# US 11,079,680 B2 · High heat resistance resist composition and pattern forming method 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 11,079,680 B2 - Document ID: US11079680B2 - Status: Granted - Kind: B2 - Application number: 15/773,029 - Filed: 2016-11-02 - Published: 2019-01-31 - Granted: 2021-08-03 - Earliest claimed: 2015-11-17 - Assignees: Merck Patent GmbH - Applicants: AZ Electronic Materials (Luxembourg) S.a.r.l. - Inventors: Masato Suzuki; Hiroshi Hitokawa; Tomohide Katayama - Web page: https://patentgrep.com/patent/US11079680B2 ## CPC - G03F 7/38: Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)} - G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors} - G03F 7/038: Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021) - G03F 7/0382: {the macromolecular compound being present in a chemically amplified negative photoresist composition} - G03F 7/2022: {Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure} - G03F 7/40: Treatment after imagewise removal, e.g. baking - G03F 7/0048: {characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents} - 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 [Problem] To provide a high heat resistance resist composition and a pattern formation method using the composition. [Solution] The present invention provides a chemically amplified negative-type resist composition comprising a particular polymer and a particular crosslinking agent, and this composition makes it possible to form a resist pattern of high sensitivity, of excellent resolution and of strong heat-resistance. ## Claims ### Claim 1 A negative pattern formation method comprising the steps of coating a substrate with a chemically amplified negative-type resist composition comprising (I) a polymer containing the repeating unit represented by the following formula (Ia): in which A is hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, B is a hydrocarbon group having 1 to 5 carbon atoms, and x is an integer of 0 or more, y is an integer of 1 or more, under the conditions of x+y≤5; (II) a crosslinking agent represented by the following formula (IIa) in which n is an integer of 1 or more, R1 is a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, and R2 is hydrogen, hydroxyl or a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms; wherein at least one of said R1 and R2 is a naphthyl group; (III) an acid generating agent; and (IV) a solvent, to form a composition layer; (1) pre-baking said composition layer; (2) exposing to light the substrate coated with the composition layer after said pre-baking step; (3) carrying out post exposure baking after said exposure step; and carrying out development with an alkali aqueous solution after said post exposure baking step. ### Claim 2 (depends on 1) The negative pattern formation method according to claim 1, wherein said polymer is represented by the following formula (Ib) in which x and y are numbers indicating the polymerization ratios provided that x is not equal to 0, the repeating units of each side may be polymerized either randomly or to form blocks, each of G and H is independently hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, each of I and J is independently a hydrocarbon group having 1 to 5 carbon atoms, and t, an integer of 0 or more u an integer of 1 or more and v an integer of 0 to 5, under the condition of t+u<5. ### Claim 3 (depends on 2) The negative pattern formation method according to claim 2, wherein said polymer represented by the above formula (Ib) has a polymerization ratio x:y in the range of 87:13 to 100:0. ### Claim 4 (depends on 2) The negative pattern formation method according to claim 2, wherein said polymer represented by the above formula (Ib) has a polymerization ratio x:y in the range of 30:70 to 100:0. ### Claim 5 (depends on 2) The negative pattern formation method according to claim 2, wherein the polymerization ratio y is 0 in said polymer represented by the above formula (Ib). ### Claim 6 (depends on 1) The negative pattern formation method according to claim 1, wherein the content of said crosslinking agent is in the range of 5 to 30 weight parts based on 100 weight parts of said polymer (I). ### Claim 7 (depends on 1) The negative pattern formation method according to claim 1, wherein said n is an integer of 1 to 3 inclusive. ### Claim 8 (depends on 1) The negative pattern formation method according to claim 1, wherein said crosslinking agent represented by the formula (IIa) has a weight average molecular weight of 300 to 2000. ### Claim 9 (depends on 1) The negative pattern formation method according to claim 1, wherein said crosslinking agent has a glass transition temperature in the range of 150 to 250° C. ### Claim 10 A negative pattern formation method comprising the steps of coating a substrate with a chemically amplified negative-type resist composition comprising (I) a polymer containing the repeating unit represented by the following formula (Ia): in which A is hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, B is a hydrocarbon group having 1 to 5 carbon atoms, and x is an integer of 0 or more, y is an integer of 1 or more, under the conditions of x+y<5; (II) a crosslinking agent represented by the following formula (IIa) (IIa′) in which n is an integer of 1 to 3 or has an average molecular weight of 500 to 800, (Ill) an acid generating agent; and (IV) a solvent, to form a composition layer; (4) pre-baking said composition layer; (5) exposing to light the substrate coated with the composition layer after said pre-baking step; (6) carrying out post exposure baking after said exposure step; and carrying out development with an alkali aqueous solution after said post exposure baking step. ### Claim 11 (depends on 10) The negative pattern formation method according to claim 10, wherein said polymer represented by the above formula (Ib) has a polymerization ratio x:y in the range of 30:70 to 100:0. ### Claim 12 (depends on 10) The negative pattern formation method according to claim 10, wherein the content of said crosslinking agent is in the range of 5 to 30 weight parts based on 100 weight parts of said polymer (Ia). ### Claim 13 (depends on 10) The negative pattern formation method according to claim 10, wherein said crosslinking agent represented by the formula (Ila) has a weight average molecular weight of 300 to 2000. ### Claim 14 (depends on 10) The negative pattern formation method according to claim 10, wherein said crosslinking agent has a glass transition temperature in the range of 150 to 250° C.