# US 2023/0069633 A1 · Substrate processing method and substrate processing apparatus > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2023/0069633 A1 - Document ID: US20230069633A1 - Status: Published application - Kind: A1 - Application number: 17/892,438 - Filed: 2022-08-22 - Published: 2023-03-02 - Earliest claimed: 2021-08-31 - Assignees: SCREEN Holdings Co., Ltd. - Applicants: SCREEN Holdings Co., Ltd. - Inventors: Kei SUZUKI; Masaki INABA - Web page: https://patentgrep.com/patent/US20230069633A1 ## CPC - H10P 72/0404: {for general liquid treatment, e.g. etching followed by cleaning} - G03F 7/42: Stripping or agents therefor - G03F 7/423: {containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds} - G03F 7/427: {using plasma means only} - H10P 72/0402: {Apparatus for fluid treatment (H10P72/0441, H10P72/0448 take precedence)} - H10P 72/0406: {for cleaning followed by drying, rinsing, stripping, blasting or the like} - H10P 72/0414: {using mainly spraying means, e.g. nozzles} - H10P 72/0424: {using mainly spraying means, e.g. nozzles} - H10P 72/0432: {mainly by conduction} - H10P 72/0602: {Temperature monitoring} - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - 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 The substrate processing method includes a liquid film forming step of forming a liquid film of a sulfuric acid-containing liquid on a principal surface of a substrate, an ozone-containing gas exposing step of filling an ozone-containing gas inside a processing chamber capable of housing the substrate to expose the liquid film to the ozone-containing gas, and a substrate heating step of heating the substrate in a state that the substrate is disposed inside the processing chamber which is filled with the ozone-containing gas and the liquid film is also formed on the principal surface of the substrate. ## Claims ### Claim 1 A substrate processing method comprising: a liquid film forming step of forming a liquid film of a sulfuric acid-containing liquid on a principal surface of a substrate; an ozone-containing gas exposing step of filling an ozone-containing gas inside a processing chamber capable of housing the substrate to expose the liquid film to the ozone-containing gas, and a substrate heating step of heating the substrate in a state that the substrate is disposed inside the processing chamber which is filled with the ozone-containing gas and the liquid film is also formed on the principal surface of the substrate. ### Claim 2 (depends on 1) The substrate processing method according to claim 1, wherein the heating of the substrate in the substrate heating step is started before the liquid film forming step and the ozone-containing gas exposing step. ### Claim 3 (depends on 1) The substrate processing method according to claim 1, wherein the ozone-containing gas exposing step includes a pressure applying/supplying step which supplies the ozone-containing gas to the processing chamber so that a pressure inside the processing chamber is made higher than a pressure outside the processing chamber. ### Claim 4 (depends on 1) The substrate processing method according to claim 1, further comprising a rinse liquid supplying step of supplying a rinse liquid to the principal surface of the substrate after the substrate heating step. ### Claim 5 (depends on 1) The substrate processing method according to claim 1, wherein the liquid film forming step includes a sulfuric acid-containing liquid supplying step which supplies the sulfuric acid-containing liquid toward the principal surface of the substrate, and a film thinning step in which after the supply of the sulfuric acid-containing liquid to the principal surface of the substrate is stopped, the substrate is rotated around a central axis which passes through a central portion of the substrate to thin the sulfuric acid-containing liquid on the principal surface of the substrate, thereby forming the liquid film. ### Claim 6 (depends on 1) The substrate processing method according to claim 1, wherein the ozone-containing gas exposing step includes a step in which supply of the ozone-containing gas to the processing chamber is started in a state that the substrate having the liquid film formed on the principal surface thereof is disposed in the processing chamber, thereby filling the ozone-containing gas inside the processing chamber. ### Claim 7 (depends on 1) The substrate processing method according to claim 1, further comprising a hydrophilization step of hydrophilizing the principal surface of the substrate before the formation of the liquid film in the liquid film forming step is started. ### Claim 8 (depends on 7) The substrate processing method according to claim 7, wherein the hydrophilization step includes an ozone hydrophilization step in which before the formation of the liquid film in the liquid film forming step is started, the ozone-containing gas is supplied to the processing chamber in a state that the substrate is disposed in the processing chamber, thereby exposing the principal surface of the substrate to the ozone-containing gas. ### Claim 9 (depends on 1) The substrate processing method according to claim 1, further comprising a substrate holding step of causing a substrate holder disposed inside a chamber to hold the substrate, wherein the ozone-containing gas exposing step includes a substrate housing step in which the processing chamber is moved relatively with respect to the substrate held by the substrate holder inside the chamber to