# US 10,480,067 B2 · Film deposition method > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,480,067 B2 - Document ID: US10480067B2 - Status: Granted - Kind: B2 - Application number: 15/420,333 - Filed: 2017-01-31 - Published: 2017-08-03 - Granted: 2019-11-19 - Earliest claimed: 2016-02-03 - Assignees: Tokyo Electron Limited - Applicants: Tokyo Electron Limited - Inventors: Hitoshi Kato; Masahiro Murata; Jun Sato; Shigehiro Miura - Web page: https://patentgrep.com/patent/US10480067B2 ## CPC - C23C 16/345: {Silicon nitride} - C23C 16/45536: {Use of plasma, radiation or electromagnetic fields} - C23C 16/45551: {for relative movement of the substrate and the gas injectors or half-reaction reactor compartments} - H01J 37/32: Gas-filled discharge tubes (heating by discharge H05B) - 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) ## Abstract A film deposition method for filling a recessed pattern with a SiN film is provided. NH2 groups are caused to adsorb on a surface of a substrate containing a recessed pattern formed in a top surface of the substrate by supplying a first process gas containing NH3 converted to first plasma to the surface of the substrate containing the recessed pattern. The NH2 groups is partially converted to N groups by supplying a second process gas containing N2 converted to second plasma to the surface of the substrate containing the recessed pattern on which the NH2 groups is adsorbed. A silicon-containing gas is caused to adsorb on the NH2 groups by supplying the silicon-containing gas to the surface of the substrate containing the recessed pattern on which the NH2 groups and the N groups are adsorbed. The above steps are cyclically repeated. ## Claims ### Claim 1 A film deposition method for filling a recessed pattern formed in a surface of a substrate with a SiN film, comprising steps of: causing NH2 groups to adsorb on a surface of a substrate containing a recessed pattern formed in a top surface of the substrate by supplying a first process gas containing NH3 converted to first plasma to the surface of the substrate containing the recessed pattern; partially converting the NH2 groups to N groups by supplying a second process gas containing N2 converted to second plasma to the surface of the substrate containing the recessed pattern on which the NH2 groups is adsorbed; and causing a silicon-containing gas to adsorb on the NH2 groups by supplying the silicon-containing gas to the surface of the substrate containing the recessed pattern on which the NH2 groups and the N groups are adsorbed; and cyclically repeating the steps of causing the NH2 groups to adsorb on the surface of the substrate, partially converting the NH2 groups to the N groups and causing the silicon-containing gas to adsorb on the NH2 groups, wherein the first plasma is generated at a first height higher and more distant from the top surface of the substrate than a second height at which the second plasma is generated, the first height being set at a height that causes the first plasma containing NH3 to reach a bottom of the recessed pattern, the second height being set at a height that causes the second plasma containing N2 to reach only an upper portion of the recessed pattern and the top surface of the substrate. ### Claim 2 (depends on 1) The film deposition method as claimed in claim 1, wherein the NH2 groups adsorbed on an upper portion of the recessed pattern and the top surface of the substrate W is converted to the N groups in the step of partially converting the NH2 groups to the N groups. ### Claim 3 (depends on 1) The film deposition method as claimed in claim 1, wherein the first process gas is a gas that does not contain N2. ### Claim 4 (depends on 3) The film deposition method as claimed in claim 3, wherein the first process gas and the second process gas further contain Ar and H2. ### Claim 5 (depends on 1) The film deposition method as claimed in claim 1, wherein the silicon-containing gas contains any one of dichlorosilane, disilane, hexachlorodisilane, diisopropylamino-silane, tris(dimethylamino)silane, bis(tertiary-butyl-amino)silane. ### Claim 6 (depends on 1) The film deposition method as claimed in claim 1, wherein a temperature of the substrate is set higher than or equal to 400 degrees C. at which nitriding the surface of the substrate containing the recessed pattern can be performed by ammonia radicals. ### Claim 7 (depends on 1) The film deposition method as claimed in claim 1, wherein the second process gas converted to the second plasma has energy higher than energy of the first process gas converted to the first plasma. ### Claim 8 (depends on 1) The film deposition method as claimed in claim 1, further comprising: supplying a purge gas to the surface of the substrate containing the recessed pattern between the steps of partially converting the NH2 groups to the N groups and causing the silicon-containing gas to adsorb on the NH2 groups, and between the steps of causing the silicon-containing gas to adsorb on the NH2 groups and causing the NH2 groups to adsorb on the surface of the substrate. ### Claim 9 (depends on 8) The film deposition method as claimed in claim 8, wherein the substrate is arranged on a turntable provided in a process chamber along a circumferential direction of the turntable, wherein the process chamber includes a first plasma processing area for performing the step of causing the NH2 groups to adsorb on the surface of the substrate, a second plasma processing area for performing the step of partially converting the NH2 groups to the N groups, a first purge area for performing the step of purging the surface of the substrate, an adsorption area for performing the step of causing the silicon-containing gas to adsorb on the NH2 groups, and a second purge area for performing the step of purging the surface of the substrate, arranged along a rotational direction of the turntable and above the turntable, and wherein the steps of causing the NH2 groups to adsorb on the surface of the substrate, partially converting the NH2 groups to the N groups, purging the surface of the substrate, causing the silicon-containing gas to adsorb on the NH2 groups, and purging the surface of the substrate, are performed on the surface of the substrate containing the recessed pattern by rotating the turntable. ### Claim 10 (depends on 9) The film deposition method as claimed in claim 9, wherein a first plasma generator and a second plasma generator are provided above the first plasma processing area and the second plasma processing area, respectively, and wherein the first plasma generator is disposed higher than the second plasma generator so as to generate the first plasma at a first height that is higher than a second height at which the second plasma is generated.