# US 12,217,954 B2 · Method of cleaning a surface > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,217,954 B2 - Document ID: US12217954B2 - Status: Granted - Kind: B2 - Application number: 17/407,839 - Filed: 2021-08-20 - Published: 2022-03-03 - Granted: 2025-02-04 - Earliest claimed: 2020-08-25 - Assignees: ASM IP Holding B.V. - Applicants: ASM IP Holding B.V. - Inventors: Shaoren Deng; Andrea Illiberi; Daniele Chiappe; Eva Tois; Giuseppe Alessio Verni; Michael Givens; Varun Sharma; Chiyu Zhu; Shinya Iwashita; Charles Dezelah; Viraj Madhiwala; Jan Willem Maes; Marko Tuominen; Anirudhan Chandrasekaran - Web page: https://patentgrep.com/patent/US12217954B2 ## CPC - H10P 70/23: {during, before or after processing of insulating materials} - H10P 70/277: {the processing being a planarisation of conductive layers} - B08B 3/08: the liquid having chemical or dissolving effect - B08B 5/00: Cleaning by methods involving the use of air flow or gas flow (cleaning hollow articles by methods or apparatus specially adapted thereto B08B9/00) - C11D 7/02: Inorganic compounds - C11D 7/04: Water-soluble compounds - C11D 7/245: {cyclic} - C11D 7/261: {Alcohols; Phenols} - C11D 7/264: {Aldehydes; Ketones; Acetals or ketals} - C11D 7/265: {Carboxylic acids or salts thereof} - C23C 16/0227: {by cleaning or etching} - C23C 16/04: Coating on selected surface areas, e.g. using masks - H10P 14/432: {using selective deposition} - H10P 70/27: {during, before or after processing of conductive materials, e.g. polysilicon or amorphous silicon layers} - C11D 2111/22: Electronic devices, e.g. PCBs or semiconductors - 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 - C11D: DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL - 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) ## Abstract Methods for cleaning a substrate are disclosed. The substrate comprises a dielectric surface and a metal surface. The methods comprise providing a cleaning agent to the reaction chamber. ## Claims ### Claim 1 A method for cleaning a substrate, the method comprising: providing a substrate comprising a dielectric and an oxidized metal surface, to a reaction chamber; providing a reducing agent to the reaction chamber, thereby contacting the substrate with the reducing agent and converting the oxidized metal surface to a metal surface; providing an oxidizing agent to the reaction chamber, thereby contacting the substrate with the oxidizing agent and oxidizing any metal contaminants on the dielectric surface, thus forming oxidized metal contaminants; and, providing a cleaning agent to the reaction chamber, thereby contacting the substrate with the cleaning agent and removing the oxidized metal contaminants from the substrate, wherein the cleaning agent comprises a halogen-containing beta diketonate. ### Claim 2 (depends on 1) The method according to claim 1 wherein the oxidizing agent is an oxygen-comprising gas or gas mixture. ### Claim 3 (depends on 1) The method according to claim 1 wherein the oxidizing agent is a gas selected from O2, O3, H2O, H2O2, and mixtures thereof. ### Claim 4 (depends on 1) The method according to claim 1 wherein the reducing agent comprises an alcohol. ### Claim 5 (depends on 1) The method according to claim 1 wherein the cleaning agent further comprises carbon monoxide. ### Claim 6 (depends on 1) The method according to claim 1 wherein the cleaning agent further comprises a carboxylic acid. ### Claim 7 (depends on 1) The method according to claim 1 wherein the step of providing a cleaning agent to the reaction chamber is followed by a step of providing a further oxidizing agent to the reaction chamber. ### Claim 8 (depends on 1) The method according to claim 1 wherein the step of providing a cleaning agent to the reaction chamber is followed by a step of providing a cleaning residue removal agent to the reaction chamber. ### Claim 9 (depends on 8) The method according to claim 8 wherein the cleaning residue removal agent comprises an alcohol. ### Claim 10 (depends on 9) The method according to claim 9 wherein the alcohol comprises an alkyl alcohol. ### Claim 11 (depends on 10) The method according to claim 10 wherein the alkyl alcohol is selected from methanol, ethanol, isopropanol, and isobutanol. ### Claim 12 (depends on 8) The method according to claim 8 wherein the cleaning residue removal agent comprises a further oxidizing agent. ### Claim 13 A method for cleaning a substrate, the method comprising: providing a substrate comprising a dielectric and an oxidized metal surface, to a reaction chamber; providing a reducing agent to the reaction chamber, thereby contacting the substrate with the reducing agent and converting the oxidized metal surface to a metal surface; providing an oxidizing agent to the reaction chamber, thereby contacting the substrate with the oxidizing agent and oxidizing any metal contaminants on the dielectric surface, thus forming oxidized metal contaminants; and, providing a cleaning agent to the reaction chamber, thereby contacting the substrate with the cleaning