# US 7,608,381 B2 · Polymer compound, positive resist composition and process for 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 7,608,381 B2 - Document ID: US7608381B2 - Status: Granted - Kind: B2 - Application number: 11/570,761 - Filed: 2005-06-10 - Published: 2008-04-24 - Granted: 2009-10-27 - Earliest claimed: 2004-06-18 - Assignees: Tokyo Ohka Kogyo Co., Ltd. - Inventors: Yohei Kinoshita; Takeshi Iwai - Web page: https://patentgrep.com/patent/US7608381B2 ## CPC - C08F 220/26: Esters containing oxygen in addition to the carboxy oxygen - C08F 220/282: {and containing two or more oxygen atoms} - G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain} - C08F 220/281: {and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate} - C08F 220/283: {and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate} - Y10S 430/111: Polymer of unsaturated acid or ester - Y10S 430/115: Cationic or anionic - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - 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 The positive resist composition of the present invention is a polymer compound comprising at least one constituent unit (a1) selected from the group consisting of constituent units represented by the following general formulas (1) and (1)′, a constituent unit (a2) derived from an (α-lower alkyl)acrylate ester having a lactone-containing monocycle or a polycyclic group, and a constituent unit (a3) which is a constituent unit other than the constituent unit (a1) and the constituent unit (a2) and is derived from an (α-lower alkyl)acrylate ester which has an aliphatic cyclic group-containing non-acid dissociable dissolution inhibiting group and does not have a polar group: wherein R represents a hydrogen atom, a fluorine atom, a lower alkyl group having 20 or less carbon atoms, or a fluorinated lower alkyl group having 20 or less carbon atoms, R1 represents at most 20-membered cyclic group which may have a substituent, n represents 0 or an integer of 1 to 5, and m represents 0 or 1. ## Claims ### Claim 1 A polymer compound comprising: a constituent unit (a1) represented by the following general formula (1): wherein R represents a hydrogen atom, a fluorine atom, a lower alkyl group having 20 or less carbon atoms, or a fluorinated lower alkyl group having 20 or less carbon atoms, R1 represents at most 20-membered cyclic group which may have a substituent, and n represents 0 or an integer of 1 to 5, a constituent unit (a2) derived from an (α-alkyl of 1 to 5 carbon atoms) acrylate ester having a lactone-containing monocycle or a polycyclic group, and a constituent unit (a3) which is a constituent unit other than the constituent unit (a1) and the constituent unit (a2) and is derived from an (α-alkyl of 1 to 5 carbon atoms) acrylate ester which has an aliphatic cyclic group-containing non-acid dissociable dissolution inhibiting group and does not have a polar group, wherein the constituent unit (a2) is a constituent unit represented by the following general formula (5): wherein R′ represents an alkyl group of 1 to 5 carbon atoms or a hydrogen atom, and R2 and R3 each independently represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms. ### Claim 2 (depends on 1) The polymer compound according to claim 1, wherein the constituent unit (a1) is a constituent unit represented by the following general formula (2): wherein R and n are as defined above, X represents a polar group, and 1 represents 0 or an integer of 1 to 3. ### Claim 3 (depends on 1) The polymer compound according to claim 1, wherein the constituent unit (a3) is a constituent unit represented by the following general formula (10): wherein R′ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, Y represents an aliphatic cyclic group whose basic ring has 4 to 15 carbon atoms, and wherein the aliphatic cyclic group may have 1 to 3 alkyl groups having 1 to 10 carbon atoms as substituents to be attached to the basic ring. ### Claim 4 (depends on 3) The polymer compound according to claim 3, wherein the constituent unit (a3) is at least one constituent unit selected from constituent units represented by the following general formulas (11) to (13): wherein R′ is as defined above, wherein R′ is as defined above, and wherein R′ is as defined above. ### Claim 5 (depends on 4) The polymer compound according to claim 4, comprising at least one of: a combination of constituent units represented by the following general formula (14) and a combination of constituent units represented by the following general formula (14)′: wherein R, and R′ are as defined above, and ### Claim 6 (depends on 1) A positive resist composition comprising a base material resin component (A), the alkali solubility of which varies under action of an acid, and an acid generator (B) which generates an acid upon irradiation with radiation, wherein the base material resin component (A) is the polymer compound of claim 1. ### Claim 7 (depends on 6) The positive resist composition according to claim 6, further comprising a nitrogen-containing organic compound (D). ### Claim 8 (depends on 6) A process for forming a resist