# US 12,769,198 B2 · Methods and apparatus for ruthenium oxide reduction on extreme ultraviolet photomasks > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,769,198 B2 - Document ID: US12769198B2 - Status: Granted - Kind: B2 - Application number: 18/276,760 - Filed: 2022-02-08 - Published: 2024-04-11 - Granted: 2026-10-20 - Earliest claimed: 2021-02-25 - Assignees: Applied Materals, Inc. - Applicants: Applied Materials, Inc. - Inventors: Banqiu Wu; Khalid Makhamreh; Eliyahu Shlomo Dagan - Web page: https://patentgrep.com/patent/US12769198B2 ## CPC - G03F 1/24: Reflection masks; Preparation thereof - G03F 1/74: by charged particle beam [CPB], e.g. focused ion beam - 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) ## Abstract Methods and apparatus for reducing ruthenium oxide on an extreme ultraviolet (EUV) photomask leverage temperature, plasma, and chamber pressure to increase the reduction. In some embodiments, a method includes heating the EUV photomask with a ruthenium (Ru) capping layer with a top surface which has a Ru oxide layer to a temperature of approximately 100 degrees Celsius to approximately a thermal budget of the EUV photomask, flowing a reducing agent gas into an EUV photomask processing chamber, and pressurizing the EUV photomask processing chamber to a process pressure to increase a reducing reaction between the reducing agent gas and a Ru oxide layer on the Ru capping layer. Other embodiments may incorporate remote plasma generators or atmospheric-pressure plasma generators to enhance the reduction of Ru oxides on the Ru capping layer. ## Claims ### Claim 1 A method for reducing ruthenium oxides on an extreme ultraviolet (EUV) photomask, comprising: heating the EUV photomask with a ruthenium (Ru) capping layer with a top surface which has a Ru oxide layer to a temperature of approximately 100 degrees Celsius to approximately a thermal budget of the EUV photomask; flowing a reducing agent gas into an EUV photomask processing chamber; and pressurizing the EUV photomask processing chamber to a process pressure to increase a reducing reaction between the reducing agent gas and the Ru oxide layer on the Ru capping layer. ### Claim 2 (depends on 1) The method of claim 1, wherein the process pressure is from zero to approximately 150 psi. ### Claim 3 (depends on 1) The method of claim 1, wherein the process pressure is from zero to approximately 1500 psi. ### Claim 4 (depends on 1) The method of claim 1, wherein the EUV photomask processing chamber is a cylindrical chamber and the process pressure is from zero to approximately 2500 psi. ### Claim 5 (depends on 1) The method of claim 1, wherein the process pressure is obtained by regulating a flow of the reducing agent gas into the EUV photomask processing chamber and effluent gases out of the EUV photomask processing chamber. ### Claim 6 (depends on 1) The method of claim 1, wherein the reducing agent gas is carbon monoxide gas, methane gas, or hydrogen gas. ### Claim 7 (depends on 1) The method of claim 1, further comprising: flowing a carrier gas along with the reducing agent gas, wherein the carrier gas reduces volatility of high concentrations of explosive reducing agent gases. ### Claim 8 (depends on 1) The method of claim 1, wherein the thermal budget of the EUV photomask is approximately 150 degrees Celsius. ### Claim 9 A method for reducing ruthenium oxides on an extreme ultraviolet (EUV) photomask, comprising: flowing a reducing agent gas and a carrier gas into a remote plasma generator; heating the EUV photomask to a temperature of approximately 100 degrees Celsius to approximately a thermal budget of the EUV photomask; generating a plasma in the remote plasma generator using an RF power source; and flowing gases from the remote plasma generator into an EUV photomask processing chamber, wherein a remote plasma is formed above the EUV photomask to generate a self-bias on the EUV photomask and wherein the gases in the EUV photomask processing chamber react with a ruthenium (Ru) oxide layer on a Ru capping layer to reduce the Ru oxide layer to Ru metal. ### Claim 10 (depends on 9) The method of claim 9, wherein EUV photomask processing chamber operates in a vacuum. ### Claim 11 (depends on 9) The method of claim 9, wherein the plasma in the remote plasma generator is inductively coupled plasma. ### Claim 12 (depends on 9) The method of claim 9, wherein the reducing agent gas is carbon monoxide gas or methane gas and the carrier gas is argon gas, helium gas, or nitrogen gas. ### Claim 13 (depends on 9) The method of claim 9, wherein the RF power source operates at a frequency of 13.56 MHz. ### Claim 14 (depends on 9) The method of claim 9, wherein the reducing agent gas is hydrogen gas and the remote plasma is adjusted to a sustainable level while providing a self-biasing power level of approximately 5 eV such that implantation of atomic hydrogen into the Ru capping layer is prevented. ### Claim 15 (depends on 9) The method of claim 9, wherein the thermal budget of the EUV photomask is approximately 150 degrees Celsius. ### Claim 16 A method for reducing ruthenium oxides on an extreme ultraviolet (EUV) photomask, comprising: flowing a reducing agent gas and a carrier gas into an atmospheric-pressure (AP) plasma generator in an EUV photomask processing chamber; heating the EUV photomask to a temperature of