# US 5,704,986 A · Semiconductor substrate dry cleaning method > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,704,986 A - Document ID: US5704986A - Status: Granted - Kind: A - Application number: 08/529,635 - Filed: 1995-09-18 - Granted: 1998-01-06 - Earliest claimed: 1995-09-18 - Assignees: Taiwan Semiconductor Manufacturing Company, Ltd. - Inventors: Chien-Fong Chen; Chia-Chun Cheng; Chi-Fu Chang; Kuo-Sheng Chuang - Web page: https://patentgrep.com/patent/US5704986A ## CPC - H10P 70/18: {by combined dry cleaning and wet cleaning (H10P70/52 takes precedence)} - B08B 7/00: Cleaning by methods not provided for in a single other subclass or a single group in this subclass - C23C 16/0236: {by etching with a reactive gas} - G03F 7/42: Stripping or agents therefor - H10D 64/0134: {with a treatment, e.g. annealing, after the formation of the insulator and before the formation of the conductor} - H10D 64/01346: {in a gaseous ambient using an oxygen or a water vapour, e.g. oxidation through a layer (H10D64/01344 takes precedence)} - H10P 14/6309: {of silicon in uncombined form, i.e. pure silicon} - H10P 14/6322: {Formation by thermal treatments (formation by plasma treatment H10P14/6319)} - H10P 14/6504: {In-situ cleaning} - H10P 50/287: {by chemical means} - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - B08B: CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL - C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) - 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) - H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES ## Abstract A method for cleaning a semiconductor substrate. Introduced into a semiconductor substrate processing chamber is a semiconductor substrate. The semiconductor substrate and the semiconductor substrate processing chamber are maintained at a temperature not exceeding about 800 degrees centigrade. Introduced substantially simultaneously with the semiconductor substrate into the semiconductor substrate processing chamber is a low flow of a first oxidant gas. Introduced into the semiconductor substrate processing chamber immediately subsequent to the low flow of the first oxidant gas is a high flow of a second oxidant gas. Introduced into the semiconductor wafer processing chamber no earlier than the high flow of the second oxidant gas is a flow of a chlorine containing getter material. The semiconductor substrate is exposed to the high flow of the second oxidant gas and the flow of the chlorine containing getter material at a temperature not exceeding 800 degrees centigrade for a time period sufficient to remove organic contaminant residues and metal ion contaminant residues from the surface of the semiconductor substrate. ## Claims ### Claim 1 A method for cleaning a semiconductor substrate consisting of: introducing a semiconductor substrate into a semiconductor substrate processing chamber, the semiconductor substrate and the semiconductor substrate processing chamber being maintained at a temperature not exceeding about 800 degrees centigrade; introducing into the semiconductor substrate processing chamber substantially simultaneously with the semiconductor substrate a low flow of a first oxidant gas, the first oxidant gas being oxygen gas, the low flow of the first oxidant gas being immediately followed by a high flow of a second oxidant gas; introducing into the semiconductor substrate processing chamber no earlier than the high flow of the second oxidant gas a flow of a chlorine containing getter material, the difference in time between introducing the high flow of the second oxidant gas and introducing the flow of the chlorine containing getter material being a time delay; and exposing the semiconductor substrate to the high flow of the second oxidant gas and the flow of the chlorine containing getter material at the temperature not exceeding about 800 degrees centigrade for a time period sufficient to remove from the semiconductor substrate organic contaminant residues and remove from or stabilize upon the semiconductor substrate metallic species which are detrimental to integrated circuit devices subsequently formed upon the semiconductor substrate, where the organic contaminant residues are removed from the semiconductor substrate and the metallic species are removed from or stabilized upon the semiconductor substrate without carbonizing the organic contaminant residues. ### Claim 2 (depends on 1) The method of claim 1 wherein the semiconductor substrate processing chamber is maintained at a pressure of about 700 to about 780 torr. ### Claim 3 (depends on 1) The method of claim 1 wherein the temperature of the semiconductor substrate and the semiconductor substrate processing chamber is from about 600 to about 800 degrees centigrade. ### Claim 4 (depends on 1) The method of claim 1 wherein the low flow of the first oxidant gas is a low flow of oxygen at about 100 to about 1000 standard cubic centimeters per minute (sccm). ### Claim 5 (depends on 1) The method of claim 1 wherein the high flow of the second oxidant gas is a high flow of oxygen at about 5 to about 15 standard liters per minute (slpm). ### Claim 6 (depends on 1) The method of claim 1 wherein the flow of chlorine containing getter material is from about 50 to about 250 standard cubic centimeters per minute (sccm). ### Claim 7 (depends on 1) The method of claim 1 wherein the chlorine containing getter material is chosen from the group of chlorine containing getter materials consisting of Tri-Chloro-Ethane (TCA), Tri-Chloro-Ethylene (TCE), Hydrogen Chloride (HCl), Trans-Di-Chloro-Ethylene (TDCE) and Cis-Di-Chloro-Ethylene (CDCE). ### Claim 8 (depends on 1) The method of claim 1 wherein the time delay is no greater than about 2 minutes. ### Claim 9 A method for cleaning a semiconductor substrate prior to a thermal process consisting of: introducing a semiconductor substrate into a semiconductor substrate processing chamber, the semiconductor substrate and the semiconductor substrate processing chamber being maintained at a temperature not exceeding about 800 degrees centigrade; introducing into the semiconductor substrate processing chamber substantially simultaneously