# US 12,216,397 B2 · Reflective mask blank for EUV lithography, mask blank for EUV lithography, and manufacturing methods thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,216,397 B2 - Document ID: US12216397B2 - Status: Granted - Kind: B2 - Application number: 18/380,956 - Filed: 2023-10-17 - Published: 2024-02-08 - Granted: 2025-02-04 - Earliest claimed: 2020-07-28 - Assignees: AGC Inc. - Applicants: AGC Inc. - Inventors: Daijiro Akagi; Hirotomo Kawahara; Toshiyuki Uno; Ichiro Ishikawa; Kenichi Sasaki - Web page: https://patentgrep.com/patent/US12216397B2 ## CPC - G03F 1/24: Reflection masks; Preparation thereof - G03F 1/26: Phase shift masks [PSM]; PSM blanks; Preparation thereof - G03F 1/32: Attenuating PSM [att-PSM], e.g. halftone PSM or PSM having semi-transparent phase shift portion,; Preparation thereof - H10P 76/405: {characterised by their composition, e.g. multilayer masks} - H10P 76/4085: {characterised by the processes involved to create the masks} - 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 reflective mask blank for EUV lithography includes: a substrate; a multilayer reflective film for reflecting EUV light; and a phase shift film for shifting a phase of EUV light, the multilayer reflective film and the phase shift film formed on or above the substrate in this order. The phase shift film includes a layer 1 including ruthenium (Ru) and at least one selected from the group consisting of oxygen (O) and nitrogen (N). Among diffraction peaks derived from the phase shift film observed at 2θ: from 20° to 50° by out-of-plane XRD method, a peak having the highest intensity has a half value width FWHM of 1.0° or more. ## Claims ### Claim 1 A reflective mask blank for EUV lithography, comprising: a substrate; a multilayer reflective film for reflecting EUV light; and a phase shift film for shifting a phase of EUV light, the multilayer reflective film and the phase shift film formed on or above the substrate in this order, wherein the multilayer reflective film is a Si/Mo multilayer reflective film; the phase shift film comprises a layer 1 comprising ruthenium (Ru) and at least one selected from the group consisting of oxygen (O) and nitrogen (N); the layer 1 further comprises at least one element (X1) selected from the group consisting of chromium (Cr) and tantalum (Ta) present in a range of 20:1 to 1:5 in terms of an atomic composition ratio (at %) (Ru:X1) of Ru to X1; and among diffraction peaks derived from the phase shift film observed at 2θ: from 20° to 50° by out-of-plane XRD method, a peak having the highest intensity has a half value width FWHM of 1.0° or more. ### Claim 2 (depends on 1) The reflective mask blank for EUV lithography according to claim 1, wherein the element (X1) is present in a range of 4:1 to 1:4 in terms of an atomic composition ratio (at %) (Ru:X1) of Ru to X1. ### Claim 3 (depends on 1) The reflective mask blank for EUV lithography according to claim 1, wherein the element (X1) is present in a range of 2:1 to 1:2 in terms of an atomic composition ratio (at %) (Ru:X1) of Ru to X1. ### Claim 4 (depends on 1) The reflective mask blank for EUV lithography according to claim 1, wherein the layer 1 has a composition which is at least one selected from the group consisting of a composition comprising from 40 to 99 at % of Ru and from 1 to 60 at % of O, and a composition comprising from 30 to 98 at % of Ru, from 1 to 69 at % of O, and from 1 to 69 at % of N. ### Claim 5 (depends on 1) The reflective mask blank for EUV lithography according to claim 1, wherein the layer 1 comprises from 30 to 98 at % of Ru and from 2 to 70 at % of N. ### Claim 6 (depends on 4) The reflective mask blank for EUV lithography according to claim 4, wherein the layer 1 has a composition which is at least one selected from the group consisting of a composition comprising from 40 to 99 at % of a total (Ru+X1) of Ru and X1 and from 1 to 60 at % of O, and a composition comprising from 30 to 98 at % of a total (Ru+X1) of Ru and X1, from 1 to 69 at % of O, and from 1 to 69 at % of N. ### Claim 7 (depends on 5) The reflective mask blank for EUV lithography according to claim 5, wherein the layer 1 comprises from 30 to 90 at % of a total (Ru+X1) of Ru and X1 and from 10 to 70 at % of N. ### Claim 8 (depends on 1) The reflective mask blank for EUV lithography according to claim 1, wherein the phase shift film further comprises a layer 2 comprising at least one element (X2) selected from the group consisting of Cr, Ta, Ti, Re, W, Bi, Mn, Pt, Cu, Ir, and V. ### Claim 9 (depends on 8) The reflective mask blank for EUV lithography according to claim 8, wherein the layer 2 further comprises at least one element selected from the group consisting of O, N, boron (B), and carbon (C). ### Claim 10 (depends on 1) The reflective mask blank for EUV lithography according to claim 1, wherein the phase shift film has a thickness of from 20 nm to 60 nm. ### Claim 11 (depends on 1) The reflective mask blank for EUV lithography according to claim 1, wherein the layer 1 has a thickness of 10 nm or more. ### Claim 12 (depends on 1) The reflective mask blank for EUV lithography according to claim 1, wherein a phase difference between a reflected light of EUV light from the multilayer reflective film and a reflected light of EUV light from the phase shift film is from 150° to 250°; and a relative reflectance between an EUV light ray reflectance on a surface of the phase shift film and an EUV light ray reflectance on a surface of the multilayer reflective film ((EUV light ray reflectance on phase shift film surface/EUV light ray reflectance on multilayer reflective film surface)×100) is from 2% to 37%. ### Claim 13 (depends on 1) The reflective mask blank for EUV lithography according to claim 1, comprising a protective film for the multilayer reflective film formed between the multilayer reflective film and the phase shift film. ### Claim 14 (depends on 13) The reflective mask blank for EUV lithography according to claim 13, wherein the protective film comprises at least one element selected from the group consisting of Ru, palladium (Pd), Ir, rhodium (Rh), Pt, zirconium (Zr), niobium (Nb), Ta, Ti, and silicon (Si). ### Claim 15 (depends on 14) The reflective mask blank for EUV lithography according to claim 14, wherein the protective film further comprises at least one element selected from the group consisting of O, N, and B. ### Claim 16 (depends on 1) The reflective mask blank for EUV lithography according to claim 1, comprising an etching mask film on the phase shift film, wherein the etching mask film comprises at least one element selected from the group consisting of Nb, Ti, molybdenum (Mo), Ta, and Si. ### Claim 17 (depends on 16) The reflective mask blank for EUV lithography according to claim 16, wherein the etching mask film further comprises at least one element selected from the group consisting of O, N, and B. ### Claim 18 (depends on 1) A reflective mask for EUV lithography, obtained by forming a pattern in the phase shift film of the reflective mask blank for EUV lithography according to claim 1. ### Claim 19 A method for manufacturing a reflective mask blank for EUV lithography, the method comprising: forming, on a substrate, a multilayer reflective film for reflecting EUV light; forming, on the multilayer reflective film, a phase shift film for shifting a phase of EUV light, and forming an etching mask film on the phase shift film; wherein the multilayer reflective film is a Si/Mo multilayer reflective film the phase shift film comprises a layer 1 comprising ruthenium (Ru) and at least one selected from the group consisting of oxygen (O) and nitrogen (N); the layer 1 further comprises at least one element (X1) selected from the group consisting of chromium (Cr) and tantalum (Ta) present in a range of 20:1 to 1:5 in terms of an atomic composition ratio (at %) (Ru:X1) of Ru to X1; among diffraction peaks derived from the phase shift film observed at 2θ: from 20° to 50° by out-of-plane XRD method, a peak having a highest intensity has a half value width FWHM of 1.0° or more; and the etching mask film is removable by cleaning with an acid or a base. ### Claim 20 (depends on 19) A method for manufacturing a reflective mask for EUV lithography, the method comprising: forming a pattern by patterning the phase shift film in the reflective mask blank for EUV lithography manufactured by the manufacturing method of a reflective mask blank for EUV lithography according to claim 19.