# US 2025/0149335 A1 · Method to pattern a semiconductor substrate using a multilayer photoresist film stack > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2025/0149335 A1 - Document ID: US20250149335A1 - Status: Published application - Kind: A1 - Application number: 18/387,619 - Filed: 2023-11-07 - Published: 2025-05-08 - Earliest claimed: 2023-11-07 - Assignees: Tokyo Electron Limited - Applicants: Tokyo Electron Limited - Inventors: Kandabara Tapily; Eric Chih-Fang Liu; Lior Huli - Web page: https://patentgrep.com/patent/US20250149335A1 ## CPC - 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 7/0043: {Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof (G03F7/0044 takes precedence)} - G03F 7/091: {characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement} - G03F 7/094: {Multilayer resist systems, e.g. planarising layers} - G03F 7/095: having more than one photosensitive layer (G03F7/075 takes precedence) - G03F 7/11: having cover layers or intermediate layers, e.g. subbing layers {(G03F7/091 - G03F7/093, B41N3/03 take 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 7/40: Treatment after imagewise removal, e.g. baking - H10P 76/4085: {characterised by the processes involved to create the masks} - 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 Embodiments of methods are provided herein to form an extreme ultra-violet (EUV) photoresist pattern on a semiconductor substrate using a multilayer photoresist film stack. The disclosed embodiments begin by forming a multilayer photoresist film stack including a plurality of relatively thin photoresist film layers, each layer comprising a different photoresist material. After EUV exposure, the disclosed embodiments selectively develop the different photoresist layers in separate different development steps. In doing so, the process flows and methods disclosed herein increase the resist film thickness and improve development selectivity to avoid the photoresist damage and photoresist pattern collapse that often occurs during conventional EUV lithography processes. ## Claims ### Claim 1 A method of processing a semiconductor substrate, the method comprising: forming a multilayer photoresist film stack on a surface of the semiconductor substrate, the multilayer photoresist film stack comprising a first photoresist layer and a second photoresist layer formed above the first photoresist layer, the first photoresist layer comprising a metal oxide resist material, and the second photoresist layer comprising a resist material that differs from the metal oxide resist material used in the first photoresist layer; exposing the multilayer photoresist film stack to extreme ultra-violet (EUV) radiation in a single exposure step to: (a) convert regions of the first photoresist layer exposed to the EUV radiation to reacted regions, while regions of the first photoresist layer not exposed to the EUV radiation remain unchanged as unreacted regions, and (b) convert regions of the second photoresist layer exposed to the EUV radiation to reacted regions, while regions of the second photoresist layer not exposed to the EUV radiation remain unchanged as unreacted regions; exposing the multilayer photoresist film stack to a first development process to selectively develop the second photoresist layer by removing the reacted regions or the unreacted regions of the second photoresist layer to form a pattern in the second photoresist layer; and exposing the multilayer photoresist film stack to a second development process to selectively develop the first photoresist layer by removing the reacted regions or the unreacted regions of the first photoresist layer to form a pattern in the first photoresist layer. ### Claim 2 (depends on 1) The method of claim 1, wherein the metal oxide resist material used in the first photoresist layer comprises an organometallic oxide containing a central metal atom of tin (Sn), zirconium (Zr), indium (In), antimony (Sb), bismuth (Bi), zinc (Zn), hafnium (Hf), aluminum (AI), or combinations thereof. ### Claim 3 (depends on 2) The method of claim 2, wherein said forming the multilayer photoresist film stack comprises: forming an EUV enhancement layer on at least one underlayer provided on the surface of the semiconductor substrate, the EUV enhancement layer comprising a metal or non-metal material that generates and emits secondary electrons when exposed to the EUV radiation; and forming the first photoresist layer on the EUV enhancement layer; wherein the EUV enhancement layer increases exposure of the first photoresist layer to the EUV radiation during the single exposure step. ### Claim 4 (depends on 2) The method of claim 2, wherein said exposing the multilayer photoresist film stack to the second development process comprises: exposing the multilayer photoresist film stack to a dry development process to remove the reacted regions or the unreacted regions of the first photoresist layer and form the pattern in the first photoresist layer. ### Claim 5 (depends on 4) The method of claim 4, wherein said exposing the multilayer photoresist film stack to the dry development process comprises: exposing the surface of the semiconductor