# US 9,753,378 B2 · Exposure apparatus, exposure method, and device manufacturing method > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,753,378 B2 - Document ID: US9753378B2 - Status: Granted - Kind: B2 - Application number: 14/719,937 - Filed: 2015-05-22 - Published: 2015-09-10 - Granted: 2017-09-05 - Earliest claimed: 2009-03-10 - Assignees: Nikon Corporation - Applicants: Nikon Corporation - Inventors: Junichi Chonan - Web page: https://patentgrep.com/patent/US9753378B2 ## CPC - G03F 7/70341: {Details of immersion lithography aspects, e.g. exposure media or control of immersion liquid supply (chemical composition of immersion liquids G03F7/2041)} - 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 An exposure apparatus exposes a substrate with exposure light via a liquid. The exposure apparatus includes an optical system including an emission surface from which the exposure light is emitted; a liquid supply port that supplies the liquid in order to fill an optical path of the exposure light emitted from the emission surface with the liquid; and a fluid supply port that supplies a fluid including a material capable of changing the specific resistance of the liquid to at least a part of a space around a liquid immersion space that is formed by the liquid. ## Claims ### Claim 1 An exposure apparatus that exposes a substrate with exposure light via a liquid, the exposure apparatus comprising: an optical system having a terminating optical element that emits the exposure light into an optical path; a substrate stage having a holder by which the substrate is held, which is movable relative to and below the optical system; and a liquid immersion member having an opening through which exposure light is projected, a liquid supply port via which the liquid is supplied to fill the optical path of the exposure light with the liquid, a liquid recovery port, and a fluid supply port that supplies carbon dioxide gas to a gas space, the gas space at least partly surrounding the optical path, the gas space being formed between the liquid immersion member on one side and an upper surface of the substrate and/or an upper surface of the substrate stage on the other side, the carbon dioxide gas being supplied from the fluid supply port in gas phase without liquid, wherein: the liquid recovery port is disposed such that the upper surface of the substrate faces the liquid recovery port, and the fluid supply port is disposed radially outward of the liquid recovery port in a radial direction in relation to an optical axis of the optical system. ### Claim 2 (depends on 1) The exposure apparatus according to claim 1, further comprising a fluid recovery port. ### Claim 3 (depends on 2) The exposure apparatus according to claim 2, wherein the fluid recovery port is disposed radially outward of the fluid supply port in a radial direction in relation to the optical axis of the optical system. ### Claim 4 (depends on 3) The exposure apparatus according to claim 3, wherein the fluid supply port is disposed between the liquid recovery port and the fluid recovery port in a radial direction in relation to the optical axis of the optical system to recover the carbon dioxide gas. ### Claim 5 (depends on 3) The exposure apparatus according to claim 3, wherein the liquid immersion member has the fluid supply port, and the fluid supply port and the fluid recovery port face the gas space, the gas space being substantially filled with gas. ### Claim 6 (depends on 3) The exposure apparatus according to claim 3, wherein the fluid supply port and the fluid recovery port face the upper surface of the substrate during exposure of the substrate. ### Claim 7 (depends on 1) The exposure apparatus according to claim 1, wherein the liquid is supplied from the liquid supply port and the liquid is recovered from the liquid recovery port to form a liquid immersion space such that at least a part of the liquid immersion space is formed between the liquid immersion member on the one side and the upper surface of the substrate and/or the upper surface of the substrate stage on the other side. ### Claim 8 (depends on 7) The exposure apparatus according to claim 7, further comprising an outer member that is disposed radially outward of the optical path and radially outward of the liquid immersion member in a radial direction in relation to the optical axis of the optical system. ### Claim 9 (depends on 8) The exposure apparatus according to claim 8, further comprising a fluid recovery port which is disposed radially outward of the fluid supply port in a radial direction in relation to the optical axis of the optical system. ### Claim 10 (depends on 9) The exposure apparatus according to claim 9, wherein the outer member has the fluid recovery port. ### Claim 11 (depends on 1) The exposure apparatus according to claim 1, wherein the terminating optical element has an emission surface and an outer surface extending upwardly with respect to the emission surface, and the liquid supply port faces the outer surface. ### Claim 12 (depends on 1) The exposure apparatus according to claim 1, wherein the gas space is disposed such that at least some of the carbon dioxide gas in the gas space is able to contact the liquid. ### Claim 13 (depends on 1) The exposure apparatus according to claim 1, wherein the carbon dioxide gas is capable of decreasing the specific resistance of the liquid. ### Claim 14 (depends on 1) The exposure apparatus according to claim 1, wherein the carbon dioxide gas supplied to the gas space is mixed with at least one additional gas. ### Claim 15 (depends on 1) A device manufacturing method comprising: exposing a substrate using the exposure apparatus according to claim 1; and developing the exposed substrate. ### Claim 16 A method of exposing a substrate with exposure light, the method comprising: supplying a liquid to an optical path of the exposure light with a liquid supply port of a liquid immersion member having an opening through which exposure light is projected; removing at least some of the liquid in the optical path with a liquid recovery port of the liquid immersion member; and supplying carbon dioxide gas to a gas space with a fluid supply port of the liquid immersion member, the gas space at least partially surrounding the optical path, the gas space being formed between the liquid immersion member on one side and an upper surface of the substrate and/or an upper surface of a substrate stage on the other side having a holder by which the substrate is held, which is movable relative to and below the optical system, the carbon dioxide gas being supplied from the fluid supply port in gas phase without liquid, wherein: the liquid recovery port is disposed such that the upper surface of the substrate faces the liquid recovery port, and the fluid supply port is disposed radially outward of the liquid recovery port in a radial direction in relation to an optical axis. ### Claim 17 (depends on 16) The method according to claim 16, wherein the liquid recovery port sucks the liquid in order to remove the liquid from the optical path. ### Claim 18 (depends on 16) The method according to claim 16, further comprising removing at least some of the carbon dioxide gas from the gas space with a fluid recovery port. ### Claim 19 (depends on 18) The method according to claim 18, wherein the fluid recovery port is disposed radially outward of the fluid supply port in a radial direction in relation to the optical axis. ### Claim 20 (depends on 19) The method according to claim 19, wherein the fluid supply port is disposed between the liquid recovery port and the fluid recovery port in a radial direction in relation to the optical axis to recover the carbon dioxide gas. ### Claim 21 (depends on 18) The method according to claim 18, wherein: the gas space is substantially filled with gas, and the fluid supply port and the fluid recovery port face the gas space. ### Claim 22 (depends on 16) The method according to claim 16, wherein at least some of the carbon dioxide gas contacts the liquid in the gas space and decreases the specific resistance of the liquid. ### Claim 23 (depends on 16) The method according to claim 16, wherein the carbon dioxide gas supplied to the gas space is mixed with at least one additional gas.