# US 7,745,097 B2 · Compound, manufacturing method thereof, acid generator, resist composition and method of forming resist pattern > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 7,745,097 B2 - Document ID: US7745097B2 - Status: Granted - Kind: B2 - Application number: 12/174,293 - Filed: 2008-07-16 - Published: 2009-01-22 - Granted: 2010-06-29 - Earliest claimed: 2007-07-18 - Assignees: Tokyo Ohka Kogyo Co., Ltd. - Inventors: Hideo Hada; Takeshi Iwai; Takehiro Seshimo; Akiya Kawaue; Keita Ishiduka - Web page: https://patentgrep.com/patent/US7745097B2 ## CPC - C07D 335/02: not condensed with other rings - C07C 309/04: containing only one sulfo group - C07D 333/46: substituted on the ring sulfur atom - G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors} - G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain} - Y10S 430/106: Binder containing - Y10S 430/111: Polymer of unsaturated acid or ester - Y10S 430/122: Sulfur compound containing - Y10S 430/123: Sulfur in heterocyclic ring - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G) - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract There are provided a novel compound represented by a general formula (b1-1) shown below, which is useful as an acid generator for a resist composition and a manufacturing method thereof, a compound useful as a precursor of the novel compound and a manufacturing method thereof, an acid generator, a resist composition and a method of forming a resist pattern. (wherein, R1 represents an aryl group or alkyl group which may contain a substituent group; R3 represents a hydrogen atom or an alkyl group; n1 represents an integer of 0 or 1, and in the case that n1 is 1, R1 and R3 may mutually be bonded to form a ring with a 3- to 7-membered ring structure together with the carbon atom with which R1 is bonded and the carbon atom with which R3 is bonded; A represents a bivalent group which forms a ring with 3- to 7-membered ring structure together with the sulfur atom with which A is bonded, and the ring may contain a substituent group; R2 represents an aromatic group which may contain a substituent group, a linear or branched alkyl group of 1 to 10 carbon atoms which may contain a substituent group, or a linear or branched alkenyl group of 2 to 10 carbon atoms which may contain a substituent group; n represents an integer of 0 or 1; and Y1 represents an alkylene group of 1 to 4 carbon atoms in which hydrogen atoms may be substituted with fluorine atoms.). ## Claims ### Claim 1 A resist composition, which comprises a base component (A) which exhibits changed solubility in an alkali developing solution under action of acid, and an acid generator component (B) which generates an acid upon exposure, wherein the acid generator component (B) comprises an acid generator (B1) represented by a general formula (b1-1) shown below: (wherein, R1 represents an aryl group or alkyl group which may contain a substituent group; R3 represents a hydrogen atom or an alkyl group; n1 represents an integer of 0 or 1, and in the case that n1 is 1, R1 and R3 may mutually be bonded to form a ring with a 3- to 7-membered ring structure together with the carbon atom with which R1 is bonded and the carbon atom with which R3 is bonded; A represents a bivalent group which forms a ring with 3- to 7-membered ring structure together with the sulfur atom with which A is bonded, and the ring may contain a substituent group; R2 represents an aromatic group which may contain a substituent group, a linear or branched alkyl group of 1 to 10 carbon atoms which may contain a substituent group, or a linear or branched alkenyl group of 2 to 10 carbon atoms which may contain a substituent group; n represents an integer of 0; and Y1 represents an alkylene group of 1 to 4 carbon atoms in which hydrogen atoms may be substituted with fluorine atoms). ### Claim 2 (depends on 1) The resist composition according to claim 1, wherein the base component (A) is a base component which exhibits increased solubility in an alkali developing solution under action of acid. ### Claim 3 (depends on 2) The resist composition according to claim 2, wherein the base component (A) comprises a resin component (A1) which exhibits increased solubility in an alkali developing solution under action of acid, and the resin component (A1) comprises a structural unit (a1) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group. ### Claim 4 (depends on 3) The resist composition according to claim 3, wherein the resin component (A1) further comprises a structural unit (a2) derived from an acrylate ester which has a lactone-containing cyclic group. ### Claim 5 (depends on 3) The resist composition according to claim 3, wherein the resin component (A1) further comprises a structural unit (a3) derived from an acrylate ester which has a polar group-containing aliphatic hydrocarbon group. ### Claim 6 (depends on 4) The resist composition according to claim 4, wherein the resin component (A1) further comprises a structural unit (a3) derived from an acrylate ester which has a polar group-containing aliphatic hydrocarbon group. ### Claim 7 (depends on 1) The resist composition according to claim 1, which comprises a nitrogen-containing organic compound (D). ### Claim 8 (depends on 1, 2, 3, 4, 5, 6, 7) A method of forming a resist pattern, comprising: forming a resist film on a substrate using the resist composition described in any one of claim 1 to 7; exposing the resist film; and alkali-developing the resist film to form a resist pattern. ### Claim 9 A compound represented by a general formula (b1-1) shown below: (wherein, R1 