diffusion control agent, the storage stability of the resist composition is improved, the resolution is improved, and the holding time before electron beam irradiation and the fluctuation of the holding time after electron beam irradiation are varied. It is possible to suppress the change in the line width of the resist pattern due to the above, and the process stability is extremely excellent.

  Examples of the acid diffusion controller include nitrogen-containing organic compounds and basic compounds that decompose upon exposure. Examples of the nitrogen-containing organic compound include a compound represented by the following general formula (19) (hereinafter referred to as “nitrogen-containing compound (I)”), a diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (I)”). , "Nitrogen-containing compound (II)"), polyamino compounds and polymers having 3 or more nitrogen atoms (hereinafter referred to as "nitrogen-containing compound (III)"), amide group-containing compounds, urea compounds, and And nitrogen heterocyclic compounds. In addition, the said acid diffusion control agent may be used individually by 1 type, and may use 2 or more types together.

In said formula (19), _R61 , _R62 and _R63 show a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, or an aralkyl group mutually independently. The alkyl group, aryl group, or aralkyl group may be unsubstituted or substituted with another functional group such as a hydroxyl group. Here, examples of the linear, branched or cyclic alkyl group include those having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, specifically, methyl group, ethyl group, n- Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, Examples include n-octyl group, n-ethylhexyl group, n-nonyl group, n-decyl group and the like. Moreover, as said aryl group, a C6-C12 thing is mentioned, Specifically, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, 1-naphthyl group, etc. are mentioned. Furthermore, examples of the aralkyl group include those having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, and specific examples include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.

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

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

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

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

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

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

  Moreover, as a basic compound decomposed | disassembled by the said exposure, the iodonium compound etc. which are represented by the sulfonium compound represented by following formula (20), and following formula (21) can be mentioned, for example.

In the above formula (20) and ^{(21), R 71, R} 72, R 73, R 74 and ^{R 75} represents independently from each other a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group or a halogen atom. Furthermore, Z ^- is HO-, R-COO- (where, R represents an alkyl group, an aryl group or alkaryl group.) Shows a or anion represented by the following formula (22).

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

  The compounding amount of the acid diffusion controller in the present invention is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight, still more preferably 0.01 to 3 parts per 100 parts by weight of the compound (A). Parts by weight. If the blending amount of the acid diffusion control agent is less than 0.001 part by weight, depending on the process conditions, there is a tendency for the resolution, pattern shape, dimensional fidelity, etc. to deteriorate, and further, from electron beam irradiation to heating after radiation irradiation If the holding time of the pattern becomes longer, the pattern shape tends to deteriorate in the upper layer portion of the pattern. On the other hand, when the compounding amount of the acid diffusion controller exceeds 10 parts by weight, the sensitivity as a resist, the developability of an unexposed part, etc. tend to be lowered.

[2] Solubility control agent The solubilization control agent has a function of appropriately reducing the dissolution rate during development by controlling the solubility when the compound (A) is too high in a developer such as an alkali. It is an ingredient. As such a dissolution control agent, those that do not chemically change in steps such as baking of the resist film, irradiation with radiation, and development are preferable.

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

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

[3] Dissolution Accelerator A dissolution accelerator increases the solubility of the compound (A) during development when the solubility of the compound (A) in a developing solution such as alkali is too low. A component having an increasing effect. As such a dissolution accelerator, those that do not chemically change in steps such as baking of the resist film, electron beam irradiation, and development are preferable. Examples of the dissolution accelerator include low molecular weight phenolic compounds having about 2 to 6 benzene rings, and specific examples include bisphenols and tris (hydroxyphenyl) methane. it can. These dissolution promoters can be used alone or in admixture of two or more.

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

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

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

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

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

[6] Acid diffusion controller, dissolution accelerator, dissolution controller, sensitizer, and other additives other than surfactants Further, the resist composition of the present invention has a range that does not impair the object of the present invention. Thus, if necessary, one or more additives other than the acid diffusion controller, the dissolution accelerator, the dissolution controller, the sensitizer, and the surfactant can be blended. Examples of other additives include dyes, pigments, and adhesion aids. For example, it is preferable to add a dye or a pigment because the latent image in the exposed area can be visualized and the influence of halation during exposure can be reduced. In addition, it is preferable to add an adhesion assistant because the adhesion to the substrate can be improved. Furthermore, examples of other additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improving agent, and the like, specifically 4-hydroxy-4′-methylchalcone.

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

  Examples of the solvent used for preparing the resist composition of the present invention include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate. Ethylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol monoalkyl ether acetates such as propylene glycol mono-n-butyl ether acetate ; Propylene glycol monomethyl ether, propylene glycol monoethyl Propylene glycol monoalkyl ethers such as ether; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate; methyl acetate, ethyl acetate, n-propyl acetate, n-acetate Aliphatic carboxylic esters such as butyl, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, 3-methoxy-3- Butyl methyl butyrate, methyl acetoacetate, pyruvate Other esters such as ruthenium and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; N, N-dimethylformamide, N- Examples include amides such as methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; lactones such as γ-lactone, but are not particularly limited. These solvents can be used alone or in combination of two or more.

