# US 7,745,093 B2 · Water soluble resin composition and method for pattern formation using the same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 7,745,093 B2 - Document ID: US7745093B2 - Status: Granted - Kind: B2 - Application number: 11/547,707 - Filed: 2005-04-08 - Published: 2008-08-14 - Granted: 2010-06-29 - Earliest claimed: 2004-04-09 - Assignees: AZ Electronic Materials USA Corp. - Inventors: Takeshi Nishibe; Sung Eun Hong; Yusuke Takano; Tetsuo Okayasu - Web page: https://patentgrep.com/patent/US7745093B2 ## CPC - G03F 7/40: Treatment after imagewise removal, e.g. baking - H10P 76/204: {of organic photoresist masks} - Y10S 430/106: Binder containing - Y10S 430/11: Vinyl alcohol polymer or derivative - Y10S 430/115: Cationic or anionic - Y10S 430/162: Protective or antiabrasion layer - Y10S 430/165: Thermal imaging composition - 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) - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract In the present invention, in a water soluble resin composition for use in a method for pattern formation in which a covering layer is provided on a resist pattern formed of a radiation-sensitive resin composition capable of coping with ArF exposure to increase the width of the resist pattern and thus to realize effective formation of higher density trench or hole pattern, the size reduction level of the resist pattern layer can be further increased as compared with that in the prior art technique, and, in addition, the size reduction level dependency of the coarse-and-fine resist pattern can be reduced. A method for pattern formation using the water soluble resin composition is also provided. The water soluble resin composition which is usable for the method for pattern formation applicable to ArF excimer laser irradiation comprises a water soluble resin, an acid generating agent capable of generating an acid upon heating, a surfactant, a crosslinking agent, and a water-containing solvent. ## Claims ### Claim 1 A water soluble resin composition for use in a semiconductor manufacturing process, where said water soluble resin composition comprises a water soluble resin, an acid generating agent capable of generating an acid upon heating, a crosslinking agent, and a water-containing solvent, wherein said acid generating agent is represented by formula wherein R0 represents —CnH2n+1−mFm where n is 1 to 20 and m is 0 to 2n+1, where R′ is —(CH2)xCH3, —OH, or —COOH in which x is 0 to 20; and R1, R2, R3, and R4 each independently represent —H, CpH2p+1, or —CpH2pOH where p is 1 to 10. ### Claim 2 (depends on 1) The water soluble resin composition according to claim 1, wherein said water soluble resin comprises a copolymer of N-vinylpyrrolidone with vinylimidazole. ### Claim 3 (depends on 1) The water soluble resin composition according to claim 1, which further comprises at least one surfactant selected from the group consisting of acetylenic alcohols, acetylenic glycols, polyethoxylates of acetylenic alcohols, and polyethoxylates of acetylenic glycols. ### Claim 4 (depends on 1) The water soluble resin composition according to claim 1, wherein said water-containing solvent consists of water alone, or a mixture of water with a water soluble organic solvent. ### Claim 5 (depends on 1) The water soluble resin composition according to claim 1, wherein said crosslinking agent is an alkylated urea, oxazoline group-containing polymer, or polyamines. ### Claim 6 (depends on 1) The water soluble resin composition according to claim 1, which comprises, based on 100 parts by weight of the water soluble resin composition, 1 to 30 parts by weight of the water soluble resin, 0.01 to 10 parts by weight of the acid generating agent. ### Claim 7 (depends on 1) A method for pattern formation, comprising the steps of: coating the water soluble resin composition according claim 1 onto a resist pattern formed of a radiation-sensitive resin composition capable of coping with ArF exposure to form a covering layer; heating the covering layer to crosslink the covering layer in its part with a predetermined thickness located near the resist pattern to form a modified covering layer insoluble in a developing solution; and developing the modified covering layer to form a pattern in which the surface of the resist pattern has been covered with the modified covering layer. ### Claim 8 (depends on 7) The method of claim 7, where the modified covering layer has a film thickness in the range of 0.01 to 100 μm. ### Claim 9 (depends on 1) A pattern covered with a modified covering layer, which is composed of resist pattern formed of a radiation-sensitive resin composition capable of coping with ArF exposure and the modified covering layer formed on the surface of the resist pattern, wherein the modifiedcovering layer is formed by coating the water soluble resin composition according to claim 1 onto the resist pattern to form a covering layer, by heating the covering layer located near the resist pattern to crosslink in its part with a predetermined thickness to form the modified covering layer insoluble in a developing solution and by developing the modified covering layer to form the pattern. ### Claim 10 (depends on 9) The pattern of claim 9, where the modified covering layer has a film thickness in the range of 0.01 to 100 μm. ### Claim 11 (depends on 1) The composition of claim 1, where the water soluble resin has the structure, wherein Ra and Rb each independently represents a hydrogen atom or a methyl group; Rc represents —OH, —COOH, —OCORd, where Rd represents an alkyl group, or and a and b each independently are 10 to 100,000.