# US 12,765,331 B2 · Photoresist and formation method thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,765,331 B2 - Document ID: US12765331B2 - Status: Granted - Kind: B2 - Application number: 18/361,361 - Filed: 2023-07-28 - Published: 2024-04-04 - Granted: 2026-10-13 - Earliest claimed: 2022-08-29 - Assignees: Taiwan Semiconductor Manufacturing Company, Ltd.; National Tsing Hua University - Applicants: Taiwan Semiconductor Manufacturing Company, Ltd.; National Tsing Hua University - Inventors: Jui-Hsiung Liu; Yu-Fang Tseng; Pin-Chia Liao; Burn Jeng Lin; Tsai-Sheng Gau; Po-Hsiung Chen; Po-Wen Chiu - Web page: https://patentgrep.com/patent/US12765331B2 ## CPC - H10P 76/2042: {using lasers} - G03F 7/0042: {with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists (G03F7/075 takes precedence)} - G03F 7/2004: {characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light} - H10P 50/73: {using masks for insulating materials} - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - 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 A method of manufacturing a semiconductor device includes the following steps. A photoresist layer is formed over a material layer on a substrate. The photoresist layer has a composition including a solvent and a first photo-active compound dissolved in the solvent. The first photo-active compound is represented by the following formula (A1) or formula (A2): R in the formula (A1) and R in the formula (A2) each include one of the following formulae (1) to (6): The photoresist layer is patterned. The material layer is etched using the photoresist layer as an etch mask. ## Claims ### Claim 1 A method of manufacturing a semiconductor device, comprising: depositing a first photoresist composition over a target layer to form a photoresist layer, wherein the first photoresist composition comprises: a solvent; and a first photo-active compound dissolved in the solvent, wherein the first photo-active compound is represented by a formula (A3): and each of R and R′ in the formula (A3) include one of formulae (1) to (7): wherein n in the formula (7) is 0 to 3; patterning the photoresist layer; and etching the target layer using the photoresist layer as an etch mask. ### Claim 2 (depends on 1) The method of claim 1, wherein the first photo-active compound includes a formula (A3-1): . ### Claim 3 (depends on 1) The method of claim 1, wherein the first photoresist composition further comprises a second photo-active compound dissolved in the solvent, and the second photo-active compound is a tin oxo cluster including 12 tin atoms. ### Claim 4 (depends on 1) The method of claim 1, wherein the first photoresist composition further comprises a second photo-active compound dissolved in the solvent, and the second photo-active compound is represented by a formula (H1): in which X in the formula (H1) is OH or BF4. ### Claim 5 (depends on 1) The method of claim 1, wherein the first photoresist composition further comprises a second photo-active compound dissolved in the solvent, the second photo-active compound is represented by a formula (A2): and R in the formula (A2) includes one of the formulae (1) to (7). ### Claim 6 (depends on 1) The method of claim 1, wherein after patterning the photoresist layer, the photoresist layer has a second photoresist composition, and the second photoresist composition is a mixture of HfO2 and HfO2-x(RCO2)2x, and R in the HfO2-x(RCO2)2x includes one of the formulae (1) to (7). ### Claim 7 (depends on 1) The method of claim 1, wherein patterning the photoresist layer comprises: exposing the photoresist layer to an EUV radiation; and developing the photoresist layer. ### Claim 8 (depends on 1) The method of claim 1, wherein the first photoresist composition further comprises: a second photo-active compound dissolved in the solvent, wherein the second photo-active compound has a composition different from a composition of the first photo-active compound. ### Claim 9 (depends on 8) The method of claim 8, wherein the second photo-active compound is represented by a formula with a number of OH group different from a number of OH group of the first photo-active compound. ### Claim 10 (depends on 9) The method of claim 9, wherein the number of OH group of the formula of the second photo-active compound is less than the number of OH group of the first photo-active compound. ### Claim 11 A method of forming a first photo-active compound, comprising: mixing a first compound and a solution in a container, wherein the first compound has a formula (A): the R and R′ in the formula (A) is represented by formulae (1) to (7): in which n is 0 to 3; and reacting the first compound in the solution using a hydrothermal method to form the first photo-active compound. ### Claim 12 (depends on 11) The method of claim 11, wherein the solution is a base. ### Claim 13 (depends on 11) The method of claim 11, wherein the solution is M′OH or M′2CO3, in which M′ is Li, Na, K, Rb, Cs or R4N, and R of R4N is an alkyl group having 1 to 4 carbon atoms. ### Claim 14 A photoresist composition, comprising: a solvent; and a first photo-active compound dissolved in the solvent, wherein the first photo-active compound comprises a formula (A1): and wherein each of R and R′ in the formula (A1) is (1) to (7): in which n is 0 to 3. ### Claim 15 (depends on 14) The photoresist composition of claim 14, further comprising: a second photo-active compound dissolved in the solvent, and the second photo-active compound is a tin oxo cluster including 12 tin atoms. ### Claim 16 (depends on 14) The photoresist composition of claim 14, further comprising: a second photo-active compound dissolved in the solvent, and the second photo-active compound is represented by a formula (H1): in which X in the formula (H1) is OH or BF4. ### Claim 17 (depends on 14) The photoresist composition of claim 14, further comprising: a second photo-active compound dissolved in the solvent, wherein the second photo-active compound has a composition different from a composition of the first photo-active compound. ### Claim 18 (depends on 17) The photoresist composition of claim 17, wherein the second photo-active compound is represented by a formula with a number of OH group, and the number of OH group is different from a number of OH group of the first photo-active compound. ### Claim 19 (depends on 18) The photoresist composition of claim 18, wherein the number of OH group of the formula of the second photo-active compound is less than the number of OH group of the first photo-active compound. ### Claim 20 (depends on 14) The photoresist composition of claim 14, further comprising: a second photo-active compound dissolved in the solvent, wherein the second photo-active compound is represented by a formula (A2): Hf6O4(OH)6(RCO2)10 Formula (A2), and R in the formula (A2) includes one of the formulae (1) to (7).