# US 3,951,709 A · Process and material for semiconductor photomask fabrication > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 3,951,709 A - Document ID: US3951709A - Status: Granted - Kind: A - Application number: 05/446,931 - Filed: 1974-02-28 - Granted: 1976-04-20 - Earliest claimed: 1974-02-28 - Assignees: LFE Corporation - Inventors: Adir Jacob - Web page: https://patentgrep.com/patent/US3951709A ## CPC - G03F 1/54: Absorbers, e.g. of opaque materials - C23F 4/00: Processes for removing metallic material from surfaces, not provided for in group C23F1/00 or C23F3/00 - G03F 1/80: Etching - H10P 50/267: {using plasmas} - 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) - C23F: NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE (working metal by laser beams B23K26/00; desurfacing by applying flames B23K7/00; working of metal by electro-erosion B23H; producing decorative effects by removing surface material, e.g. by engraving, by etching, B44C1/22; electrolytic etching or polishing C25F); INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25 - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract A process step and material for use in the manufacture of semiconductor photomasks. To facilitate the etching of unmasked chromium, gold, and other metals capable of forming oxychloride derivatives on preselected portions of a substrate material, the material is exposed to a low pressure rf generated "cold" plasma (under 300.degree.C) produced from a homogeneous gaseous mixture of oxygen and a halogen containing compound. ## Claims ### Claim 1 In a plasma process for chemically etching metallic material in the presence of organic material without significant degradation of the organic material, the improvement comprising the step of: exposing the material to a gaseous plasma to form volatile oxychloride derivatives as products within the temperature range 25.degree. to 350.degree. Centigrade wherein said gaseous plasma is formed from a mixture of oxygen and a halogen containing gas selected from one of the following groups, chlorine gas, inorganic chlorine containing compounds capable of forming volatile oxychloride derivatives as products within the temperature range 25.degree. to 350.degree. Centigrade, and a halocarbon vapor or gas having no more than two carbon atoms per molecule, wherein at least one carbon atom in said molecule is linked to a predominance of chlorine atoms. ### Claim 2 In a plasma process for chemically etching metallic material in the presence of organic material without significant degradation of the organic material, the improvement comprising the step of: exposing the material to a gaseous low temperature plasma to form volatile oxychloride derivatives as products within the temperature range 25.degree. to 350.degree. Centigrade and wherein said gaseous low temperature plasma is formed from a mixture of oxygen and a halocarbon vapor or gas having no more than two carbon atoms per molecule, wherein at least one carbon atom in said molecule is linked to a predominance of chlorine atoms. ### Claim 3 (depends on 2) A process for chemically converting material in a plasma environment in accordance with claim 2 wherein said halocarbon has only one carbon atom per molecule, said carbon atom being linked to a predominance of chlorine atoms. ### Claim 4 (depends on 2) A process as in claim 2 wherein said halocarbon includes at least one hydrogen atom. ### Claim 5 (depends on 1) A process as in claim 1 wherein said halogen containing gas and said oxygen are supplied to a reactor from separate sources. ### Claim 6 (depends on 1) A process as in claim 1 wherein said oxygen and said halogen containing gas exclusive of said halocarbon vapor are supplied to a reactor from a common premixed source. ### Claim 7 (depends on 2) A process as in claim 2 wherein said gaseous mixture contains 39.5 percent oxygen and 60.5 percent ethylene trichloride by gas phase volume, said mixture being supplied to said reactor building up a total reaction pressure in the range of 0.05 to 5 torr, and having at least 20 watts rf energy coupled to said mixture. ### Claim 8 A composition of matter useful for chemically converting material in a plasma environment comprised of a mixture of oxygen and halogen containing gas selected from one of the following groups, chlorine gas, inorganic chlorine containing compounds capable of forming volatile oxychloride derivatives as products within the temperature range 25.degree. to 350.degree. Centigrade, and a halocarbon vapor or gas having no more than two carbon atoms per molecule, wherein at least one carbon atom in said molecule is linked to a predominance of chlorine atoms, wherein said mixture contains 25 to 80% oxygen by volume. ### Claim 9 A composition of matter, useful for chemically converting material in a plasma environment, comprised of a binary gaseous mixture of oxygen and a halocarbon having no more than two carbon atoms per molecule, wherein at least one carbon atom in said molecule is linked to a predominance of chlorine atoms, and wherein said mixture contains 