# US 4,028,155 A · Process and material for manufacturing thin film integrated circuits > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,028,155 A - Document ID: US4028155A - Status: Granted - Kind: A - Application number: 05/713,128 - Filed: 1976-08-10 - Granted: 1977-06-07 - Earliest claimed: 1974-02-28 - Assignees: LFE Corporation - Inventors: Adir Jacob - Web page: https://patentgrep.com/patent/US4028155A ## CPC - H10P 50/283: {by chemical means} - H10P 50/287: {by chemical means} - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract A process step for use in the manufacture of thin film integrated circuits, to enable, in one process, the removal of all the photoresist material from underlying metallic films without concomitant degradation of the metallic surface and in another process, preferential etching of silicon nitrides and oxides without significant simultaneous etching of single crystal silicon. The material is exposed to a low pressure (few torr) rf generated "cold" plasma, where the plasma is a homogeneous gaseous mixture of oxygen, a halogen containing compound and a noble gas. ## Claims ### Claim 1 A process for use in the manufacture of multi-layer thin film integrated circuits for selective removal of specific layers, comprising the step of: exposing the multi-layer thin film integrated circuit to a low temperature, low pressure plasma formed from a gaseous multi-component mixture of oxygen, a noble gas carrier and a halogen containing gas selected from the group consisting of: organohalides defined as having no more than two carbon atoms per molecule and being at least partially substituted by halogens including a pedominance of fluorine atoms, inorganic halides defined as having at least one fluorine atom per molecule, and fluorine gas. ### Claim 2 A process for etching silicon oxides and silicon nitrides preferentially to single crystal silicons during the manufacture of thin film integrated circuits comprising the step of: exposing a thin film integrated circuit to a low temperature, low ressure plasma formed from a gaseous multicomponent mixture of oxygen, a noble gas carrier and CF.sub.4. ### Claim 3 (depends on 2) A process in accordance with claim 2 wherein the pressure is maintained between 0.5 and 2 torr, wherein the plasma is generated by the application of an RF field with the RF power supplied to the plasma lying within the range of 100 and 350 watts. ### Claim 4 (depends on 2) A process in accordance with claim 2 wherein the noble gas carrier is helium, wherein the helium and oxygen form a binary mixture with 0.5% oxygen and 99.5% helium and wherein the CF.sub.4 equals 3% of that binary mixture. ### Claim 5 (depends on 4) The process in accordance with claim 4 wherein the pressure of the plasma equals 0.5 torr and wherein the plasma is generated by the application of RF power to the gaseous mixture at a power level of 250 watts. ### Claim 6 A process in accordance with cliam 4 wherein the pressure of the plasma equals 0.65 torr and the plasma is generated by the application of an RF field to the gaseous mixture at a power level of 350 watts. ### Claim 7 (depends on 4) A process in accordance with claim 4 wherein the pressure equals 0.8 torr and wherein the plasma is generated by the application of an RF field to the gaseous mixture at an RF power level of 350 watts. ### Claim 8 (depends on 2) A process in accordance with claim 2 wherein the gas carrier is argon. ### Claim 9 (depends on 2) A process in accordance with claim 2 wherein the inert gas carrier is nitrogen. ### Claim 10 A composition of matter useful in the process for selective etching of silicon oxides and nitrides in the presence of single crystal silicon in a low pressure RF plasma during the manufacture of thin film integrated circuits, comprising: a gaseous multi-component mixture of oxygen, a noble gas carrier and CF.sub.4 wherein the oxygen consists between 0.25 and 6% of the mixture, CF.sub.4 constitutes between 0.5 and 7% of the mixture and the balance is one of the group of inert gases including helium, argon, or nitrogen. ### Claim 11 (depends on 10) A composition of matter in accordance with claim 10 wherein the noble gas carrier is helium, and wherein the helium and oxygen form a binary mixture including 0.5% oxygen and 99.5% helium and wherein the CF.sub.4 constitutes 3%of said binary mixture. ### Claim 12 In a composite process for removing photoresist