# US 2019/0355575 A1 · Method of manufacturing semiconductor device > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2019/0355575 A1 - Document ID: US20190355575A1 - Status: Published application - Kind: A1 - Application number: 16/528,048 - Filed: 2019-07-31 - Published: 2019-11-21 - Earliest claimed: 2017-03-27 - Assignees: Kokusai Electric Corporation - Applicants: Kokusai Electric Corporation - Inventors: Yuichiro TAKESHIMA; Masanori NAKAYAMA; Katsunori FUNAKI; Yasutoshi TSUBOTA; Hiroto IGAWA - Web page: https://patentgrep.com/patent/US20190355575A1 ## CPC - H10P 14/6519: {the substance being oxygen} - H10P 14/69215: {the material being a silicon oxide, e.g. SiO2} - C23C 16/401: {containing silicon} - C23C 16/50: using electric discharges {(generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34)} - H10P 14/6336: {in the presence of a plasma [PECVD]} - H10P 14/6522: {introduced into a nitride material, e.g. changing SiN to SiON} - H10P 14/6532: {by exposure to a plasma} - H10P 50/283: {by chemical means} - H01J 37/32: Gas-filled discharge tubes (heating by discharge H05B) - H10B 41/27: the channels comprising vertical portions, e.g. U-shaped channels - H10B 43/27: the channels comprising vertical portions, e.g. U-shaped channels - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - 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) - H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H) - H10B: ELECTRONIC MEMORY DEVICES ## Abstract Described herein is a technique capable of improving electrical characteristics of a semiconductor device. According to the technique, there is provided a method of manufacturing a semiconductor device including: (a) generating oxygen and hydrogen active species; and (b) forming an oxide layer by supplying the oxygen and hydrogen active species to a substrate with a concave structure to subject a film on an inner surface of the concave structure to oxidation, wherein the oxide layer is formed in (b) such that a thickness of the oxide layer is greater on the inner surface than at an upper end portion of the concave structure by setting a ratio of a flow rate of the hydrogen active species to a total flow rate to a predetermined ratio greater than a first ratio at which a rate of forming the oxide layer is maximized at the upper end portion of the concave structure. ## Claims ### Claim 1 A method of manufacturing a semiconductor device comprising: (a) generating an oxygen active species and a hydrogen active species by exciting a process gas containing an oxygen-containing gas and a hydrogen-containing gas; and (b) forming an oxide layer by supplying the oxygen active species and the hydrogen active species to a substrate with a concave structure formed thereon to subject a film formed on an inner surface of the concave structure to oxidation from a surface of the film, wherein the oxide layer is formed in (b) such that a thickness of the oxide layer on the inner surface of the concave structure is greater than that of the oxide layer at an upper end portion of the concave structure by setting a ratio of a flow rate of the hydrogen active species to a total flow rate of the oxygen active species and the hydrogen active species supplied to the substrate to a predetermined ratio greater than a first ratio at which a rate of forming the oxide layer is maximized at the upper end portion of the concave structure. ### Claim 2 (depends on 1) The method of claim 1, wherein the oxide layer is formed in (b) such that the thickness of the oxide layer increases toward a bottom of the concave structure by setting the ratio of the flow rate of the hydrogen active species to the total flow rate of the oxygen active species and the hydrogen active species supplied to the substrate to the predetermined ratio greater than a second ratio at which a thickness distribution of the oxide layer in a depth direction of the concave structure is uniform. ### Claim 3 (depends on 1) The method of claim 1, wherein the oxide layer is formed in (b) such that the thickness of the oxide layer increases toward a bottom of the concave structure and is maximized at the bottom of the concave structure by setting the ratio of the flow rate of the hydrogen active species to the total flow rate of the oxygen active species and the hydrogen active species supplied to the substrate to the predetermined ratio equal to or greater than a third ratio at which the rate of forming the oxide layer is maximized at the bottom of the concave structure. ### Claim 4 (depends on 3) The method of claim 3, wherein the third ratio is greater than the first ratio. ### Claim 5 (depends on 1) The method of claim 1, wherein a ratio of a flow rate of the hydrogen-containing gas to a total flow rate of the process gas is set in (a) such that a ratio of the hydrogen active species generated in (a) to a total of the oxygen active species and the hydrogen active species generated in (a) is equal to the predetermined ratio. ### Claim 6 (depends on 3) The method of claim 3, wherein a ratio of a flow rate of the hydrogen-containing gas to a total flow rate of the process gas is set in (a) such that a ratio of the hydrogen active species generated in (a) to a total of the oxygen active species and the hydrogen active species generated in (a) is equal to the predetermined ratio. ### Claim 7 (depends on 5) The method of claim 5, wherein the ratio of the flow rate of the hydrogen-containing gas to the total flow rate of the process gas is greater than 5%. ### Claim 8 (depends on 6) The method of claim 6, wherein the ratio of the flow rate of the hydrogen-containing gas to the total flow rate of the process gas is greater than 5% and equal to or less than 20%. ### Claim 9 (depends on 6) The method of claim 6, further comprises (c) loading the substrate into a process chamber before (a), wherein the oxygen active species and the hydrogen active species are generated in (a) by plasma-exciting the process gas supplied into the process chamber. ### Claim 10 (depends on 9) The method of claim 9, wherein each of a supply system of the oxygen-containing gas and a supply system of the hydrogen-containing gas are controlled in order to adjust the ratio of the flow rate of the hydrogen-containing gas to the total flow rate of the process gas and a ratio of a flow rate of the oxygen-containing gas to the total flow rate of the process gas. ### Claim 11 (depends on 3) The method of claim 3, wherein the film formed on the inner surface of the concave structure comprises an exposed layer whose oxygen concentration is reduced by an etching process, and the oxygen concentration of the exposed layer is lowest at the bottom of the concave structure. ### Claim 12 (depends on 1) The method of claim 1, wherein the film formed on the inner surface of the concave structure is constituted by an oxide film and a base film of the oxide film, and a thickness of the oxide film decreases toward the bottom of the concave structure. ### Claim 13 A method of manufacturing a semiconductor device comprising: (a) generating an oxygen active species and a hydrogen active species by exciting a process gas containing an oxygen-containing gas and a hydrogen-containing gas; and (b) forming an oxide layer by supplying the oxygen active species and the hydrogen active species to a substrate with a concave structure formed thereon to subject a film formed on an inner surface of the concave structure to oxidation from a surface of the film, wherein a ratio of a flow rate of the hydrogen active species to a total flow rate of the oxygen active species and the hydrogen active species supplied to the substrate in (b) is set to a ratio at which a rate of forming the oxide layer has a desired distribution in a depth direction of the concave structure. ### Claim 14 A method of manufacturing a semiconductor device comprising: (a) generating an oxygen active species and a hydrogen active species by exciting a process gas containing an oxygen-containing gas and a hydrogen-containing gas; and (b) forming an oxide layer by supplying the oxygen active species and the hydrogen active species to a substrate with a concave structure formed thereon to subject a film formed on an inner surface of the concave structure to oxidation from a surface of the film, wherein the oxide layer is formed in (b) such that a thickness of the oxide layer increases toward a bottom of the concave structure by adjusting a flow velocity of the oxygen active species and the hydrogen active species flowing on a surface of the substrate. ### Claim 15 (depends on 14) The method of claim 14, wherein the oxide layer is formed in (b) such that the thickness of the oxide layer increases toward the bottom of the concave structure by setting the flow velocity of the oxygen active species and the hydrogen active species flowing on the surface of the substrate to a predetermined flow velocity greater than a flow velocity at which a thickness distribution of the oxide layer in a depth direction of the concave structure is uniform.