agent and removing the oxidized metal contaminants from the substrate, wherein the step of providing a cleaning agent to the reaction chamber is followed by a step of providing a further oxidizing agent to the reaction chamber, and wherein the step of providing a further oxidizing agent to the reaction chamber comprises, in the following order, providing O2 to the reaction chamber in an O2 pulse and providing H2O to the reaction chamber in a H2O pulse. ### Claim 14 (depends on 1) A system comprising one or more reaction chambers, a cleaning gas source, and a controller, the controller being configured for causing the system to carry out a method according to claim 1. ### Claim 15 A method for cleaning a substrate, the method comprising: providing a substrate comprising a dielectric and an oxidized metal surface, to a reaction chamber; providing a reducing agent to the reaction chamber, thereby contacting the substrate with the reducing agent and converting the oxidized metal surface to a metal surface; providing an oxidizing agent to the reaction chamber, thereby contacting the substrate with the oxidizing agent and oxidizing any metal contaminants on the dielectric surface, thus forming oxidized metal contaminants; and, providing a cleaning agent to the reaction chamber, thereby contacting the substrate with the cleaning agent and removing the oxidized metal contaminants from the substrate, wherein the step of providing a cleaning agent to the reaction chamber is followed by a step of providing a cleaning residue removal agent to the reaction chamber, wherein the cleaning residue removal agent comprises a further oxidizing agent, and wherein the step of providing a cleaning residue removal agent to the reaction chamber comprises, in the following order, providing O2 to the reaction chamber in an O2 pulse and providing H2O to the reaction chamber in a H2O pulse. ### Claim 16 A method for cleaning a substrate, the method comprising: providing a substrate comprising a dielectric and an oxidized metal surface, to a reaction chamber; providing a reducing agent to the reaction chamber, thereby contacting the substrate with the reducing agent and converting the oxidized metal surface to a metal surface; providing an oxidizing agent to the reaction chamber, thereby contacting the substrate with the oxidizing agent and oxidizing any metal contaminants on the dielectric surface, thus forming oxidized metal contaminants; and, providing a cleaning agent to the reaction chamber, thereby contacting the substrate with the cleaning agent and removing the oxidized metal contaminants from the substrate, wherein the step of providing a cleaning agent to the reaction chamber is followed by a step of providing a cleaning residue removal agent to the reaction chamber, and wherein the step of providing a cleaning residue removal agent to the reaction chamber comprises a first sub step and a second sub step, the first sub step comprising providing an alcohol to the reaction chamber, and the second sub step comprising providing an oxidizing agent to the reaction chamber. ### Claim 17 A method for selectively depositing a material on a substrate comprising a metal surface and a dielectric surface, comprising the steps: cleaning the substrate by means of a method comprising: providing a substrate comprising a dielectric and an oxidized metal surface, to a reaction chamber; providing a reducing agent to the reaction chamber, thereby contacting the substrate with the reducing agent and converting the oxidized metal surface to a metal surface; providing an oxidizing agent to the reaction chamber, thereby contacting the substrate with the oxidizing agent and oxidizing any metal contaminants on the dielectric surface, thus forming oxidized metal contaminants; and, providing a cleaning agent to the reaction chamber, thereby contacting the substrate with the cleaning agent and removing the oxidized metal contaminants from the substrate; and selectively depositing the material on one of the metal surface or the dielectric surface. ### Claim 18 (depends on 17) The method according to claim 17 wherein the material comprises a metal, and wherein the metal is deposited on the metal surface. ### Claim 19 A method for cleaning a substrate, the method comprising: providing a substrate comprising a dielectric and an oxidized metal surface, to a reaction chamber; providing a reducing agent to the reaction chamber, thereby contacting the substrate with the reducing agent and converting the oxidized metal surface to a metal surface; providing an oxidizing agent to the reaction chamber, thereby contacting the substrate with the oxidizing agent and oxidizing any metal contaminants on the dielectric surface, thus forming oxidized metal contaminants; and, providing a cleaning agent to the reaction chamber, thereby contacting the substrate with the cleaning agent and removing the oxidized metal contaminants from the substrate, wherein the cleaning agent comprises a compound comprising an alkyl-substituted cyclopentadienyl group.