  The resist composition of the present invention can be used in combination with a compound and / or resin that is soluble in an alkaline aqueous solution as long as the object of the present invention is not impaired. Although it does not specifically limit as a compound soluble in alkaline aqueous solution, For example, the phenolic compound which has phenolic hydroxyl groups, such as a polyphenol compound, is mentioned, As a resin soluble in alkaline aqueous solution, a novolak resin, polyvinylphenols , Polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as monomer units, or derivatives thereof. In addition, a vinyl group which is a cross-linking reactive group that causes a cross-linking reaction by irradiation with visible light, ultraviolet light, excimer laser, electron beam, X-ray and ion beam or a chemical reaction induced thereby without departing from the object of the present invention. , An allyl group, a cinnamoyl group, a vinylsilyl group, an epoxy group, a chloromethyl group, and a halogenated phenyl group and / or a resin can be used in combination. The compound and / or resin having a crosslinking reactive group is not particularly limited, but the compound and / or resin soluble in the alkaline aqueous solution, visible light, ultraviolet light, excimer laser, electron beam, X-ray and ion beam. Examples include compounds and / or polymers produced by reacting a crosslinking reactive group-introducing agent that undergoes a crosslinking reaction by irradiation or a chemical reaction induced thereby under a basic catalyst, or derivatives thereof. The term “crosslinking reactive group introduction reagent” as used herein refers to an acid having a crosslinking reactive group, an acid chloride, an acid anhydride, a carboxylic acid derivative compound such as dicarbonate, an alkyl halide, or the like. Of these, acid chlorides are particularly preferred. The crosslinking reactive group is a vinyl group, an allyl group, a cinnamoyl group, a vinylsilyl group, an epoxy group, a chloromethyl group, or a halogenated phenyl group. One or more of these may be mixed and used.

  The composition of the resist composition of the present invention is usually 65 to 96.9% by weight of the compound (A), 0.1 to 30% by weight of the acid generator (B), and the acid crosslinking agent (C) 0 in the total solid. 0.3 to 34.9% by weight, other components (D) 0 to 30% by weight are preferred, (A) 65 to 96.9% by weight, (B) 0.1 to 30% by weight, (C) 0. 3 to 34.9% by weight, (D) 0 to 10% by weight is more preferable, (A) 65 to 96.9% by weight, (B) 0.1 to 30% by weight, and (C) 0.6 to 34%. 9.9 wt%, (D) 0-5 wt% is more preferred, (A) 65-96.9 wt%, (B) 0.1-30 wt%, (C) 0.6-30 wt%, (D) 0% by weight is particularly preferred. By setting it within the above range, the performance such as sensitivity, resolution, and alkali developability is excellent.

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

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

  Next, the coated substrate is heated as necessary. Although the heating conditions vary depending on the composition of the resist composition, 20 to 250 ° C is preferable, and 20 to 150 ° C is more preferable. Heating may improve the adhesion of the resist to the substrate, which is preferable. Next, the resist film is exposed to a desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, X-ray, and ion beam. The exposure conditions and the like are appropriately selected according to the composition of the resist composition. In the present invention, in order to stably form a high-precision fine pattern in exposure, heating is preferably performed after irradiation with radiation. The heating condition varies depending on the composition of the resist composition, but is preferably 20 to 250 ° C, more preferably 20 to 150 ° C.

  Next, the exposed resist film is developed with an alkaline developer to form a predetermined resist pattern. Examples of the alkaline developer include alkaline such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), choline and the like. An alkaline aqueous solution in which one or more compounds are dissolved so as to have a concentration of preferably 1 to 10% by weight, more preferably 1 to 5% by weight is used. When the concentration of the alkaline aqueous solution is 10% by weight or less, it is preferable because the exposed portion can be prevented from being dissolved in the developer.

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

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

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

The resist pattern can be peeled off with an organic solvent or a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate) and the like. As the strong alkaline aqueous solution, for example, 1 to 20% by weight sodium hydroxide aqueous solution And 1-20% by weight potassium hydroxide aqueous solution. Examples of the peeling method include a dipping method and a spray method.
In addition, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.

  The wiring board can also be formed by a method in which after the resist pattern is formed using the pattern-formed substrate obtained in the present invention, a metal is vapor-deposited in a vacuum and then the resist pattern is dissolved in a solution, that is, a lift-off method.