with the semiconductor substrate a low flow of a first oxidant gas, the first oxidant gas being oxygen gas, the low flow of the first oxidant gas being immediately followed by a high flow of a second oxidant gas; introducing into the semiconductor substrate processing chamber no earlier than the high flow of the second oxidant gas a flow of a chlorine containing getter material, the difference in time between introducing the high flow of the second oxidant gas and introducing the flow of the chlorine containing getter material being a time delay; exposing the semiconductor substrate to the high flow of the second oxidant gas and the flow of the chlorine containing getter material at the temperature not exceeding about 800 degrees centigrade for a time period sufficient to remove from the semiconductor substrate organic contaminant residues and remove from or stabilize upon the semiconductor substrate metallic species which are detrimental to integrated circuit devices subsequently formed upon the semiconductor substrate, where the organic contaminant residues are removed from the semiconductor substrate and the metallic species are removed from or stabilized upon the semiconductor substrate without carbonizing the organic contaminant residues; and exposing then the semiconductor substrate to a thermal process. ### Claim 10 (depends on 9) The method of claim 9 wherein the semiconductor substrate processing chamber is a semiconductor wafer furnace tube maintained at a pressure of from about 700 to about 780 torr. ### Claim 11 (depends on 10) The method of claim 10 wherein the temperature of the semiconductor substrate and the semiconductor wafer furnace tube is from about 600 to about 800 degrees centigrade. ### Claim 12 (depends on 9) The method of claim 9 wherein the low flow of the first oxidant gas is a low flow of oxygen at about 100 to about 1000 standard cubic centimeters per minute (sccm). ### Claim 13 (depends on 9) The method of claim 9 wherein the high flow of the second oxidant gas is a high flow of oxygen at about 5 to about 15 standard liters per minute (slpm). ### Claim 14 (depends on 9) The method of claim 9 wherein the flow of chlorine containing getter material is from about 50 to about 250 standard cubic centimeters per minute (sccm). ### Claim 15 (depends on 9) The method of claim 9 wherein the chlorine containing getter material is chosen from the group of chlorine containing getter materials consisting of Tri-Chloro-Ethane (TCA), Tri-Chloro-Ethylene (TCE), Hydrogen Chloride (HCl), Trans-Di-Chloro-Ethylene (TDCE) and Cis-Di-Chloro-Ethylene (CDCE). ### Claim 16 (depends on 9) The method of claim 9 wherein the time delay is no greater than about 2 minutes. ### Claim 17 A method for cleaning in-situ and subsequently thermally processing a semiconductor substrate consisting of: introducing a semiconductor substrate into a semiconductor substrate processing chamber, the semiconductor substrate and the semiconductor substrate processing chamber being maintained at a temperature not exceeding about 800 degrees centigrade; introducing into the semiconductor substrate processing chamber substantially simultaneously with the semiconductor substrate a low flow of a first oxidant gas, the first oxidant gas being oxygen gas, the low flow of the first oxidant gas being immediately followed by a high flow of a second oxidant gas; introducing into the semiconductor substrate processing chamber no earlier than the high flow of the second oxidant gas a flow of a chlorine containing getter material, the difference in time between introducing the high flow of the second oxidant gas and introducing the flow of the chlorine containing getter material being a time delay; exposing the semiconductor substrate to the high flow of the second oxidant gas and the flow of the chlorine containing getter material at the temperature not exceeding about 800 degrees centigrade for a time period sufficient to remove from the semiconductor substrate organic contaminant residues and remove from or stabilize upon the semiconductor substrate metallic species which are detrimental to integrated circuit devices subsequently formed upon the semiconductor substrate, where the organic contaminant residues are removed from the semiconductor substrate and the metallic species are removed from or stabilized upon the semiconductor substrate without carbonizing the organic contaminant residues; and exposing then in-situ the semiconductor substrate to a thermal process. ### Claim 18 (depends on 17) The method of claim 17 wherein the semiconductor substrate process chamber is a semiconductor wafer furnace tube maintained at a pressure of from about 700 to about 780 torr. ### Claim 19 (depends on 18) The method of claim 18 wherein the temperature of the semiconductor substrate and the semiconductor wafer furnace tube is from about 600 to about 800 degrees centigrade. ### Claim 20 (depends on 17) The method of claim 17 wherein the low flow of the first oxidant gas is a low flow of oxygen at about 100 to about 1000 standard cubic centimeters per minute (sccm) and the high flow of the second oxidant gas is a high flow of oxygen at about 5 to about 15 standard liters per minute (slpm). ### Claim 21 (depends on 17) The method of claim 17 wherein the flow of chlorine containing getter material is from about 50 to about 250 standard cubic centimeters per minute (sccm) and the chlorine containing getter material is chosen from the group of chlorine containing getter materials consisting of Tri-Chloro-Ethane (TCA), Tri-Chloro-Ethylene (TCE), Hydrogen Chloride (HCl), Trans-Di-Chloro-Ethylene (TDCE) and Cis-Di-Chloro-Ethylene (CDCE). ### Claim 22 (depends on 17) The method of claim 17 wherein the time delay is no greater than about 2 minutes. ### Claim 23 (depends on 17) The method of claim 17 wherein the thermal process is chosen from the group of thermal processes consisting of thermal oxide growth processes and thermal annealing processes. ### Claim 24 (depends on 23) The method of claim 23 wherein the thermal process is undertaken at a higher temperature than the temperature employed in cleaning the semiconductor substrate wafer.