# US 9,753,370 B2 · Multiple-pattern forming methods > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,753,370 B2 - Document ID: US9753370B2 - Status: Granted - Kind: B2 - Application number: 14/836,050 - Filed: 2015-08-26 - Published: 2016-03-03 - Granted: 2017-09-05 - Earliest claimed: 2014-08-27 - Assignees: Dow Global Technologies LLC; Rohm and Haas Electronic Materials LLC; Rohm and Haas Electronic Materials Korea Ltd. - Applicants: Rohm and Haas Electronic Materials LLC; Dow Global Technologies LLC; Rohm and Haas Electronic Materials Korea Ltd. - Inventors: Chang-Young Hong; Cheng-Bai Xu; Jung Woo Kim; Cong Liu; Shintaro Yamada; Lori Anne Joesten; Choong-Bong Lee; Phillip D. Hustad; James C. Taylor - Web page: https://patentgrep.com/patent/US9753370B2 ## CPC - G03F 7/40: Treatment after imagewise removal, e.g. baking - G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain} - G03F 7/2041: {in the presence of a fluid, e.g. immersion; using fluid cooling means} - G03F 7/322: {Aqueous alkaline compositions} - G03F 7/325: {Non-aqueous compositions} - G03F 7/405: {Treatment with inorganic or organometallic reagents after imagewise removal} - H10P 76/204: {of organic photoresist masks} - H10P 76/4085: {characterised by the processes involved to create the masks} - 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 ## Abstract Multiple-pattern forming methods are provided. The methods comprise: (a) providing a semiconductor substrate comprising one or more layers to be patterned; (b) forming a photoresist layer over the one or more layers to be patterned, wherein the photoresist layer is formed from a composition comprising: a matrix polymer comprising an acid labile group; a photoacid generator; and a solvent; (c) patternwise exposing the photoresist layer to activating radiation; (d) baking the exposed photoresist layer; (e) contacting the baked photoresist layer with a first developer to form a first resist pattern; (f) treating the first resist pattern with a coating composition comprising an expedient for switching solubility of a sidewall region of the first resist pattern from soluble to insoluble with respect to a second developer that is different from the first developer; and (g) contacting the treated first resist pattern with the second developer to remove portions of the first resist pattern, leaving the solubility-switched sidewall region to form a multiple-pattern. The methods have particular applicability to the semiconductor manufacturing industry for the formation of fine lithographic patterns. ## Claims ### Claim 1 A multiple-pattern forming method, comprising: (a) providing a semiconductor substrate comprising one or more layers to be patterned; (b) forming a photoresist layer over the one or more layers to be patterned, wherein the photoresist layer is formed from a composition comprising: a matrix polymer comprising an acid labile group; a photoacid generator; and a solvent; (c) patternwise exposing the photoresist layer to activating radiation; (d) baking the exposed photoresist layer; (e) contacting the baked photoresist layer with a first developer to form a first resist pattern; (f) treating the first resist pattern with a coating composition comprising an expedient for switching solubility of a sidewall region of the first resist pattern from soluble to insoluble with respect to a second developer that is different from the first developer, wherein the expedient comprises an acid or an acid generator chosen from thermal acid generators, photoacid generators, and combinations thereof, or a combination of any of the foregoing; and (g) contacting the treated first resist pattern with the second developer to remove portions of the first resist pattern, leaving the solubility-switched sidewall region to form a multiple-pattern. ### Claim 2 (depends on 1) The multiple-pattern forming method of claim 1, wherein the coating composition comprises a polymer which is soluble in the second developer. ### Claim 3 (depends on 1) The multiple-pattern forming method of claim 1, wherein the coating composition comprises an organic solvent. ### Claim 4 (depends on 1) The multiple-pattern forming method of claim 1, wherein the coating composition further comprises a surface active additive that migrates to an upper surface of a layer formed from the composition during the treatment of the first pattern with the coating composition. ### Claim 5 (depends on 1) The multiple-pattern forming method of claim 1, wherein the first developer is an aqueous alkaline developer and the second developer is an organic solvent developer. ### Claim 6 (depends on 1) The multiple-pattern forming method of claim 1, wherein the first developer is an organic solvent developer and the second developer is an aqueous alkaline developer. ### Claim 7 (depends on 1) The multiple-pattern forming method of claim 1, further comprising after forming the multiple-pattern, coating the multiple-pattern with a shrink composition comprising a polymer and a solvent to increase a width of the multiple-pattern, thereby reducing spacing in the multiple-pattern. ### Claim 8 (depends on 7) The multiple-pattern forming method of claim 7, wherein the polymer of the shrink composition comprises a group chosen from a nitrogen-containing group, epoxy, carboxylic acid, ester, alcohol, or a combination thereof. ### Claim 9 (depends on 7) The multiple-pattern forming method of claim 7, wherein the polymer of the shrink composition comprises a functional group that forms a bond with carboxylic acid groups present on a surface of the multiple-pattern. ### Claim 10 (depends on 7) The multiple-pattern forming method of claim 7, wherein the solvent of the shrink composition is an aqueous solvent or an organic solvent. ### Claim 11 (depends on 1) The multiple-pattern forming method of claim 1, wherein the expedient comprises an acid. ### Claim 12 (depends on 1) The multiple-pattern forming method of claim 1, wherein the expedient comprises a thermal acid generator. ### Claim 13 (depends on 1) The multiple-pattern forming method of claim 1, wherein the expedient comprises a photoacid generator.