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

Each measurement method is shown below.
(1) Evaluation of film formability of resist film A 10 × 10 mm square resist film was divided into 100 sections, the sections where the resist film was not formed and the sections that were crystallized were counted and evaluated according to the following criteria.
Zero: Good 1 or more: Defect (2) 5 μmL & S of resist pattern
The developed resist pattern was observed with an optical microscope, and it was confirmed whether or not a 5 μm line and space was formed.
(3) Substrate adhesion of resist pattern A 10 × 10 mm square resist film was divided into 100 sections, and the sections where the resist film was peeled off were counted and evaluated according to the following criteria.
Zero: Good One or more points: Poor (4) Resistance to etching of resist pattern Aluminum (alloy with Si and Cu) thin film (about 200 nm) is deposited on a silicon wafer using SH-550 type high-rate sputtering device manufactured by Japan Vacuum Technology. I let you. A resist film was formed thereon, a pattern was formed by exposure and development, and then etching was performed.
Etching solution: 0.1N sodium hydroxide aqueous solution Etching time: 3 min
After etching under the above conditions, the resist was washed with pure water and the residual resist was dissolved with acetone. The etching pattern at that time was observed with an optical microscope, and the shape of the pattern was judged visually.

<Example 1>
5,5 ′, 6,6′-tetrahydroxy-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the formula (23) as the compound (A) (0.067 g), 1,2-naphthoquinone-2-diazide-5-sulfonate sodium (0.01 g) as the acid generator (B), Nicalac MW-100LM (Sanwa Chemical ( (Made by Co., Ltd.) (0.033 g) and a solvent (ethyl lactate / propylene glycol monomethyl ether acetate = 5/2) (3.89 g) in a uniform solution, then a Teflon (registered trademark) membrane filter having a pore size of 0.2 μm To prepare a resist solution.

The obtained resist solution was spin-coated on a clean silicon wafer to form a resist film. The film formability was good.
Pre-exposure baking (PB) was performed in an oven at 100 ° C. for 10 minutes to form a resist film having a thickness of 0.2 μm. The resist film was exposed by being irradiated with i-line having a wavelength of 365 nm under the condition of 220 mJ / cm @ 2. Thereafter, the film was baked after exposure in an oven at 175 ° C. for 10 minutes, and developed at 23 ° C. by standing in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 5 seconds. Thereafter, it was washed with water for 30 seconds and dried to form a negative resist pattern. A 5 μmL & S pattern having a good pattern shape was obtained. The substrate adhesion of the resist pattern was good.
In addition, when a resist solution was spin-coated on a silicon wafer on which an aluminum thin film was deposited, a resist film was formed, a pattern was formed, and etching resistance was evaluated.

Claims (11)

Compound (A) represented by formula (1), visible light, ultraviolet light, excimer laser, electron beam, X-ray, and ion beam are directly or indirectly irradiated with any radiation selected from the group consisting of ions. A resist composition comprising a generated acid generator (B) and an acid crosslinking agent (C).

(In formula (1), R1 to R8 are independently a hydrogen atom or a hydroxy group, and at least two are hydroxy groups. R9 to R12 are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Z is an oxygen atom or a single bond.) The radiation-sensitive composition according to claim 1, wherein R1 to R4 in formula (1) are hydrogen atoms, R9 to R12 are methyl groups, and R5 to R8 are hydroxy groups. The resist composition according to claim 1, comprising two or more of the compounds (A). The resist according to any one of claims 1 to 3, wherein the acid crosslinking agent (C) is a compound selected from the group consisting of compounds represented by formulas (2) to (4) and an alkoxymethylated melamine compound. Composition.

(In formulas (2) to (4), each R ¹³ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acyl group having 2 to 6 carbon atoms. In formula (2), R ¹⁴ to R ¹⁷ each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or an alkoxyl group having 1 to 5 carbon atoms, and X ² represents a single bond, a methylene group, or an oxygen atom. ) Compound (A) 65-96.9% by weight, acid generator (B) 0.1-30% by weight, acid crosslinking agent (C) 0.3-34.9% by weight, other components in the total solid (D) It is 0-30 weight%, The resist composition in any one of Claims 1-4. Compound (A) 65-96.9 wt%, acid generator (B) 0.1-30 wt%, acid crosslinking agent (C) 0.6-30 wt%, other components (D) The resist composition according to claim 1, wherein the resist composition is 0% by weight. A resist substrate comprising a resist film made of the resist composition according to claim 1 on a substrate. A pattern-formed substrate, wherein a resist film comprising the resist composition according to claim 1 is patterned. A step of forming a resist film by applying the resist composition according to any one of claims 1 to 6 on a substrate, the resist film comprising visible light, ultraviolet light, excimer laser, electron beam, X-ray, and ion beam. A resist pattern comprising a step of irradiating and exposing one of the radiations selected from the group, and a step of developing the exposed resist film with an alkali developer after heat treatment as necessary Forming method. A step of coating the resist composition according to claim 1 on a substrate to form a resist film, a step of heat-treating the resist film, a heat-treated resist film with visible light, ultraviolet rays, excimer laser, A step of irradiating with radiation selected from the group consisting of an electron beam, an X-ray, and an ion beam and exposing the exposed resist film with an alkali developer after heat treatment as necessary A resist pattern forming method comprising the steps of: A pattern wiring board obtained by performing etching after performing the pattern forming method according to claim 9.