# US 12,191,147 B2 · Coating composition for photolithography > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,191,147 B2 - Document ID: US12191147B2 - Status: Granted - Kind: B2 - Application number: 17/443,574 - Filed: 2021-07-27 - Published: 2022-12-22 - Granted: 2025-01-07 - Earliest claimed: 2021-05-27 - Assignees: Taiwan Semiconductor Manufacturing Company, Ltd. - Applicants: Taiwan Semiconductor Manufacturing Company, Ltd. - Inventors: Ya-Ting Lin; Yen-Ting Chen; Wei-Han Lai - Web page: https://patentgrep.com/patent/US12191147B2 ## CPC - C09D 125/18: Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen - H10P 76/2043: {using an anti-reflective coating} - C08L 25/08: Copolymers of styrene (C08L29/08, C08L35/06, C08L55/02 take precedence) - G03F 7/091: {characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement} - G03F 7/34: Imagewise removal by selective transfer, e.g. peeling away - H10P 50/71: {using masks for conductive or resistive materials} - H10P 76/202: {for lift-off processes} - 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 - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - 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 Methods for making a semiconductor device using an improved BARC (bottom anti-reflective coating) are provided herein. The improved BARC comprises a polymer formed from at least a styrene monomer having at least one or two hydrophilic substituents. The monomer(s) and substituents can be varied as desired to obtain a balance between film adhesion and wet etch resistance. Also provided is a semiconductor device produced using such methods. ## Claims ### Claim 1 A method for making a semiconductor device, comprising applying a bottom anti-reflective coating composition upon a surface of a substrate, wherein the coating composition comprises a polymer that includes a repeating unit of Formula (I) derived from a styrene monomer: wherein each X is a hydrophilic substituent independently selected from the group consisting of —NH2, —NHR, —NR2, —SH, —(C═O)H, —(C═O)R, —CO—NR2, —NR—(C═O)R, —SO3, —SO4, and —PO4, and salts and protected substituents thereof, wherein R is independently hydrogen, alkyl, alkenyl, alkynyl, or aryl; and where y is 2 to 5; and a crosslinker. ### Claim 2 (depends on 1) The method of claim 1, wherein a weight ratio of the polymer to the crosslinker is from about 10:90 to about 90:10, or from about 80:20 to about 60:40. ### Claim 3 (depends on 1) The method of claim 1, wherein the composition further comprises a solvent or a photo acid generator. ### Claim 4 (depends on 1) The method of claim 1, wherein the substrate is reflective; or wherein the surface includes three-dimensional structures, and the coating composition fills gaps between the three-dimensional structures; or wherein the substrate is metal. ### Claim 5 (depends on 1) The method of claim 1, wherein the polymer has a weight average molecular weight of about 1,000 to about 100,000. ### Claim 6 (depends on 1) The method of claim 1, wherein a backbone of the polymer contains only carbon-carbon bonds. ### Claim 7 (depends on 1) The method of claim 1, wherein when the styrene monomer has three or more hydrophilic substituents, the three or more substituents are not on continuous carbon atoms. ### Claim 8 (depends on 1) The method of claim 1, wherein the polymer is a copolymer formed from the styrene monomer and at least one co-monomer. ### Claim 9 (depends on 8) The method of claim 8, wherein the at least one co-monomer is a C2-C8 olefin, a substituted C2-C8 olefin, an acrylate, a diene, an acrylamide, acrylonitrile, acrylophenone, a different styrene monomer, or maleic acid. ### Claim 10 (depends on 9) The method of claim 9, wherein the styrene monomer is from about 10 mole % to about 90 mole % of the copolymer. ### Claim 11 A method of making a semiconductor device, comprising applying a bottom anti-reflective coating (BARC) layer upon a surface, wherein the BARC layer comprises a polymer that includes a repeating unit of Formula (I) derived from a styrene monomer: wherein each X is a hydrophilic substituent independently selected from the group consisting of —NH2, —NHR, —NR2, —SH, —(C═O)H, —(C═O)R, —CO—NR2, —NR—(C═O)R, —SO3, —SO4, and —PO4, and salts and protected substituents thereof, wherein R is independently hydrogen, alkyl, alkenyl, alkynyl, or aryl; and wherein y is 2 to 5; applying a photoresist layer upon the BARC layer; forming a masking pattern in the photoresist layer; and transferring the masking pattern to the BARC layer by etching. ### Claim 12 (depends on 11) The method of claim 11, wherein the BARC layer is applied to the surface of a metal layer, and further comprising: removing the photoresist layer; transferring the masking pattern to the metal layer by etching; and removing the BARC layer. ### Claim 13 (depends on 11) The method of claim 11, wherein the BARC layer is applied to the surface of a wafer substrate, and further comprising: removing the photoresist layer; applying metal to the patterned BARC layer; and removing the BARC layer. ### Claim 14 (depends on 11) The method of claim 11, wherein the BARC layer is applied to the surface of a wafer substrate, and further comprising: removing the photoresist layer; etching the wafer substrate or implanting ions through the patterned BARC layer; and removing the BARC layer. ### Claim 15 A bottom anti-reflective coating (BARC) composition, comprising: a polymer that includes a repeating unit of Formula (I) derived from a styrene monomer: wherein each X is a hydrophilic substituent independently selected from the group consisting of —NH2, —NHR, —NR2, —SH, —(C═O)H, —(C═O)R, —CO—NR2, —NR—(C═O)R, —SO3, —SO4, and —PO4, and salts and protected substituents thereof, wherein R is independently hydrogen, alkyl, alkenyl, alkynyl, or aryl; and wherein y is 2 to 5; and a crosslinker. ### Claim 16 (depends on 15) The composition of claim 15, further comprising a solvent, an acid generator, or a dye. ### Claim 17 (depends on 15) The composition of claim 15, wherein the polymer is a copolymer formed from the styrene monomer and at least one co-monomer. ### Claim 18 (depends on 15) The composition of claim 15, wherein the polymer has a weight average molecular weight of about 1,000 to about 100,000. ### Claim 19 (depends on 15) The composition of claim 15, wherein when the styrene monomer has three or more hydrophilic substituents, the three or more substituents are not on continuous carbon atoms. ### Claim 20 (depends on 15) The composition of claim 15, wherein a weight ratio of the polymer to the crosslinker is from about 10:90 to about 90:10, or from about 80:20 to about 60:40.