# US 10,372,030 B2 · Halftone phase shift mask blank and halftone phase shift mask > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,372,030 B2 - Document ID: US10372030B2 - Status: Granted - Kind: B2 - Application number: 15/077,258 - Filed: 2016-03-22 - Published: 2016-10-06 - Granted: 2019-08-06 - Earliest claimed: 2015-03-31 - Assignees: Shin-Etsu Chemical Co., Ltd. - Applicants: Shin-Etsu Chemical Co., Ltd. - Inventors: Kouhei Sasamoto; Takuro Kosaka; Yukio Inazuki; Hideo Kaneko - Web page: https://patentgrep.com/patent/US10372030B2 ## CPC - G03F 1/32: Attenuating PSM [att-PSM], e.g. halftone PSM or PSM having semi-transparent phase shift portion,; Preparation thereof - G03F 1/26: Phase shift masks [PSM]; PSM blanks; Preparation thereof - 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 halftone phase shift mask blank is provided comprising a transparent substrate and a halftone phase shift film which is composed of a silicon base material having a Si+N+O content of at least 90 at %, a Si content of 30-70 at %, a N+O content of 30-60 at %, and an O content of up to 30 at %, and has a thickness of up to 70 nm. The halftone phase shift film is thin enough for mask pattern processing, undergoes minimal pattern size variation degradation upon exposure to sub-200 nm radiation, and maintains a necessary phase shift and transmittance. ## Claims ### Claim 1 A halftone phase shift mask blank comprising a transparent substrate and a halftone phase shift film thereon having a phase shift of 150° to 200° and a transmittance of 3% to 30% with respect to light of wavelength up to 200 nm, wherein said halftone phase shift film is a single layer or a multilayer film, each layer comprising silicon and nitrogen and oxygen, when the halftone phase shift film is a single layer, the overall single layer is composed of a silicon base material, or when the halftone phase shift film is a multilayer film, at least 60% of its thickness is composed of a silicon base material, said silicon base material having a total content of silicon, nitrogen and oxygen of at least 90 at %, a silicon content of 30 to 70 at %, a total content of nitrogen and oxygen of 30 to 60 at %, an oxygen content of up to 2 at %, and a transition metal content of 0.01 to 0.9 at %, and said halftone phase shift film has a thickness of up to 70 nm. ### Claim 2 (depends on 1) The mask blank of claim 1 wherein the halftone phase shift film has a transmittance of 20% to 30%, and said silicon base material contains oxygen and has a total content of silicon, nitrogen and oxygen of at least 95 at %. ### Claim 3 (depends on 1) The mask blank of claim 1, further comprising a second film on the halftone phase shift film, the second film being a single layer or a multilayer film composed of a chromium-containing material. ### Claim 4 (depends on 3) The mask blank of claim 3 wherein the second film is a light-shielding film, a combination of light-shielding film and antireflective film, or an auxiliary film which functions as a hard mask during pattern formation of the halftone phase shift film. ### Claim 5 (depends on 3) The mask blank of claim 3, further comprising a third film on the second film, the third film being a single layer or a multilayer film composed of a silicon-containing material. ### Claim 6 (depends on 5) The mask blank of claim 5 wherein the second film is a light-shielding film or a combination of light-shielding film and antireflective film, and the third film is an auxiliary film which functions as a hard mask during pattern formation of the second film. ### Claim 7 (depends on 5) The mask blank of claim 5 wherein the second film is an auxiliary film which functions as a hard mask during pattern formation of the halftone phase shift film and as an etch stopper during pattern formation of the third film, and the third film is a light-shielding film or a combination of light-shielding film and antireflective film. ### Claim 8 (depends on 5) The mask blank of claim 5, further comprising a fourth film on the third film, the fourth film being a single layer or a multilayer film composed of a chromium-containing material. ### Claim 9 (depends on 8) The mask blank of claim 8 wherein the second film is an auxiliary film which functions as a hard mask during pattern formation of the halftone phase shift film and as an etch stopper during pattern formation of the third film, the third film is a light-shielding film or a combination of light-shielding film and antireflective film, and the fourth film is an auxiliary film which functions as a hard mask during pattern formation of the third film. ### Claim 10 (depends on 1) A halftone phase shift mask prepared from the halftone phase shift mask blank of claim 1. ### Claim 11 (depends on 1) The mask blank of claim 1 wherein the oxygen content of the silicon base material is up to 1 at %. ### Claim 12 A halftone phase shift mask blank comprising a transparent substrate and a halftone phase shift film thereon having a phase shift of 150° to 200° and a transmittance of 3% to 30% with respect to light of wavelength up to 200 nm, wherein said halftone phase shift film is a single layer or a multilayer film, each layer comprising silicon and nitrogen, when the halftone phase shift film is a single layer, the overall single layer is composed of a silicon base material, or when the halftone phase shift film is a multilayer film, at least 60% of its thickness is composed of a silicon base material being free of oxygen, said silicon base material having a total content of silicon and nitrogen of at least 90 at %, a silicon content of 30 to 70 at %, a nitrogen content of 40 to 60 at %, and a transition metal content of 0.01 to 0.9 at %, and said halftone phase shift film has a thickness of up to 70 nm. ### Claim 13 (depends on 12) The mask blank of claim 12 wherein the halftone phase shift film has a transmittance of 3% to less than 20%, and said silicon base material has a total content of silicon and nitrogen of at least 95 at %. ### Claim 14 (depends on 12) The mask blank of claim 12, further comprising a second film on the halftone phase shift film, the second film being a single layer or a multilayer film composed of a chromium-containing material. ### Claim 15 (depends on 14) The mask blank of claim 14 wherein the second film is a light-shielding film, a combination of light-shielding film and antireflective film, or an auxiliary film which functions as a hard mask during pattern formation of the halftone phase shift film. ### Claim 16 (depends on 14) The mask blank of claim 14, further comprising a third film on the second film, the third film being a single layer or a multilayer film composed of a silicon-containing material. ### Claim 17 (depends on 16) The mask blank of claim 16 wherein the second film is a light-shielding film or a combination of light-shielding film and antireflective film, and the third film is an auxiliary film which functions as a hard mask during pattern formation of the second film. ### Claim 18 (depends on 16) The mask blank of claim 16 wherein the second film is an auxiliary film which functions as a hard mask during pattern formation of the halftone phase shift film and as an etch stopper during pattern formation of the third film, and the third film is a light-shielding film or a combination of light-shielding film and antireflective film. ### Claim 19 (depends on 16) The mask blank of claim 16, further comprising a fourth film on the third film, the fourth film being a single layer or a multilayer film composed of a chromium-containing material. ### Claim 20 (depends on 19) The mask blank of claim 19 wherein the second film is an auxiliary film which functions as a hard mask during pattern formation of the halftone phase shift film and as an etch stopper during pattern formation of the third film, the third film is a light-shielding film or a combination of light-shielding film and antireflective film, and the fourth film is an auxiliary film which functions as a hard mask during pattern formation of the third film. ### Claim 21 (depends on 12) A halftone phase shift mask prepared from the halftone phase shift mask blank of claim 12.