# US 10,481,495 B2 · Topcoat compositions containing fluorinated thermal acid generators > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,481,495 B2 - Document ID: US10481495B2 - Status: Granted - Kind: B2 - Application number: 16/269,615 - Filed: 2019-02-07 - Published: 2019-08-08 - Granted: 2019-11-19 - Earliest claimed: 2016-10-31 - Assignees: Rohm and Haas Electronic Materials LLC - Applicants: Rohm and Haas Electronic Materials LLC - Inventors: Irvinder Kaur; Doris Kang; Cong Liu; Gerhard Pohlers; Mingqi Li - Web page: https://patentgrep.com/patent/US10481495B2 ## CPC - G03F 7/11: having cover layers or intermediate layers, e.g. subbing layers {(G03F7/091 - G03F7/093, B41N3/03 take precedence)} - C09D 133/10: Homopolymers or copolymers of methacrylic acid esters - G03F 7/0002: {Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping} - G03F 7/0046: {with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence)} - G03F 7/2041: {in the presence of a fluid, e.g. immersion; using fluid cooling means} - G03F 7/327: {Non-aqueous alkaline compositions, e.g. anhydrous quaternary ammonium salts} - G03F 7/38: Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)} - G03F 7/40: Treatment after imagewise removal, e.g. baking - H10P 76/2041: {Photolithographic processes} - G03F 7/16: Coating processes; Apparatus therefor (applying coatings to base materials in general B05; applying photosensitive compositions to base for photographic purposes G03C1/74) - 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) - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract Provided are topcoat compositions that include: a matrix polymer; a surface active polymer; an ionic thermal acid generator comprising an anion and a cation, wherein the anion, the cation, or the anion and the cation are fluorinated; and a solvent. Also provided are coated substrates and pattern-forming methods which make use of the topcoat compositions. The invention has particular applicability in photolithographic processes as a photoresist topcoat layer in the manufacture of semiconductor devices. ## Claims ### Claim 1 A topcoat composition, comprising: a matrix polymer; a surface active polymer; an ionic thermal acid generator comprising an anion and a cation, wherein the anion, the cation, or the anion and the cation are fluorinated, wherein the cation is of the general formula (I): (BH)+ (I) which is the monoprotonated form of a nitrogen-containing base B; and a solvent. ### Claim 2 (depends on 1) The topcoat composition of claim 1, wherein the anion is fluorinated. ### Claim 3 (depends on 1) The topcoat composition of claim 1, wherein the cation is fluorinated. ### Claim 4 (depends on 1) The topcoat composition of claim 1, wherein the anion is polycyclic. ### Claim 5 (depends on 1) The topcoat composition of claim 1, wherein the ionic thermal acid generator comprises a fluorinated alcohol group comprising a fluorine atom bonded to a carbon at the alpha position of the hydroxyl group and/or or a fluorinated group bonded pendant to a carbon at the alpha position of the hydroxyl group. ### Claim 6 (depends on 5) The topcoat composition of claim 5, wherein the fluorinated alcohol group is bonded to an aromatic ring of the anion through an ester group. ### Claim 7 (depends on 6) The topcoat composition of claim 6, wherein the anion comprises a plurality of fluorinated alcohol groups bonded to the aromatic ring through a respective ester group. ### Claim 8 (depends on 1) The topcoat composition of claim 1, wherein the ionic thermal acid generator comprises a nitrogen-containing cation. ### Claim 9 (depends on 1) The topcoat composition of claim 1, further comprising a photoacid generator. ### Claim 10 (depends on 1) The topcoat composition of claim 1, wherein the solvent comprises a mixture of organic solvents comprising a first organic solvent having a boiling point of from 120 to 140° C., a second organic solvent having a boiling point of from 140 to 180° C. and a third organic solvent having a boiling point of from 170 to 200° C. ### Claim 11 (depends on 1) The topcoat composition of claim 1, wherein the base has a pKa from 0 to 5.0. ### Claim 12 (depends on 1) The topcoat composition of claim 1, wherein the cation is a substituted or unsubstituted C3-30 aryl amine. ### Claim 13 (depends on 1) A coated substrate, comprising: a semiconductor substrate; a photoresist layer over the semiconductor substrate; and a topcoat layer over the photoresist layer, wherein the topcoat layer is formed from a topcoat composition of claim 1. ### Claim 14 (depends on 1) A pattern-forming method, comprising: (a) forming a photoresist layer over a substrate; (b) forming a topcoat layer over the photoresist layer, wherein the topcoat layer is formed from a topcoat composition of claim 1; (c) exposing the topcoat layer and the photoresist layer to activating radiation; and (d) contacting the exposed topcoat layer and photoresist layer with a developer to form a photoresist pattern. ### Claim 15 (depends on 14) The pattern-forming method of claim 14, wherein the base has a pKa from 0 to 5.0. ### Claim 16 (depends on 14) The pattern-forming method of claim 14, wherein the cation is a substituted or unsubstituted C3-30 aryl amine. ### Claim 17 (depends on 14) The pattern-forming method of claim 14, wherein the ionic thermal acid generator comprises a fluorinated alcohol group comprising a fluorine atom bonded to a carbon at the alpha position of the hydroxyl group and/or or a fluorinated group bonded pendant to a carbon at the alpha position of the hydroxyl group. ### Claim 18 (depends on 17) The pattern-forming method of claim 17, wherein the fluorinated alcohol group is bonded to an aromatic ring of the anion through an ester group. ### Claim 19 (depends on 18) The pattern-forming method of claim 18, wherein the anion comprises a plurality of fluorinated alcohol groups bonded to the aromatic ring through a respective ester group.