# US 11,443,936 B2 · Methods and apparatus for aluminum oxide surface recovery > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,443,936 B2 - Document ID: US11443936B2 - Status: Granted - Kind: B2 - Application number: 16/906,999 - Filed: 2020-06-19 - Published: 2021-12-23 - Granted: 2022-09-13 - Earliest claimed: 2020-06-19 - Assignees: Applied Materials, Inc. - Applicants: Applied Materials, Inc. - Inventors: Carmen Leal Cervantes; Alexander Jansen; Xiangjin Xie - Web page: https://patentgrep.com/patent/US11443936B2 ## CPC - H10P 70/10: {Cleaning before device manufacture, i.e. Begin-Of-Line process} - H10P 70/273: {the processing being a delineation of conductive layers, e.g. by RIE} - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract A method of cleaning a surface of a substrate uses alcohol and water treatments. The method may include applying an alcohol treatment on a surface of the substrate with the alcohol treatment configured to provide surface reduction and applying a water treatment to the surface of the substrate with the water treatment configured to enhance selectivity of at least a portion of the surface for a subsequent barrier layer process by removing alcohol from the at least a portion of the surface. The water treatment may be performed simultaneously with the alcohol treatment or performed after the alcohol treatment. The water treatment may include vaporized water or water injected into a plasma to produce hydrogen or oxygen radicals. ## Claims ### Claim 1 A method of cleaning a surface of a substrate, comprising: applying an alcohol treatment on a surface of the substrate, the alcohol treatment configured to provide surface reduction of a metal oxide layer; and applying a water treatment to the surface of the substrate after applying the alcohol treatment, the water treatment configured to enhance selectivity of at least a portion of the surface of the substrate for a subsequent barrier layer process by removing alcohol from the at least a portion of the surface to reduce an alcohol induced nucleation delay on the surface and wherein the water treatment includes exposing the surface of the substrate to radicals from a plasma produced with water. ### Claim 2 (depends on 1) The method of claim 1, wherein the alcohol treatment includes ethanol or methanol. ### Claim 3 (depends on 1) The method of claim 1, wherein the surface of the substrate includes at least a portion of an etch stop layer. ### Claim 4 (depends on 1) The method of claim 1, wherein the water treatment is performed at a pressure of greater than zero Torr to approximately 1 Torr. ### Claim 5 (depends on 1) The method of claim 1, wherein the water treatment is performed using a remote plasma source (RPS). ### Claim 6 (depends on 1) The method of claim 1, wherein the surface of the substrate includes at least a portion of a contact surface. ### Claim 7 (depends on 1) The method of claim 1, wherein the alcohol treatment is performed until an underlying metal surface beneath the metal oxide layer is exposed. ### Claim 8 (depends on 1) The method of claim 1, wherein the surface reduction of the metal oxide layer includes removing at least a portion of a copper oxide layer on a copper contact. ### Claim 9 (depends on 1) The method of claim 1, wherein the water treatment has a duration of approximately 5 seconds to approximately 120 seconds. ### Claim 10 (depends on 1) The method of claim 1, wherein the water treatment includes a water treatment mixture including a carrier gas and water used to produce the plasma. ### Claim 11 (depends on 10) The method of claim 10, wherein the water treatment mixture has greater than zero to approximately 100% water. ### Claim 12 (depends on 11) The method of claim 11, wherein the water treatment mixture has approximately 50% water. ### Claim 13 (depends on 10) The method of claim 10, wherein the carrier gas is helium or argon. ### Claim 14 A method of cleaning a surface of a substrate, comprising: applying an alcohol treatment on a surface of the substrate, the alcohol treatment configured to provide surface reduction; and applying a water treatment to the surface of the substrate for a duration of approximately 5 seconds to approximately 120 seconds and at a pressure of greater than zero Tor to approximately 1 Torr after applying the alcohol treatment, wherein the water treatment includes exposing the surface of the substrate to hydrogen radicals or oxygen radicals generated by injecting a water treatment mixture into plasma, and wherein the water treatment is configured to enhance selectivity of at least a portion of the surface of the substrate for a subsequent barrier layer process by removing alcohol from the portion of the surface to reduce an alcohol induced nucleation delay on the surface. ### Claim 15 (depends on 14) The method of claim 14, wherein the water treatment mixture includes water and a carrier gas. ### Claim 16 (depends on 15) The method of claim 15, wherein the carrier gas is helium or argon. ### Claim 17 (depends on 15) The method of claim 15, wherein the water treatment mixture contains greater than zero to approximately 100% water. ### Claim 18 (depends on 17) The method of claim 17, wherein the water treatment mixture contains approximately 50% water and approximately 50% of the carrier gas. ### Claim 19 A non-transitory, computer readable medium having instructions stored thereon that, when executed, cause a method for cleaning a surface of a substrate to be performed, the method comprising: applying an alcohol treatment on a surface of the substrate, the alcohol treatment configured to provide surface reduction; applying a water treatment to the surface of the substrate after applying the alcohol treatment, the water treatment configured to enhance selectivity of at least a portion of the surface of the substrate for a subsequent barrier layer process by removing alcohol from the at least a portion of the surface to reduce an alcohol induced nucleation delay on the surface and wherein the water treatment includes exposing the surface of the substrate to radicals from a plasma produced with water. ### Claim 20 (depends on 19) The non-transitory, computer readable medium of claim 19, further comprising: performing the water treatment at a pressure of greater than zero Torr to approximately 1 Torr; performing the water treatment with a mixture including a carrier gas and water to produce the plasma; or performing the water treatment for a duration of approximately 5 seconds to approximately 120 seconds.