pattern comprising: forming a resist film on a substrate using the positive resist composition of claim 6; exposing the resist film; and developing the resist film to form a resist pattern. ### Claim 9 A polymer compound comprising: a constituent unit (a1) represented by the following general formula (1)′: wherein R represents a hydrogen atom, a fluorine atom, a lower alkyl group having 20 or less carbon atoms, or a fluorinated lower alkyl group having 20 or less carbon atoms, R1 represents at most 20-membered cyclic group which may have a substituent, n represents 0 or an integer of 1 to 5, and m represents 0 or 1, a constituent unit (a2) derived from an (α-alkyl of 1 to 5 carbon atoms) acrylate ester having a lactone-containing monocycle or a polycyclic group, and a constituent unit (a3) which is a constituent unit other than the constituent unit (a1) and the constituent unit (a2) and is derived from an (α-alkyl of 1 to 5 carbon atoms) acrylate ester which has an aliphatic cyclic group-containing non-acid dissociable dissolution inhibiting group and does not have a polar group. ### Claim 10 (depends on 9) The polymer compound according to claim 9, wherein the constituent unit (a2) is a constituent unit represented by the following general formula (5): wherein R′ represents an alkyl group of 1 to 5 carbon atoms or a hydrogen atom, and R2 and R3 each independently represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms. ### Claim 11 (depends on 9) The polymer compound according to claim 9, wherein the constituent unit (a3) is a constituent unit represented by the following general formula (10): wherein R′ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, Y represents an aliphatic cyclic group whose basic ring has 4 to 15 carbon atoms, and wherein the aliphatic cyclic group may have 1 to 3 alkyl groups having 1 to 10 carbon atoms as substituents to be attached to the basic ring. ### Claim 12 (depends on 11) The polymer compound according to claim 11, wherein the constituent unit (a3) is at least one constituent unit selected from constituent units represented by the following general formulas (11) to (13): wherein R′ is as defined above, wherein R′ is as defined above, and wherein R′ is as defined above. ### Claim 13 (depends on 9) A positive resist composition comprising a base material resin component (A), the alkali solubility varies under action of an acid, and an acid generator (B) which generates an acid upon irradiation with radiation, wherein the base material resin component (A) is the polymer compound of claim 9. ### Claim 14 (depends on 13) The positive resist composition according to claim 13, further comprising a nitrogen-containing organic compound (D). ### Claim 15 (depends on 13) A process for forming a resist pattern comprising: forming a resist film on a substrate using the positive resist composition of claim 13; exposing the resist film; and developing the resist film to form a resist pattern. ### Claim 16 A polymer compound comprising: a constituent unit (a1) represented by the following general formula (1): wherein R represents a hydrogen atom, a fluorine atom, a lower alkyl group having 20 or less carbon atoms, or a fluorinated lower alkyl group having 20 or less carbon atoms, R1 represents at most 20-membered cyclic group which may have a substituent, and n represents 0 or an integer of 1 to 5, a constituent unit (a2) derived from an (α-alkyl of 1 to 5 carbon atoms)acrylate ester having a lactone-containing monocycle or a polycyclic group, and a constituent unit (a3) which is a constituent unit other than the constituent unit (a1) and the constituent unit (a2) and is derived from an (α-alkyl of 1 to 5 carbon atoms)acrylate ester which has an aliphatic cyclic group-containing non-acid dissociable dissolution inhibiting group and does not have a polar group; wherein the constituent unit (a1) is a constituent unit represented by the following general formula (2): wherein R and n are as defined above, X represents a polar group, and 1 represents 0 or an integer of 1 to 3. ### Claim 17 (depends on 16) The polymer compound according to claim 16, wherein the constituent unit (a3) is a constituent unit represented by the following general formula (10): wherein R′ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms; and Y represents an aliphatic cyclic group whose basic ring has 4 to 15 carbon atoms, and the aliphatic cyclic group may have 1 to 3 alkyl groups having 1 to 10 carbon atoms as substituents to be attached to the basic ring. ### Claim 18 (depends on 16) A positive resist composition comprising a base material resin component (A), the alkali solubility of which varies under action of an acid, and an acid generator (B) which generates an acid upon irradiation with radiation, wherein the base material resin component (A) is the polymer compound of claim 16. ### Claim 19 (depends on 18) A process for forming a resist pattern comprising: forming a resist film on a substrate using the positive resist composition of claim 18; exposing the resist film; and developing the resist film to form a resist pattern.