# US 9,519,218 B2 · Resin, resist composition and method for producing resist pattern > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,519,218 B2 - Document ID: US9519218B2 - Status: Granted - Kind: B2 - Application number: 14/854,881 - Filed: 2015-09-15 - Published: 2016-03-17 - Granted: 2016-12-13 - Earliest claimed: 2014-09-16 - Assignees: Sumitomo Chemical Company, Limited - Applicants: Sumitomo Chemical Company, Limited - Inventors: Masahiko Shimada; Takashi Nishimura; Koji Ichikawa - Web page: https://patentgrep.com/patent/US9519218B2 ## CPC - G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain} - C08F 28/06: by a heterocyclic ring containing sulfur - C08F 214/186: {with non-fluorinated comonomers} - C08F 220/22: Esters containing halogen - G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors} - G03F 7/0046: {with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence)} - G03F 7/2041: {in the presence of a fluid, e.g. immersion; using fluid cooling means} - G03F 7/30: Imagewise removal using liquid means - G03F 7/322: {Aqueous alkaline compositions} - G03F 7/325: {Non-aqueous compositions} - G03F 7/38: Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)} - C08F 222/185: {the ester chains containing seven or more carbon atoms} - C08F 222/245: {the ester chains containing seven or more carbon atoms} - 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) - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract 1. A resist composition includes (A1) a resin which includes a structural unit represented by formula (a4), and a structural unit having a sulfonyl group, and the resin has no acid-labile group, (A2) a resin having an acid-labile group, and an acid generator. wherein R3 represents a hydrogen atom or a methyl group, and R4 represents a C1 to C24 saturated hydrocarbon group having a fluorine atom, and a methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or a carbonyl group. ## Claims ### Claim 1 A resist composition comprising (A1) a resin which comprises a structural unit represented by formula (a4): wherein R3 represents a hydrogen atom or a methyl group, and R4 represents a C1 to C24 saturated hydrocarbon group having a fluorine atom, and a methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or a carbonyl group, and a structural unit having a sultone ring, and the resin having no acid-labile group, (A2) a resin having an acid-labile group, and an acid generator. ### Claim 2 (depends on 1) The resist composition according to claim 1, wherein the sultone ring is a ring represented by formula (T1): wherein R8 represents a C1 to C12 alkyl group that may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, a C1 to C12 alkoxy group, a C6 to C12 aryl group, a C7 to C18 aralkyl group, a glycidyloxy group, a C2 to C12 alkoxycarbonyl group or a C2 to C4 acyl group, and m represents an integer 0 to 9. ### Claim 3 (depends on 1) The resist composition according to claim 1, wherein the resin (A1) further comprises a structural unit represented by formula (I): wherein R1 represents a hydrogen atom or a methyl group, L1 represents a single bond or a C1 to C18 divalent saturated hydrocarbon group where a methylene group may be replaced by an oxygen atom or a carbonyl group, and R2 represents a C3 to C18 alicyclic hydrocarbon group where a hydrogen atom may be replaced by a C1 to C8 aliphatic hydrocarbon group or a hydroxy group, provided that the carbon atom directly bonded to L1 has no aliphatic hydrocarbon group by which a hydrogen atom has been replaced. ### Claim 4 (depends on 3) The resist composition according to claim 3, wherein R2 is an unsubstituted C3 to C18 alicyclic hydrocarbon group. ### Claim 5 (depends on 1) The resist composition according to claim 1, wherein the structural unit represented by the formula (a4) is at least one structural unit selected from the group consisting of a structural unit represented by formula (a4-0), a structural unit represented by formula (a4-1), a structural unit represented by formula (a4-2) and a structural unit represented by formula (a4-3): wherein Rf1 represents a hydrogen atom or a methyl group, and Rf2 represents a C1 to C20 saturated hydrocarbon group having a fluorine atom; wherein Rf3 represents a hydrogen atom or a methyl group, L3 represents a C1 to C18 divalent saturated hydrocarbon group where a methylene group may be replaced by an oxygen atom or a carbonyl group, and Rf4 represents a C1 to C20 saturated hydrocarbon group having a fluorine atom; wherein Rf5 represents a hydrogen atom or a methyl group, L4 represents a C1 to C18 divalent saturated hydrocarbon group where a methylene group may be replaced by an oxygen atom or a carbonyl group, and Rf6 represents a C1 to C20 saturated hydrocarbon group having a