house the substrate held by the substrate holder inside the processing chamber, an ozone-containing gas supplying step in which the ozone-containing gas is supplied to the processing chamber in a state that the substrate is housed in the processing chamber, and a substrate detaching step in which after the ozone-containing gas supplying step, the processing chamber is moved relatively with respect to the substrate held by the substrate holder inside the chamber to detach the substrate held by the substrate holder from the processing chamber. ### Claim 10 A substrate processing apparatus comprising: a substrate holder to hold a substrate in a predetermined processing posture; a processing chamber capable of housing the substrate held by the substrate holder: a substrate heating member to heat the substrate held by the substrate holder: an ozone-containing gas supplying member to supply an ozone-containing gas into the processing chamber; a sulfuric acid-containing liquid ejecting member to eject a sulfuric acid-containing liquid toward a principal surface of the substrate held by the substrate holder: and a controller programmed to control the substrate heating member, the ozone-containing gas supplying member, and the sulfuric acid-containing liquid ejecting member, wherein the controller is programmed so that in a state that the substrate held by the substrate holder is disposed inside the processing chamber and the substrate is also heated by the substrate heating member, the sulfuric acid-containing liquid is ejected from the sulfuric acid-containing liquid ejecting member toward the principal surface of the substrate, thereby forming a liquid film of the sulfuric acid-containing liquid on the principal surface of the substrate, and the ozone-containing gas is also supplied from the ozone-containing gas supplying member to the processing chamber. ### Claim 11 (depends on 10) The substrate processing apparatus according to claim 10, further comprising a temperature sensor to detect a temperature of the substrate heating member, wherein the controller is programmed so as to execute functions as a temperature judging unit to judge whether a detection temperature by the temperature sensor has reached a temperature within a processing temperature range or not and as a first starting unit to start at least one of the ejection of the sulfuric acid-containing liquid from the sulfuric acid-containing liquid ejecting member and the supply of the ozone-containing gas from the ozone-containing gas supplying member when the temperature judging unit judges that the detection temperature by the temperature sensor has reached a temperature within the processing temperature range. ### Claim 12 (depends on 11) The substrate processing apparatus according to claim 11, wherein the first starting unit starts the ejection of the sulfuric acid-containing liquid from the sulfuric acid-containing liquid ejecting member when the temperature judging unit judges that the detection temperature by the temperature sensor has reached a temperature within the processing temperature range, and the controller is programmed so as to further execute functions as an elapsed time judging unit to judge whether a liquid film forming time has elapsed or not after the ejection of the sulfuric acid-containing liquid from the sulfuric acid-containing liquid ejecting member starts and as a second starting unit to start the supply of the ozone-containing gas from the ozone-containing gas supplying member when the elapsed time judging unit judges that the liquid film forming time has elapsed. ### Claim 13 (depends on 10) The substrate processing apparatus according to claim 10, further comprising: a chamber which houses the substrate holder and the processing chamber; and a processing chamber driving mechanism which relatively moves the processing chamber with respect to the substrate holder so that the substrate held by the substrate holder relatively moves between an inside of the processing chamber and an outside of the processing chamber. ### Claim 14 (depends on 13) The substrate processing apparatus according to claim 13, wherein the sulfuric acid-containing liquid ejecting member includes a sulfuric acid-containing liquid nozzle which ejects the sulfuric acid-containing liquid, and the substrate processing apparatus further comprising a nozzle driving mechanism which moves the sulfuric acid-containing liquid nozzle to a processing position between the processing chamber and the principal surface of the substrate in a state that the substrate held by the substrate holder is positioned outside the processing chamber. ### Claim 15 (depends on 13) The substrate processing apparatus according to claim 13, wherein the processing chamber has a housing which demarcates an internal space of the processing chamber, and the ozone-containing gas supplying member has a plurality of ozone-containing gas ejecting ports which are exposed from the housing and connected to the internal space. ### Claim 16 (depends on 10) The substrate processing apparatus according to claim 10, further comprising: a sulfuric acid-containing liquid recovering unit to recover the sulfuric acid-containing liquid discharged from the principal surface of the substrate held by the substrate holder, and a sulfuric acid-containing liquid supplying unit to supply the sulfuric acid-containing liquid recovered by the sulfuric acid-containing liquid recovering unit to the sulfuric acid-containing liquid ejecting member.