# US 2015/0147702 A1 · 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 2015/0147702 A1 - Document ID: US20150147702A1 - Status: Published application - Kind: A1 - Application number: 14/608,887 - Filed: 2015-01-29 - Published: 2015-05-28 - Earliest claimed: 2011-09-22 - Assignees: Tokyo Ohka Kogyo Co., Ltd. - Applicants: Tokyo Ohka Kogyo Co., Ltd. - Inventors: Tsuyoshi Nakamura; Jiro Yokoya; Hiroaki Shimizu; Hideto Nito - Web page: https://patentgrep.com/patent/US20150147702A1 ## CPC - G03F 7/38: Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)} - G03F 7/004: Photosensitive materials (G03F7/12, G03F7/14 take precedence) - 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 7/0382: {the macromolecular compound being present in a chemically amplified negative photoresist composition} - G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain} - G03F 7/0755: {Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence)} - G03F 7/0758: {with silicon- containing groups in the side chains} - G03F 7/20: Exposure; Apparatus therefor (photographic printing apparatus for making copies G03B27/00) - 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 method of forming a resist pattern, including forming a resist film by coating a resist composition including a base component (A) that exhibits increased solubility in an alkali developing solution, a photo-base generator component (C) that generates a base upon exposure, an acid supply component (Z) and a compound (F) containing at least one selected from the group consisting of a fluorine atom and a silicon atom and containing no acid decomposable group which exhibits increased polarity by the action of acid on a substrate; subjecting the resist film to exposure baking the exposed resist film; and subjecting the resist film to alkali development, thereby forming a negative-tone resist pattern. ## Claims ### Claim 1 A method of forming a resist pattern, comprising: a step (1) in which a resist composition comprising a base component (A) that exhibits increased solubility in an alkali developing solution under the action of acid, a photo-base generator component (C) that generates a base upon exposure, an acid supply component (Z) and a compound (F) containing at least one selected from the group consisting of a fluorine atom and a silicon atom is applied to a substrate to form a resist film; a step (2) in which the resist film is subjected to exposure; a step (3) in which baking is conducted after the step (2), such that, at an exposed portion of the resist film, the base generated from the photo-base generator component (C) upon the exposure and an acid derived from the acid supply component (Z) are neutralized, and at an unexposed portion of the resist film, the solubility of the base component (A) in an alkali developing solution is increased by the action of the acid derived from the acid supply component (Z); and a step (4) in which the resist film is subjected to an alkali development, thereby forming a negative-tone resist pattern in which the unexposed portion of the resist film has been dissolved and removed, wherein the compound (F) contains no acid decomposable group which exhibits increased polarity by the action of acid. ### Claim 2 (depends on 1) The method according to claim 1, wherein the compound (F) contains a polymer having a structural unit represented by general formula (f1-1) shown below, or a compound represented by general formula (f11-1) shown below: wherein R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; A represents —O— or —NH—; X0 represents a single bond or a divalent linking group; R0 represents an organic group; at least one of X0 and R0 contains a fluorine atom or a silicon atom; and v is 0 or 1. ### Claim 3 (depends on 1) The method according to claim 1, wherein the acid supply component (Z) comprises an acidic compound component (G). ### Claim 4 (depends on 3) The method according to claim 3, wherein the resist composition further comprises an amine (D). ### Claim 5 (depends on 3) The method according to claim 3, wherein the acidic compound component (G) includes an acid salt component (G1) having an acid strength capable of increasing the solubility of the base component (A) in an alkali developing solution. ### Claim 6 (depends on 5) The method according to claim 5, wherein the component (G1) is an ionic compound composed of a nitrogen-containing cation and a counteranion. ### Claim 7 (depends on 5) The method according to claim 5, wherein the component (G1) is an ionic compound composed of a cation moiety represented by general formula (G1c-1) shown below and a counteranion: wherein R101d, R101e, R101f and R101g each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, an alkenyl group, an oxoalkyl group or an oxoalkenyl group of 1 to 12 carbon atoms, an aryl group or an arylalkyl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 12 carbon atoms or an aryloxoalkyl group, and part or all of the hydrogen atoms of these groups may be substituted with a halogen atom, an alkoxy group or a sulfur atom. R101d and R101e, or R101d, R101e and R101f may be mutually bonded with the nitrogen atom to form a ring, provided that, when a ring is formed, each of R101d and R101e, or each of R101d, R101e and R101f independently represents an alkylene group of 3 to 10 carbon atoms, or forms a heteroaromatic ring containing the nitrogen atom in the ring thereof. ### Claim 8 (depends on 5) The method according to claim 5, wherein the component (G1) is an ionic compound comprising: a nitrogen-containing cation; and a counteranion having at least one anion group selected from the group consisting of a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis(alkylsulfonyl)imide anion and a tris(alkylsulfonyl)methide anion. ### Claim 9 A method of forming a resist pattern, comprising: a step (1) in which a resist composition comprising a base component (A) that exhibits increased solubility in an alkali developing solution under the action of acid, a photo-base generator component (C) that generates a base upon exposure, an acidic compound component (G) and an amine (D) is applied to a substrate to form a resist film; a step (2) in which the resist film is subjected to exposure; a step (3) in which baking is conducted after the step (2), such that, at an exposed portion of the resist film, the base generated from the photo-base generator component (C) upon the exposure and the acidic compound component (G) are neutralized, and at an unexposed portion of the resist film, the solubility of the base component (A) in an alkali developing solution is increased by the action of the acidic compound component (G); and a step (4) in which the resist film is subjected to an alkali development, thereby forming a negative-tone resist pattern in which the unexposed portion of the resist film has been dissolved and removed, wherein the amount of the amine (D) is 1 mol or more, per 1 mol of the acidic compound component (G). ### Claim 10 (depends on 9) The method according to claim 9, wherein the amount of the amine (D) is 1 to 10 mol, per 1 mol of the acidic compound component (G). ### Claim 11 A method of forming a resist pattern, comprising: a step (1) in which a resist composition comprising a base component (A) that exhibits increased solubility in an alkali developing solution under the action of acid, a photo-base generator component (C) that generates a base upon exposure, and an acidic compound component (G) is applied to a substrate to form a resist film; a step (2) in which the resist film is subjected to exposure; a step (3) in which baking is conducted after the step (2), such that, at an exposed portion of the resist film, the base generated from the photo-base generator component (C) upon the exposure and the acidic compound component (G) are neutralized, and at an unexposed portion of the resist film, the solubility of the base component (A) in an alkali developing solution is increased by the action of the acidic compound component (G); and a step (4) in which the resist film is subjected to an alkali development, thereby forming a negative-tone resist pattern in which the unexposed portion of the resist film has been dissolved and removed, wherein the acidic compound component (G) comprises a compound (G1C) composed of a nitrogen-containing cation having a pKa value of 7 or less and a counteranion. ### Claim 12 (depends on 11) The method according to claim 11, wherein the resist composition further comprises an amine (D).