# US 9,436,093 B2 · Pattern forming process and shrink agent > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,436,093 B2 - Document ID: US9436093B2 - Status: Granted - Kind: B2 - Application number: 14/930,772 - Filed: 2015-11-03 - Published: 2016-05-05 - Granted: 2016-09-06 - Earliest claimed: 2014-11-04 - Assignees: Shin-Etsu Chemical Co., Ltd. - Applicants: Shin-Etsu Chemical Co., Ltd. - Inventors: Jun Hatakeyama; Masayoshi Sagehashi - Web page: https://patentgrep.com/patent/US9436093B2 ## CPC - G03F 7/40: Treatment after imagewise removal, e.g. baking - 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 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain} - G03F 7/094: {Multilayer resist systems, e.g. planarising layers} - G03F 7/11: having cover layers or intermediate layers, e.g. subbing layers {(G03F7/091 - G03F7/093, B41N3/03 take 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 7/32: Liquid compositions therefor, e.g. developers - G03F 7/325: {Non-aqueous compositions} - G03F 7/38: Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)} - G03F 7/405: {Treatment with inorganic or organometallic reagents after imagewise removal} - 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) ## Abstract A negative pattern is formed by applying a resist composition onto a substrate, exposing the resist film, and developing the exposed resist film in an organic solvent developer. The process further involves coating the negative pattern with a shrink agent solution of a polymer comprising recurring units capable of forming lactam under the action of acid in a C7-C16 ester or C7-C16 ketone solvent, baking the coating, and removing the excessive shrink agent via organic solvent development for thereby shrinking the size of spaces in the pattern. ## Claims ### Claim 1 A pattern forming process comprising the steps of: applying a resist composition onto a substrate, said resist composition comprising a polymer comprising recurring units having an acid labile group-substituted carboxyl group, an acid generator and an organic solvent, prebaking to form a resist film, exposing the resist film to high-energy radiation, baking the film, developing the exposed resist film in an organic solvent-based developer to form a negative resist pattern, applying a shrink agent onto the negative resist pattern, said shrink agent being a solution of a polymer comprising recurring units (a1) having the general formula (1) in a solvent selected from the group consisting of ester solvents of 7 to 16 carbon atoms and ketone solvents of 7 to 16 carbon atoms, baking, and removing the excessive shrink agent with the organic solvent-based developer for thereby shrinking the size of spaces in the pattern, wherein R1 is hydrogen or methyl, R2 is a straight or branched C2-C8 alkylene group, R3 is a straight, branched or cyclic C1-C8 alkyl group which may contain an ether moiety, ester moiety or halogen, or an acid labile group, X1 is phenylene or —C(═O)—O—R4—, R4 is a single bond, a straight, branched or cyclic C1-C8 alkylene group, or phenylene group. ### Claim 2 (depends on 1) The pattern forming process of claim 1 wherein the polymer comprising recurring units (a1) in the shrink agent further comprises recurring units (b) having a hydroxyl, carboxyl, lactone ring, lactam ring, sultone ring, sulfone, sulfonic acid ester, sulfonamide, carboxylic acid amide, nitro, cyano, thienyl, furyl, pyrrole, acid anhydride, imide, —NH—(C═O)—O—, —S—(C═O)—O—, or —ON(═O2)—. ### Claim 3 (depends on 1) The pattern forming process of claim 1 wherein the solvent in the shrink agent is at least one solvent selected from the group consisting of ester solvents of 7 to 16 carbon atoms including amyl acetate, isoamyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, hexyl formate, ethyl valerate, propyl valerate, isopropyl valerate, butyl valerate, isobutyl valerate, tert-butyl valerate, amyl valerate, isoamyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, tert-butyl isovalerate, isoamyl isovalerate, ethyl 2-methylvalerate, butyl 2-methylvalerate, ethyl pivalate, propyl pivalate, isopropyl pivalate, butyl pivalate, tert-butyl pivalate, ethyl pentenoate, propyl pentenoate, isopropyl pentenoate, butyl pentenoate, tert-butyl pentenoate, propyl crotonate, isopropyl crotonate, butyl crotonate, tert-butyl crotonate, butyl propionate, isobutyl propionate, tert-butyl propionate, benzyl propionate, ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, tert-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, ethyl phenylacetate, and 2-phenylethyl acetate, and ketone solvents of 7 to 16 carbon atoms including 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, diisobutyl ketone, ethylcyclohexanone, ethylacetophenone, ethyl n-butyl ketone, di-n-butyl ketone, and diisobutyl ketone. ### Claim 4 (depends on 1) The pattern forming process of claim 1 wherein the polymer in the resist composition comprises recurring units (a2) having the general formula (2): wherein R5 is hydrogen or methyl, R6 is an acid labile group, Z is a single bond or —C(═O)—O—R7—, R7 is a straight, branched or cyclic C1-C10 alkylene group which may contain ether or ester, or naphthylene group, and 0