fluorine atom; wherein Rf7 represents a hydrogen atom or a methyl group, L5 represent a C1 to C6 alkanediyl group, Af13 represents a C1 to C18 divalent saturated hydrocarbon group that may have a fluorine atom, Xf12 represents an oxycarbonyl group or a carbonyloxy group, and Af14 represents a C1 to C17 saturated hydrocarbon group that may have a fluorine atom, provided that at least one of Af13 and Af14 represents a saturated hydrocarbon group having a fluorine atom. ### Claim 6 (depends on 1) The resist composition according to claim 1, wherein the resin (A2) comprises a structural unit selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2): wherein La1 and La2 independently represent —O— or *—O—(CH2)k1—CO—O—, k1 represents an integer of 1 to 7, * represents a binding site to —CO—, Ra4 and Ra5 each independently represent a hydrogen atom or a methyl group, Ra6 and Ra7 each independently represent a C1 to C8 alkyl group, a C3 to C18 alicyclic hydrocarbon group or a combination thereof, m1 represents an integer of 0 to 14, n1 represents an integer of 0 to 10, and n1′ represents an integer of 0 to 3. ### Claim 7 (depends on 6) The resist composition according to claim 6, wherein the resin (A2) comprises a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2). ### Claim 8 (depends on 1) A method for producing a resist pattern comprising steps (1) to (5); (1) applying the resist composition according to claim 1 onto a substrate; (2) drying the applied composition to form a composition layer; (3) exposing the composition layer; (4) heating the exposed composition layer, and (5) developing the heated composition layer. ### Claim 9 A resin comprising a structural unit represented by formula (a4): wherein R3 represents a hydrogen atom or a methyl group, R4 represents a C1 to C24 saturated hydrocarbon group having a fluorine atom and a methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or a carbonyl group and a structural unit having a sultone ring, the resin having no acid-labile group. ### Claim 10 (depends on 9) The resin according to claim 9, wherein the sultone ring is a ring represented by formula (T1): wherein R8 represents a C1 to C12 alkyl group that may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, a C1 to C12 alkoxy group, a C6 to C12 aryl group, a C7 to C18 aralkyl group, a glycidyloxy group, a C2 to C12 alkoxycarbonyl group or a C2 to C4 acyl group, and m represents an integer 0 to 9. ### Claim 11 (depends on 9) The resin according to claim 9, wherein the resin (A1) further comprises a structural unit represented by formula (I): wherein R1 represents a hydrogen atom or a methyl group, L1 represents a single bond or a C1 to C18 divalent saturated hydrocarbon group where a methylene group may be replaced by an oxygen atom or a carbonyl group, and R2 represents a C3 to C18 alicyclic hydrocarbon group where a hydrogen atom may be replaced by a C1 to C8 aliphatic hydrocarbon group or a hydroxy group, provided that the carbon atom directly bonded to L1 has no aliphatic hydrocarbon group by which a hydrogen atom has been replaced. ### Claim 12 (depends on 11) The resin according to claim 11, wherein R2 is an unsubstituted C3 to C18 alicyclic hydrocarbon group. ### Claim 13 (depends on 9) The resin according to claim 9, wherein the structural unit represented by the formula (a4) is at least one structural unit selected from the group consisting of a structural unit represented by formula (a4-0), a structural unit represented by formula (a4-1), a structural unit represented by formula (a4-2) and a structural unit represented by formula (a4-3): wherein Rf1 represents a hydrogen atom or a methyl group, and Rf2 represents a C1 to C20 saturated hydrocarbon group having a fluorine atom; wherein Rf3 represents a hydrogen atom or a methyl group, L3 represents a C1 to C18 divalent saturated hydrocarbon group where a methylene group may be replaced by an oxygen atom or a carbonyl group, and Rf4 represents a C1 to C20 saturated hydrocarbon group having a fluorine atom; wherein Rf5 represents a hydrogen atom or a methyl group, L4 represents a C1 to C18 divalent saturated hydrocarbon group where a methylene group may be replaced by an oxygen atom or a carbonyl group, and Rf6 represents a C1 to C20 saturated hydrocarbon group having a fluorine atom; wherein Rf7 represents a hydrogen atom or a methyl group, L5 represent a C1 to C6 alkanediyl group, Af13 represents a C1 to C18 divalent saturated hydrocarbon group that may have a fluorine atom, Xf12 represents an oxycarbonyl group or a carbonyloxy group, and Af14 represents a C1 to C17 saturated hydrocarbon group that may have a fluorine atom, provided that at least one of Af13 and Af14 represents a saturated hydrocarbon group having a fluorine atom.