25 to 80% oxygen by volume. ### Claim 10 (depends on 9) A composition of matter, in accordance with claim 9 wherein said halocarbon is ethylene trichloride. ### Claim 11 (depends on 9) A composition of matter in accordance with claim 9 wherein said halocarbon is carbon tetrachloride. ### Claim 12 (depends on 9) A composition of matter in accordance with claim 9 wherein said halocarbon is trichlorofluoromethane. ### Claim 13 (depends on 9) A composition of matter, in accordance with claim 9 wherein said halocarbon is 1, 1,2-trichloro-1, 2, 2-trifluoroethane. ### Claim 14 A composition of matter, useful in a process for chemically converting material by forming oxychloride-based compounds volatile in a low pressure, low temperature plasma, comprise of a ternary gaseous mixture of oxygen, ethylene trichloride, and carbon tetrachloride, and wherein said mixture contains 25% to 80% oxygen by volume. ### Claim 15 A composition of matter, useful in a process for chemically converting material by forming oxychloride-based compounds volatile in a low pressure, low temperature plasma, comprised of a ternary gaseous mixture of oxygen, ethylene trichloride, and trichlorofluoromethane, and wherein said mixture contains 25% to 80% oxygen by volume. ### Claim 16 A composition of matter, useful in a process for chemically converting material by forming oxychloride-based compounds volatile in a low pressure, low temperature plasma, comprised of a ternary gaseous mixture of oxygen, carbon tetrachloride, and trichlorofluoromethane, and wherein said mixture contains 25% to 80% oxygen by volume. ### Claim 17 A composition of matter, useful in a process for chemically converting material by forming oxychloride based compounds volatile in a low pressure, low temperature plasma, comprised of a ternary gaseous mixture of oxygen, carbon tetrachloride and 1, 1, 2-trichloro-1, 2, 2-trifluoroethane, and wherein said mixture contains 25% to 80% oxygen by volume. ### Claim 18 A composition of matter useful in a process for chemically converting material by forming oxychloride based compounds volatile in a low pressure, low temperature plasma comprised of a ternary gaseous mixture of oxygen, ethylene trichloride and 1, 1, 2-trichloro-1, 2, 2-trifluoroethane, and wherein said mixture contains 25% to 80% oxygen by volume. ### Claim 19 A composition of matter useful in a process for chemically converting material by forming oxychloride based compounds volatile in a low pressure, low temperature plasma comprised of a ternary gaseous mixture of oxygen, trichlorofluoromethane and 1, 1, 2-trichloro-1, 2, 2-trifluoroethane, and wherein said mixture contains 25% to 85% oxygen by volume. ### Claim 20 In a plasma process for etching metallic material in the presence of an organic etch mask without significant degradation of the organic etch mask, the improvement comprising; the step of exposing the material and the organic etch mask to a low temperature, low pressure gaseous plasma to form volatile oxychloride derivatives as products within the temperature range 25.degree. to 350.degree. Centigrade and wherein the low pressure gaseous plasma is formed from a mixture of oxygen and a halogen containing gas selected from one of the following groups, chlorine gas, inorganic chlorine compounds capable of forming volatile oxychloride derivatives as products within the temperature range 25.degree. to 350.degree. Centigrade, and a halocarbon vapor or gas having no more than two carbon atoms per molecule, wherein at least one carbon atom in said molecule is linked to a predominance of chlorine atoms. ### Claim 21 A process for chemically converting materials in a plasma environment, comprising the step of exposing the material to a gaseous low pressure, low temperature plasma formed from a binary mixture of chlorine gas and oxygen wherein oxygen comprises between 40% and 80% of said mixture. ### Claim 22 A process for chemically etching metallic materials in the presence of organic materials without significant degradation of the organic materials in a plasma environment comprising the step of: exposing the material to a low pressure, gaseous plasma formed from a binary mixture of oxygen and inorganaic chloride gas or vapor and thereby forming volatile oxychloride based compounds within the temperature range of 25.degree. to 350.degree. Centigrade. ### Claim 23 (depends on 22) A process in accordance with claim 22 wherein said chloride is boron trichloride. ### Claim 24 (depends on 22) A process in accordance with claim 22 wherein said chloride is phosphorous pentachloride. ### Claim 25 A composition of matter, useful for chemically converting material in a plasma environment comprising, a binary mixture of oxygen and inorganic chloride gas, wherein said inorganic chloride gas comprises from 20% to 60% of said mixture. ### Claim 26 (depends on 25) A composition in accordance with claim 25 wherein said inorganic halide is boron trichloride. ### Claim 27 (depends on 25) A composition in accordance with claim 25 wherein said inorganic chloride is phosphorous pentachloride.