approximately 100 degrees Celsius to approximately a thermal budget of the EUV photomask; generating a plasma above the EUV photomask with the AP plasma generator using an RF power source; and flowing the reducing agent gas and the carrier gas into the plasma and onto a top surface of the EUV photomask, wherein the reducing agent gas reacts with a ruthenium (Ru) oxide layer on a Ru capping layer to reduce the Ru oxide layer to Ru metal. ### Claim 17 (depends on 16) The method of claim 16, wherein the thermal budget of the EUV photomask is approximately 150 degrees Celsius. ### Claim 18 (depends on 16) The method of claim 16, wherein the plasma in the AP plasma generator is dielectric barrier discharge plasma. ### Claim 19 (depends on 16) The method of claim 16, wherein the reducing agent gas is carbon monoxide gas, methane gas, or hydrogen gas and the carrier gas is argon gas, helium gas, or nitrogen gas. ### Claim 20 (depends on 16) The method of claim 16, wherein the RF power source operates at a frequency of 13.56 MHz. ### Claim 21 An apparatus for reducing ruthenium (RU Ru) oxides on an extreme ultraviolet (EUV) photomask, comprising: an EUV photomask processing chamber with a photomask support body attached to a photomask support, the photomask support body supporting an EUV photomask when present; a reducing agent gas supply fluidly connected to the EUV photomask processing chamber; a heater electrode in the photomask support body that is configured to heat the EUV photomask when present to a range of approximately 100 degrees to approximately 150 degrees; a first valve that controls a reducing agent gas that enters into the EUV photomask processing chamber; a second valve that controls effluent gases that exit the EUV photomask processing chamber; and a controller that regulates the first valve and the second valve to adjust a pressure inside of the EUV photomask processing chamber, wherein the pressure is adjustable from zero psi to 2500 psi and is adjusted, by the controller, to control a reduction rate to reduce Ru oxides on a Ru capping layer on the EUV photomask. ### Claim 22 An apparatus for reducing ruthenium (Ru) oxides on an extreme ultraviolet (EUV) photomask, comprising: an EUV photomask processing chamber with a photomask support body attached to a photomask support, the photomask support body supporting an EUV photomask when present; a heater electrode in the photomask support body that is configured to heat the EUV photomask when present to a range of approximately 100 degrees to approximately 150 degrees to enhance a reduction rate of Ru oxides; a reducing agent gas supply fluidly connected to the EUV photomask processing chamber; a carrier gas supply fluidly connected to the EUV photomask processing chamber; and a remote plasma generator fluidly connected to the EUV photomask processing chamber, wherein the remote plasma generator is configured to form a remote plasma above the EUV photomask to generate a self-bias on the EUV photomask and is configured to allow a reducing agent gas from the reducing agent gas supply and a carrier gas from the carrier gas supply flow through the remote plasma generator when plasma is generated in the remote plasma generator and subsequently allow the reducing agent gas, the carrier gas, and the plasma to flow into the EUV photomask processing chamber to interact with the EUV photomask when present to reduce Ru oxides on a Ru capping layer on the EUV photomask. ### Claim 23 (depends on 22) The apparatus of claim 22, further comprising: a controller that regulates a reduction rate of the Ru oxides by regulating a power applied to the plasma in the remote plasma generator or by regulating a temperature of the EUV photomask when present by adjusting power to the heater electrode. ### Claim 24 An apparatus for reducing ruthenium (Ru) oxides on an extreme ultraviolet (EUV) photomask, comprising: an EUV photomask processing chamber with a photomask support body attached to a photomask support, the photomask support body supporting an EUV photomask when present; a heater electrode in the photomask support body that is configured to heat the EUV photomask when present to a range of approximately 100 degrees to approximately 150 degrees to enhance a reduction rate of Ru oxides; a reducing agent gas supply fluidly connected to the EUV photomask processing chamber; a carrier gas supply fluidly connected to the EUV photomask processing chamber; and an atmospheric-pressure (AP) plasma generator in the EUV photomask processing chamber, wherein the AP plasma generator is configured to allow a reducing agent gas from the reducing agent gas supply and a carrier gas from the carrier gas supply to flow through the AP plasma generator when dielectric barrier discharge plasma is generated by the AP plasma generator directly above the EUV photomask and subsequently allow the reducing agent gas and the carrier gas to flow onto a top surface of the EUV photomask to reduce Ru oxides on a Ru capping layer on the EUV photomask. ### Claim 25 (depends on 24) The apparatus of claim 24, further comprising: a controller that regulates a reduction rate of the Ru oxides by adjusting a power applied to the dielectric barrier discharge plasma in the AP plasma generator or by adjusting a temperature of the EUV photomask when present by adjusting power to the heater electrode.