material in the presence of metallic materials without significant degradation of the metallic materials during the manufacture of thin film integrated circuits, the improvement comprising the step of: exposing the layer of photoresist material to a low temperature, low pressure plasma formed from a gaseous multicomponent mixture at pressures of a few torr of oxygen, a noble gas carrier and a halogen containing gas selected from the group consisting of organohalides defined as having no more than two carbon atoms per molecule and being at least partially substituted by halogens including a predominance of fluorine atoms, inorganic halides defined as having at least one fluorine atom per molecule, and fluorine gas and wherein the oxygen is in the range of 1 to 10% by volume of the noble gas carrier and said oxygen-noble gas components comprise more than 90% by volume of said gaseous multicomponent mixture. ### Claim 13 In a composite process for removing photoresist material in the presence of metallic materials without significant degradation of the metallic materials during the manufacture of thin film integrated circuits, the improvement comprising the step of: exposing the layer of photoresist materialto a low temperature, low pressure plasma formed from a gaseous multicomponent mixture at pressures of a few torr of oxygen, organohalide, and noble gas carrier in which the organohalide is selected from a group of organohalides defined as having no more than two carbon atoms per molecule and being at least partially substituted by halogens including a predominance of fluorine atoms, and wherein the oxygen is in the range of 1 to 10% by volume of the noble gas carrier and said oxygen-noble gas components comprise more than 90% by volume of said gaseous multi-component mixture. ### Claim 14 In a composite process for removing photoresist material in the presence of metallic materials without significant degradation of the metallic materials during the manufacture of thin film integrated circuits, the improvement comprising the step of: exposing the layer of photoresist material to a low temperature, low pressure plasma formed from a gaseous muticomponent mixture at pressures of a few torr of oxygen, inorganic halide, and a noble gas carrier in which the inorganic halide is selected from a group of halides defined as having at least one fluroine atom per molecule, and wherein the oxygen is in the range of 1 to 10% by volume of the noble gas carrier and said oxygen-noble gas components comprise more than 90% by volume of said gaseous multi-component mixture. ### Claim 15 In a composite process for removing photoresist material in the presence of metallic materials without significant degradation of the metallic materials during the manufacture of thin film integrated circuits, the improvement comprising the step of: exposing the layer of photoresist material to a low temperature, low pressure plasma formed from a gaseous multicomponent mixture at pressures of a few torr of oxygen, fluorine and a noble gas carrier, and wherein the oxygen is in the range of 1 to 10% by volume of the noble gas carrier and said oxygen-noble gas components comprise more than 90% by volume of said gaseous multi-component mixture. ### Claim 16 (depends on 2) A process as in claim 2 wherein the defined group of organohalides are fully fluorine substituted. ### Claim 17 (depends on 2) A process as in claim 2 wherein the defined group of organohalides contain at least one hydrogen atom per molecule. ### Claim 18 (depends on 2) A process as in claim 2 wherein each member of the defined group of organohalides contains at least one halogen atom other than fluorine. ### Claim 19 (depends on 2) A process as in claim 2 wherein the defined organohalide constitutes a mixture of organohalides. ### Claim 20 (depends on 3) A process as in claim 3 wherein the defined group of inorganic halides are fully fluorinated. ### Claim 21 (depends on 3) A process as in claim 3 wherein the defined group of inorganic halides contain at least one hydrogen atom per molecule. ### Claim 22 (depends on 3) A process as in claim 3 wherein the defined inorganic halide constitutes a mixture of inorganic halides. ### Claim 23 In a composite process for removing photoresist material in the presence of metallic material without significant degradation of the metallic material during the manufacture of thin film integrated circuits, the