represents an aryl group or alkyl group which may contain a substituent group; R3 represents a hydrogen atom or an alkyl group; n1 represents an integer of 0 or 1, and in the case that n1 is 1, R1 and R3 may mutually be bonded to form a ring with a 3- to 7-membered ring structure together with the carbon atom with which R1 is bonded and the carbon atom with which R3 is bonded; A represents a bivalent group which forms a ring with 3- to 7-membered ring structure together with the sulfur atom with which A is bonded, and the ring may contain a substituent group; R2 represents an aromatic group which may contain a substituent group, a linear or branched alkyl group of 1 to 10 carbon atoms which may contain a substituent group, or a linear or branched alkenyl group of 2 to 10 carbon atoms which may contain a substituent group; n represents an integer of 0; and Y1 represents an alkylene group of 1 to 4 carbon atoms in which hydrogen atoms may be substituted with fluorine atoms). ### Claim 10 A method of manufacturing a compound represented by a general formula (b1-1-1) shown below, which comprises reacting a compound represented by a general formula (I) shown below, a compound represented by a general formula (II) shown below, and a copper catalyst, thereby obtaining the compound represented by the general formula (b1-1-1): (wherein, A represents a bivalent group which forms a ring with a 3- to 7-membered ring structure together with the sulfur atom with which A is bonded, and the ring may contain a substituent group; R2 represents an aromatic group which may contain a substituent group, a linear or branched alkyl group of 1 to 10 carbon atoms which may contain a substituent group, or a linear or branched alkenyl group of 2 to 10 carbon atoms which may contain a substituent group; n represents an integer of 0; Y1 represents an alkylene group of 1 to 4 carbon atoms in which hydrogen atoms may be substituted with fluorine atoms; and R1 each independently represents an aryl group or alkyl group which may contain a substituent group). ### Claim 11 A compound represented by a general formula (I) shown below: (wherein, R2 represents an aromatic group which may contain a substituent group, a linear or branched alkyl group of 1 to 10 carbon atoms which may contain a substituent group, or a linear or branched alkenyl group of 2 to 10 carbon atoms which may contain a substituent group; n represents an integer of 0; Y1 represents an alkylene group of 1 to 4 carbon atoms in which hydrogen atoms may be substituted with fluorine atoms; and R1 each independently represents an aryl group or alkyl group which may contain a substituent group). ### Claim 12 A method of manufacturing a compound represented by a general formula (I) shown below, which comprises reacting a compound represented by a general formula (I-1) shown below, a compound represented by a general formula (I-2) shown below, thereby obtaining the compound represented by the general formula (I): (wherein, R2 represents an aromatic group which may contain a substituent group, a linear or branched alkyl group of 1 to 10 carbon atoms which may contain a substituent group, or a linear or branched alkenyl group of 2 to 10 carbon atoms which may contain a substituent group; n represents an integer of 0; Y1 represents an alkylene group of 1 to 4 carbon atoms in which hydrogen atoms may be substituted with fluorine atoms; M+ represents an alkali metal ion; R1 each independently represents an aryl group or alkyl group which may contain a substituent group; and R7 represents an alkyl group or a fluorinated alkyl group). ### Claim 13 (depends on 9) An acid generator composed of the compound described in claim 9. ### Claim 14 (depends on 1) The resist composition according to claim 1, wherein the anionic site of the acid generator (B1) is an anionic site represented by a general formula (b1″-1) shown below: (wherein, Y1 is as defined above; R53 represents an alkenyl group or aryl group of 2 to 10 carbon atoms; and R54 represents a linear or branched alkylene group of 1 to 5 carbon atoms). ### Claim 15 (depends on 9) The compound according to claim 9, wherein the anionic site of the compound represented by the general formula (b1-1) is an anionic site represented by a general formula (b1″-1) shown below: (wherein, Y1 is as defined above; R53 represents an alkenyl group or aryl group of 2 to 10 carbon atoms; and R54 represents a linear or branched alkylene group of 1 to 5 carbon atoms). ### Claim 16 (depends on 1) The resist composition according to claim 1, wherein Y1 is —CF2CF2—, —CF2CF2CF2—, or —CH2CF2CF2—. ### Claim 17 (depends on 9) The compound according to claim 9, wherein Y1 is —CF2CF2—, —CF2CF2CF2—, or —CH2CF2CF2—. ### Claim 18 (depends on 1) The resist composition according to claim 1, wherein said aromatic group which may contain a substituent group is a phenyl group, a biphenyl group, or a naphthyl group; a heteroaryl group in which a part of the carbon atoms which constitutes the rings of a phenyl group, a biphenyl group or a naphthyl group are substituted with heteroatoms; or a benzyl group, a phenylhyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group. ### Claim 19 (depends on 9) The compound according to claim 9, wherein said aromatic group which may contain a substituent group is a phenyl group, a biphenyl group, or a naphthyl group; a heteroaryl group in which a part of the carbon atoms which constitutes the rings of a phenyl group, a biphenyl group or a naphthyl group are substituted with heteroatoms; or a benzyl group, a phenylhyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group.