substrate to one or more process gases, which react with exposed surfaces of the first photoresist layer to remove the reacted regions or the unreacted regions of the first photoresist layer; wherein the one or more process gases comprise hydrogen (H2), ammonia (NH3), a halogen containing gas or combinations thereof. ### Claim 6 (depends on 2) The method of claim 2, wherein the second photoresist layer comprises a chemically amplified resist (CAR) material, and wherein said exposing the multilayer photoresist film stack to the first development process comprises: exposing the multilayer photoresist film stack to a wet development process to remove the reacted regions or the unreacted regions of the second photoresist layer and form the pattern in the second photoresist layer. ### Claim 7 (depends on 6) The method of claim 6, wherein exposing the multilayer photoresist film stack to the wet development process comprises: exposing the surface of the semiconductor substrate to a develop solution to dissolve the reacted regions or the unreacted regions of the second photoresist layer; wherein the develop solution comprises propylene glycol methyl ether acetate (PGMEA), tetramethylammonium hydroxide (TMAH), normal butyl alcohol (NBA), 2-heptanone or an organic solvent with an acid additive. ### Claim 8 (depends on 6) The method of claim 6, wherein said forming the multilayer photoresist film stack comprises: forming a barrier layer on the first photoresist layer, the barrier layer comprising a hydrophilic material; and forming the second photoresist layer on the barrier layer; wherein the barrier layer improves adhesion for the second photoresist layer and provides an etch stop during the first development process. ### Claim 9 (depends on 2) The method of claim 2, wherein the second photoresist layer comprises a metal oxide resist material that differs from the metal oxide resist material used in the first photoresist layer, and wherein said exposing the multilayer photoresist film stack to the first development process comprises: exposing the multilayer photoresist film stack to a dry development process to remove the reacted regions or the unreacted regions of the second photoresist layer and form the pattern in the second photoresist layer. ### Claim 10 (depends on 9) The method of claim 9, wherein the metal oxide resist material used in the second photoresist layer comprises an organometallic oxide containing a central metal atom of tin (Sn), zirconium (Zr), indium (In), antimony (Sb), bismuth (Bi), zinc (Zn), hafnium (Hf), or aluminum (Al), or combinations thereof, and wherein the organometallic oxide included within the second photoresist layer differs from the organometallic oxide included within the first photoresist layer. ### Claim 11 (depends on 9) The method of claim 9, wherein exposing the multilayer photoresist film stack to the dry development process comprises: exposing the surface of the semiconductor substrate to one or more process gases, which react with exposed surfaces of the second photoresist layer to remove the reacted regions or the unreacted regions of the second photoresist layer; wherein the one or more process gases comprise hydrogen (H2), ammonia (NH3), a halogen containing gas or combinations thereof. ### Claim 12 (depends on 1) The method of claim 1, wherein said forming the multilayer photoresist film stack comprises: forming an EUV enhancement layer on at least one underlayer provided on the surface of the semiconductor substrate, wherein the EUV enhancement layer comprises a metal or non-metal material that generates and emits secondary electrons when exposed to the EUV radiation, and wherein the EUV enhancement layer has a thickness ranging between 0.5 nm and 5 nm; forming the first photoresist layer on the EUV enhancement layer, wherein the metal oxide resist material used in the first photoresist layer comprises a first organometallic oxide and has a thickness ranging between 1 nm and 15 nm; forming a barrier layer on the first photoresist layer, wherein the barrier layer comprises a hydrophilic material and has a thickness ranging between about one monolayer to less than 2 nm; and forming the second photoresist layer on the barrier layer, wherein the second photoresist layer comprises: (a) a chemically amplified resist (CAR) material, or (b) a metal oxide resist material that differs from the metal oxide resist material used in the first photoresist layer, and has a thickness ranging between 1 nm and 15 nm. ### Claim 13 (depends on 12) The method of claim 12, wherein said forming the multilayer photoresist film stack comprises: forming the EUV enhancement layer, the first photoresist layer, the barrier layer and the second photoresist layer such that a combined thickness of the multilayer photoresist film stack ranges between 2 nm and 35 nm. ### Claim 14 A method of processing a semiconductor substrate, the method comprising: forming a multilayer photoresist film stack on a surface of the semiconductor substrate by: (a) depositing an extreme ultra-violet (EUV) enhancement layer on at least one underlayer provided on the surface of the semiconductor substrate; (b) depositing