improvement comprising the step of: exposing the layer of photoresist material to a low temperature, low pressure plasma formed from a gaseous multicomponent mixture at pressures of a few torr of oxygen, fluorine, organohalide, inorganic halide, and noble gas carrier in which the organohalide is selected from a group of organohalides defined as having no more than two carbon atoms per molecule and being at least partially substituted by halogens including a predominance of fluorine atoms and in which the inorganic halide is selected from a group of halides defined as having at least one fluorine atom per molecule and wherein the oxygen is in the range of 1 to 10% by volume of the noble gas carrier and said oxygen-noble gas components comprise more than 90% by volume of said gaseous multicomponent mixture. ### Claim 24 (depends on 2) A process as in claim 2 wherein the gaseous multicomponent mixture is supplied from a single pressurized source. ### Claim 25 (depends on 3) A process as in claim 3 wherein the gaseous multicomponent mixture is supplied from a single pressurized source. ### Claim 26 (depends on 12) A process as in claim 12 wherein the gaseous multicomponent mixture is supplied from a single pressurized source. ### Claim 27 (depends on 2) A process as in claim 2 wherein the organohalide component is tetrafluoromethane and the noble gas is helium in a range of mixtures from 1 to 10% oxygen, 1 to 10% tetrafluoromethane, balance helium by volume. ### Claim 28 (depends on 16) A process as in claim 16 wherein the noble gas is argon. ### Claim 29 (depends on 2) A process as in claim 2 wherein the organohalide is trifluoromethane and the noble gas is helium in a range of mixtures from 1 to 10% oxygen, 1 to 10% trifluoromethane, balance helium by volume. ### Claim 30 (depends on 18) A process as in claim 18 wherein the noble gas is argon. ### Claim 31 (depends on 4) A process as in claim 4 wherein the noble gas is helium and where the range of mixture is from 1 to 10% oxygen, 1 to 10% fluorine, balance helium by volume. ### Claim 32 (depends on 4) A process as in claim 4 wherein the noble gas is argon and wherein the range of mixtures is from 1 to 10% oxygen, 1 to 10% fluorine, balance argon by volume. ### Claim 33 (depends on 3) A process as in claim 3 wherein the inorganic halide component is gaseous hydrogen fluoride and wherein the mixture includes one of the noble gases helium or argon and wherein the range of mixtures is from 1 to 10% oxygen, 1 to 10% hydrogen fluoride, balance noble gas by volume. ### Claim 34 (depends on 12) A process as in claim 12 wherein the organohalide is tetrafluoromethane, the inorganic halide is fluorine, and the noble gas is helium in a range of mixtures from 1 to 10% oxygen, 1 to 10% tetrafluoromethane, 1 to 10% fluorine, balance helium by volume. ### Claim 35 (depends on 23) A process as in claim 23 wherein the organohalide is trifluoromethane. ### Claim 36 (depends on 23) A process as in claim 23 where the noble gas is argon. ### Claim 37 (depends on 24) A process as in claim 24 where the noble gas is argon. ### Claim 38 (depends on 8) A process as in claim 8 wherein the mixture of organohalides contain tetrafluoromethane and trifluoromethane in a range of mixtures from 1 to 10% oxygen, 1 to 10% tetrafluoromethane, 1 to 10% trifluoromethane, balance helium by volume. ### Claim 39 (depends on 27) A process in claim 27 wherein the noble gas is argon. ### Claim 40 (depends on 12) A process as in claim 12 wherein the organohalide is a mixture of tetrafluoromethane and trifluoromethane and the inorganic halide is fluorine in a range of mixtures from 1 to 10% oxygen, 1 to 10% tetrafluoromethane, 1 to 10% trifluoromethane, 1 to 10% fluorine, balance helium by volume. ### Claim 41 (depends on 29) A process as in claim 29 wherein the noble gas is argon. ### Claim 42 A composition of matter useful in a process for removing photoresist material in a low temperature, low pessure rf plasma during the manufacture of thin film integrated circuits, comprising, a gaseous multicomponent mixture of oxygen, a noble gas carrier and a halogen containing gas selected from the group consisting of; organo halides defined as having no more than two carbon atoms per molecule and being at least partially substituted by halogens including a predominance of fluorine atoms, inorganic halides defined as having at least one fluorine atom per molecule, and fluorine gas