# US 12,002,675 B2 · Photoresist layer outgassing prevention > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,002,675 B2 - Document ID: US12002675B2 - Status: Granted - Kind: B2 - Application number: 17/156,365 - Filed: 2021-01-22 - Published: 2022-01-27 - Granted: 2024-06-04 - Earliest claimed: 2020-06-18 - Assignees: Taiwan Semiconductor Manufacturing Company, Ltd. - Applicants: Taiwan Semiconductor Manufacturing Co., Ltd. - Inventors: Yen-Yu Chen; Chih-Cheng Liu; Yi-Chen Kuo; Jr-Hung Li; Tze-Liang Lee; Ming-Hui Weng; Yahru Cheng - Web page: https://patentgrep.com/patent/US12002675B2 ## CPC - G03F 7/11: having cover layers or intermediate layers, e.g. subbing layers {(G03F7/091 - G03F7/093, B41N3/03 take precedence)} - H10P 76/2041: {Photolithographic processes} - G03F 7/0042: {with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists (G03F7/075 takes precedence)} - G03F 7/167: {from the gas phase, by plasma deposition (G03F7/2035 takes precedence)} - G03F 7/168: {Finishing the coated layer, e.g. drying, baking, soaking} - G03F 7/325: {Non-aqueous compositions} - G03F 7/36: Imagewise removal not covered by groups G03F7/30 - G03F7/34, e.g. using gas streams, using plasma - H10P 50/695: {characterised by the process involved to create the mask, e.g. lift-off masks or sidewalls or to modify the mask} - H10P 50/73: {using masks for insulating materials} - 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) - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract A method of manufacturing a semiconductor device includes forming a photoresist layer over a substrate and forming a dehydrated film over the photoresist layer. The photoresist layer is selectively exposed to actinic radiation to form an exposed portion and an unexposed portion of the photoresist layer. The photoresist layer is developed to remove the unexposed portion of the photoresist layer and a first portion of the dehydrated film over the unexposed portion of the photoresist layer. In an embodiment, the method includes etching the substrate by using the exposed portion of the photoresist layer as a mask. ## Claims ### Claim 1 A method for manufacturing a semiconductor device, comprising: forming a metal-containing photoresist layer over a substrate, wherein the metal-containing photoresist layer is formed from a first precursor and a second precursor, wherein the first precursor is an organometallic having a formula: MaRbXc where M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, or Lu, R is a substituted or unsubstituted alkyl, alkenyl, or carboxylate group, X is a halide or sulfonate group, and 1≤a≤2, b≥1, c≥1, and b+c≤5; and the second precursor is at least one of an amine, a borane, a phosphine, or water; forming a dehydrated film over the photoresist layer; selectively exposing the photoresist layer to actinic radiation after forming the dehydrated film to form an exposed portion and an unexposed portion of the photoresist layer; and developing the photoresist layer to remove the unexposed portion of the photoresist layer and a first portion of the dehydrated film over the unexposed portion of the photoresist layer. ### Claim 2 (depends on 1) The method according to claim 1, further comprising etching the substrate by using the exposed portion of the photoresist layer as a mask. ### Claim 3 (depends on 1) The method according to claim 1, further comprising removing the exposed portion of the photoresist layer and a second portion of the dehydrated film over the exposed portion of the photoresist layer. ### Claim 4 (depends on 1) The method according to claim 1, wherein the forming a dehydrated film comprises heating a surface of the photoresist layer at a temperature ranging from 80° C. to 150° C. ### Claim 5 (depends on 1) The method according to claim 1, wherein the forming a dehydrated film comprises applying an oxidant to a surface of the photoresist layer. ### Claim 6 (depends on 1) The method according to claim 1, wherein the forming a dehydrated film comprises applying an organic solvent vapor to a surface of the photoresist layer. ### Claim 7 (depends on 1) The method according to claim 1, wherein the forming a dehydrated film comprises exposing a surface of the photoresist layer to ultraviolet radiation. ### Claim 8 (depends on 1) The method according to claim 1, wherein the forming a dehydrated film comprises at least two of heating a surface of the photoresist layer at a temperature ranging from 80° C. to 150° C., applying an oxidant to a surface of the photoresist layer, applying an organic solvent vapor to a surface of the photoresist layer, and exposing a surface of the photoresist layer to ultraviolet radiation. ### Claim 9 (depends on 1) The method according to claim 1, further comprising forming a layer to be patterned over the substrate before the forming a photoresist