a first photoresist layer on the EUV enhancement layer, the first photoresist layer comprising a metal oxide resist material; (c) depositing a barrier layer on the first photoresist layer; and (d) depositing a second photoresist layer on the barrier layer, the second photoresist layer comprising a resist material that differs from the metal oxide resist material used in the first photoresist layer; exposing the multilayer photoresist film stack to EUV radiation in a single exposure step to convert regions of the first photoresist layer and regions of the second photoresist layer exposed to the EUV radiation to reacted regions, while regions of the first photoresist layer and regions of the second photoresist layer not exposed to the EUV radiation remain unchanged as unreacted regions; exposing the multilayer photoresist film stack to a first development process to selectively develop the second photoresist layer by removing the reacted regions or the unreacted regions of the second photoresist layer to form a pattern in the second photoresist layer; and exposing the multilayer photoresist film stack to a second development process to selectively develop the first photoresist layer by removing the reacted regions or the unreacted regions of the first photoresist layer to form a pattern in the first photoresist layer. ### Claim 15 (depends on 14) The method of claim 14, wherein a combined thickness of the multilayer photoresist film stack ranges between 2 nm and 35 nm, and wherein said forming the multilayer photoresist film stack, said exposing the multilayer photoresist film stack to the first development process and said exposing the multilayer photoresist film stack to the second development process forms a pattern in the second photoresist layer and in the first photoresist layer that avoids pattern collapse. ### Claim 16 (depends on 14) The method of claim 14, wherein said depositing the first photoresist layer comprises: depositing the metal oxide resist material on the EUV enhancement layer, the metal oxide resist material comprising an organometallic oxide and having a thickness ranging between 1 nm and 15 nm. ### Claim 17 (depends on 16) The method of claim 16, wherein said exposing the multilayer photoresist film stack to the second development process comprises: exposing the multilayer photoresist film stack to a dry development process to remove the reacted regions or the unreacted regions of the first photoresist layer and form the pattern in the first photoresist layer. ### Claim 18 (depends on 14) The method of claim 14, wherein said depositing the second photoresist layer comprises: depositing a chemically amplified resist (CAR) material on the barrier layer, the CAR material having a thickness ranging between 1 nm and 15 nm. ### Claim 19 (depends on 18) The method of claim 18, wherein said exposing the multilayer photoresist film stack to the first development process comprises: exposing the multilayer photoresist film stack to a wet development process to remove the reacted regions or the unreacted regions of the second photoresist layer and form the pattern in the second photoresist layer. ### Claim 20 (depends on 14) The method of claim 14, wherein said depositing the second photoresist layer comprises: depositing a metal oxide resist material, which differs from the metal oxide resist material used in the first photoresist layer, on the barrier layer, the metal oxide resist material used within the second photoresist layer comprising an organometallic oxide, which differs from an organometallic oxide included within the first photoresist layer, and having a thickness ranging between 1 nm and 15 nm. ### Claim 21 (depends on 20) The method of claim 20, wherein said exposing the multilayer photoresist film stack to the first development process comprises: exposing the multilayer photoresist film stack to a dry development process to remove the reacted regions or the unreacted regions of the second photoresist layer and form the pattern in the second photoresist layer. ### Claim 22 (depends on 14) The method of claim 14, wherein the EUV enhancement layer, the first photoresist layer and the barrier layer are deposited in situ within the same process chamber. ### Claim 23 (depends on 14) The method of claim 14, wherein the first photoresist layer and the second photoresist each comprise a negative photoresist, and wherein said exposing the multilayer photoresist film stack to the EUV radiation, said exposing the multilayer photoresist film stack to the first development process and said exposing the multilayer photoresist film stack to the second development process forms a negative tone EUV photoresist pattern. ### Claim 24 (depends on 14) The method of claim 14, wherein the first photoresist layer comprises a negative photoresist and the second photoresist comprises a positive photoresist, and wherein said exposing the multilayer photoresist film stack to the EUV radiation, said exposing the multilayer photoresist film stack to the first development process and said exposing the multilayer photoresist film stack to the second development process forms a positive tone EUV photoresist pattern.