and where said oxygen is in the range of 1 to 10% by volume of the noble gas carrier and said oxygen-noble gas components comprise more than 90% by volume of said gaseous multi-component mixture. ### Claim 43 A composition of matter useful in a process for removing photoresist material in a low temperature, low pressure rf plasma during the manufacture of thin film integrated circuits, comprising: a gaseous multi-component mixture of oxygen, organohalide, and noble gas carrier in which the organohalide is selected from a group of organohalides defined as having no more than two carbon atoms per molecule and being at least partially substituted by halogens including a predominance of fluorine atoms and where said oxygen is in the range of 1 to 10% by volume of the noble gas carrier and said oxygen-noble gas components comprise more than 90% by volume of said gaseous multi-components mixture. ### Claim 44 A composition of matter useful in a process for removing photoresist material in a low temperature, low pressure rf plasma comprising, a ternary mixture of oxygen, inorganic halide, and a noble gas carrier in which the inorganic halide is selected from a group of halides defined as having at least one fluorine atom per molecule and where said oxygen is in the range of 1 to 10% by volume of the noble gas carrier and aid oxygen-noble gas components comprise more than 90% by volume of said gaseous multi-component mixture. ### Claim 45 (depends on 32) A composition as in claim 32 wherein the defined group of organohalides are fully fluorine substituted. ### Claim 46 (depends on 33) A composition as in claim 33 wherein the defined group of inorganic halides are fully fluorinated. ### Claim 47 (depends on 32) A composition as in claim 32 wherein the defined organic halide constitutes a mixture of organic halides. ### Claim 48 (depends on 33) A composition as in claim 33 wherein the defined inorganic halide constitutes a mixture of inorganic halides. ### Claim 49 A composition of matter useful in a process for removing photoresist material in a low temperature, low pressure rf plasma during the manufacture of thin film integrated circuits, comprising, a gaseous multi-component mixture of oxygen, organohalide, inorganic halide, and noble gas carrier in which the organohalide is selected from a group of organohalides defined as having no more than two carbon atoms per molecule and being at least partially substituted by halogens including a predominance of fluorine atoms and in which the inorganic halide is selected from a group of halides defined as having at least one fluorine atom per molecule and where said oxygen is in the range of 1 to 10% by volume of the noble gas carrier and said oxygen-noble gas components comprise more than 90% by volume of said gaseous multi-component mixture. ### Claim 50 (depends on 32) A composition as in claim 32 wherein the organohalide component is tetrafluoromethane and the range of mixture is from 1 to 10% by volume oxygen, 1 to 10% by volume tetrafluoromethane, balance is selected from the group of noble gases including argon and helium. ### Claim 51 (depends on 32) A composition as in claim 32 wherein the organohalide is trifluoromethane and the noble gas is selected from the group including argon and helium in a range of mixtures from 1 to 10% oxygen, 1 to 10% tetrafluoromethane, balance noble gas by volume. ### Claim 52 (depends on 33) A composition as in claim 33 wherein the inorganic halide component is fluorine gas and the noble gas selected from the group including argon and helium in a range of mixtures from 1 to 10% oxygen, 1 to 10% fluorine, balance noble gas by volume. ### Claim 53 (depends on 33) A composition as in claim 33 wherein the inorganic halide component is gaseous hydrogen fluoride and the noble gas is selected from the group including argon and helium in a range of mixtures from 1 to 10% oxygen, 1 to 10% hydrogen fluoride, balance noble gas by volume. ### Claim 54 A composition of matter useful in the process for removing photoresist material in a low temperature, low pressure rf plasma during the manufacture of thin film integrated circuits, comprising, a gaseous multi-component mixture of oxygen, tegrafluoromethane and trifluoromethane, and fluorine gas in a range of mixtures from 1 to 10% by volume trifluoromethane, 1 to 10% by volume fluorine and the balance a noble gas selected from the group including helium and argon.