# US 12,222,650 B2 · Photoresist underlayer and method of manufacturing a semiconductor device > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,222,650 B2 - Document ID: US12222650B2 - Status: Granted - Kind: B2 - Application number: 17/150,309 - Filed: 2021-01-15 - Published: 2021-09-02 - Granted: 2025-02-11 - Earliest claimed: 2020-02-27 - Assignees: Taiwan Semiconductor Manufacuring Company, Ltd. - Applicants: Taiwan Semiconductor Manufacturing Co., Ltd. - Inventors: An-Ren Zi; Ching-Yu Chang - Web page: https://patentgrep.com/patent/US12222650B2 ## CPC - G03F 7/094: {Multilayer resist systems, e.g. planarising layers} - C08L 101/02: characterised by the presence of specified groups {, e.g. terminal or pendant functional groups} - G03F 7/0042: {with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists (G03F7/075 takes precedence)} - G03F 7/039: Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023) - G03F 7/0392: {the macromolecular compound being present in a chemically amplified positive photoresist composition} - G03F 7/091: {characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement} - G03F 7/095: having more than one photosensitive layer (G03F7/075 takes precedence) - G03F 7/26: Processing photosensitive materials; Apparatus therefor (G03F7/12 - G03F7/24 take precedence) - 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) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract A method of manufacturing a semiconductor device includes forming a photoresist underlayer including a photoresist underlayer composition over a semiconductor substrate and forming a photoresist layer comprising a photoresist composition over the photoresist underlayer. The photoresist layer is selectively exposed to actinic radiation, and the photoresist layer is developed to form a pattern in the photoresist layer. The photoresist underlayer composition includes: a first polymer having one or more of pendant acid-labile groups and pendant epoxy groups, a second polymer having one or more crosslinking groups, an acid generator, a quencher or photodecomposable base, and a solvent. The photoresist underlayer composition includes 0 wt. % to 10 wt. % of the quencher or photodecomposable base based on a total weight of the first and second polymers. ## Claims ### Claim 1 A method of manufacturing a semiconductor device, comprising: forming a photoresist underlayer comprising a photoresist underlayer composition over a semiconductor substrate; forming a photoresist layer comprising a photoresist composition over the photoresist underlayer; selectively exposing the photoresist layer to actinic radiation; and developing the photoresist layer to form a pattern in the photoresist layer, wherein the photoresist underlayer composition comprises: a first polymer comprising pendant acid-labile groups including one or more structures selected from a second polymer comprising one or more crosslinking groups; an acid generator; a photodecomposable base, wherein the photoresist underlayer composition comprises 0.1 wt. % to 10 wt. % of the photodecomposable base based on a total weight of the first and second polymers; and a solvent. ### Claim 2 (depends on 1) The method according to claim 1, wherein the photoresist composition comprises: a third polymer; a photoactive compound; and a solvent. ### Claim 3 (depends on 1) The method according to claim 1, wherein the acid generator is a photoacid generator. ### Claim 4 (depends on 1) The method according to claim 1, further comprising heating the photoresist underlayer at a temperature of 40° C. to 300° C. for 10 seconds to 10 minutes before forming the photoresist layer. ### Claim 5 (depends on 1) The method according to claim 1, further comprising heating the photoresist layer at a temperature of 80° C. to 300° C. for 10 seconds to 10 minutes after the selectively exposing the photoresist layer to actinic radiation. ### Claim 6 (depends on 1) The method according to claim 1, wherein the photoresist composition comprises a metal-containing photoresist. ### Claim 7 (depends on 1) The method according to claim 1, wherein the first polymer further comprises pendant epoxy groups, and the pendant acid-labile groups and the pendant epoxy groups are greater than 5 wt. % to 50 wt. % of the first polymer. ### Claim 8 (depends on 1) The method according to claim 1, wherein the crosslinking groups are greater than 30 wt. % to 70 wt. % of the second polymer. ### Claim 9 (depends on 1) The method according claim 1, wherein the first polymer further comprises pendant epoxy groups. ### Claim 10 (depends on 1) The method according to claim 1, further comprising selectively exposing the photoresist underlayer to actinic radiation, wherein portions of the photoresist layer and portions of the photoresist underlayer selectively exposed to actinic radiation are removed during the developing. ### Claim 11 A method of manufacturing a semiconductor device, comprising: forming a photoresist underlayer comprising a photoresist underlayer composition over a semiconductor substrate; crosslinking the photoresist underlayer; forming a photoresist layer comprising a photoresist composition over the photoresist underlayer; and patterning the photoresist layer; wherein the photoresist underlayer composition comprises: a first polymer comprising pendant acid-labile groups including one or more structures selected from a second polymer comprising crosslinking groups; an acid generator, a photodecomposable base; and a solvent. ### Claim 12 (depends on 11) The method according to claim 11, wherein the photoresist composition comprises: a third polymer; a photoactive compound; and a solvent. ### Claim 13 (depends on 11) The method according to claim 11, wherein the photoresist underlayer composition comprises greater than 0 wt. % to 10 wt. % of the photodecomposable base based on a total weight of the first and second polymers. ### Claim 14 (depends on 11) The method according to claim 11, wherein the first polymer further comprises pendant epoxy groups, and one or more selected from the pendant acid labile groups and the pendant epoxy groups are connected to the first polymer by a connecting group selected from substituted and unsubstituted, branched and unbranched aliphatic groups, branched and unbranched aromatic groups, unsubstituted or halogen-substituted 1-9 carbon cyclic and non-cyclic groups, or —S—, —P—, —P(O2)—, —C(═O)S—, —C(═O)O—, —O—, —N—, —C(═O)N—, —SO2O—, —SO2S—, —SO—, and —SO2—, or a carboxylic acid group, ether group, ketone group, ester group, or benzene group. ### Claim 15 (depends on 11) The method according to claim 11, wherein the crosslinking groups are connected to the second polymer by a connecting group selected from substituted and unsubstituted, branched and unbranched aliphatic groups, branched and unbranched aromatic groups, unsubstituted or halogen-substituted 1-9 carbon cyclic and non-cyclic groups, or —S—, —P—, —P(O2)—, —C(═O)S—, —C(═O)O—, —O—, —N—, —C(═O)N—, —SO2O—, —SO2S—, —SO—, and —SO2—, or a carboxylic acid group, ether group, ketone group, ester group, or benzene group. ### Claim 16 A method of manufacturing a semiconductor device, comprising: forming a first layer over a substrate, wherein the first layer includes a first layer composition comprising: a first polymer comprising pendant acid-labile groups including one or more structures selected from a second polymer comprising crosslinking groups; a photodecomposable base; and an acid generator; heating the first layer; forming a resist layer over the first layer, wherein the resist layer includes a resist composition comprising: a third polymer; and a photoactive compound; and patterning the resist layer and the first layer. ### Claim 17 (depends on 16) The method according to claim 16, further comprising extending a pattern formed in the resist layer and the first layer into the substrate. ### Claim 18 (depends on 17) The method according to claim 17, wherein the extending a pattern formed in the resist layer and the first layer into the substrate comprises etching. ### Claim 19 (depends on 16) The method according to claim 16, wherein the first polymer further comprises pendant epoxy groups, and the heating the first layer includes crosslinking the first layer. ### Claim 20 (depends on 16) The method according to claim 16, wherein the patterning the resist layer and the first layer includes: patternwise exposing the resist layer and the first layer to actinic radiation; heating the patternwise exposed resist layer and first layer; and developing the patternwise exposed resist layer and first layer.