layer, wherein the layer to be patterned is formed of a different material than the substrate. ### Claim 10 (depends on 1) The method according to claim 1, wherein a ratio of a thickness of the dehydrated film to an original thickness of the photoresist layer as formed ranges from 1/100 to 1/10. ### Claim 11 A method of manufacturing a semiconductor device, comprising: forming a photoresist layer over a substrate, comprising: combining a first precursor and a second precursor in a vapor state to form a photoresist material, wherein the first precursor is an organometallic having a formula: MaRbXc where M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, or Lu, R is a substituted or unsubstituted alkyl, alkenyl, or carboxylate group, X is a halide or sulfonate group, and 1≤a≤2, b≥1, c≥1, and b+c≤5; and the second precursor is at least one of an amine, a borane, a phosphine, or water, and depositing the photoresist material over the substrate, wherein the photoresist layer has a first surface facing the substrate and an opposing second surface; treating the second surface of the photoresist layer to form a dehydrated film overlying the photoresist layer; selectively exposing the photoresist layer to actinic radiation to form a latent pattern in the photoresist layer; developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern in the photoresist layer, wherein a portion of the dehydrated film remains over the photoresist layer after the developing the latent pattern. ### Claim 12 (depends on 11) The method according to claim 11, further comprising extending the pattern in the photoresist layer into the substrate. ### Claim 13 (depends on 11) The method according to claim 11, wherein the photoresist material is deposited over the substrate by atomic layer deposition (ALD) or chemical vapor deposition (CVD). ### Claim 14 (depends on 11) The method according to claim 11, wherein the treating the second surface of the photoresist layer to form a dehydrated film comprises at least one of: heating the second surface of the photoresist layer at a temperature ranging from 80° C. to 150° C., applying ozone to the second surface of the photoresist layer, applying an organic solvent vapor to the second surface of the photoresist layer, and exposing the second surface of the photoresist layer to ultraviolet radiation. ### Claim 15 A method for preventing outgassing of a metal-containing photoresist, comprising: forming a metal-containing photoresist layer over a substrate, wherein the metal-containing photoresist layer has a first main surface facing the substrate and an opposing second main surface; treating the second main surface of the photoresist layer to form a treated photoresist layer including a barrier film over the photoresist layer to prevent outgassing from the photoresist layer, wherein the treating the second main surface of the photoresist layer includes one or more of: applying ozone to the second main surface of the photoresist layer and applying an organic solvent vapor to the second main surface of the photoresist layer; patternwise exposing the treated photoresist layer to actinic radiation to form an exposed portion and an unexposed portion of the treated photoresist layer; and removing the unexposed portion of the treated photoresist layer and a first portion of the barrier film over the unexposed portion of the treated photoresist layer. ### Claim 16 (depends on 15) The method according to claim 15, further comprising forming a layer to be patterned over the substrate before forming the photoresist layer, wherein the layer to be patterned comprises a different material composition than the substrate. ### Claim 17 (depends on 16) The method according to claim 16, further comprising etching the layer to be patterned by using the exposed portion of the treated photoresist layer and a second portion of the barrier film remaining over the exposed portion of the treated photoresist layer as a mask. ### Claim 18 (depends on 15) The method according to claim 15, wherein the barrier film has a thickness ranging from 0.1 nm to 5 nm. ### Claim 19 (depends on 15) The method according to claim 15, wherein a ratio of a thickness of the barrier film to an original thickness of the photoresist layer as formed ranges from 1/100 to 1/10. ### Claim 20 (depends on 15) The method according to claim 15, wherein the metal-containing photoresist layer is formed from a first precursor and a second precursor, wherein the first precursor is an organometallic having a formula: MaRbXc where M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, or Lu, R is a substituted or unsubstituted alkyl, alkenyl, or carboxylate group, X is a halide or sulfonate group, and 1≤a≤2, b≥1, c≥1, and b+c≤5; and the second precursor is at least one of an amine, a borane, a phosphine, or water.