# US 12,601,048 B2 · Film forming method and film forming apparatus > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,601,048 B2 - Document ID: US12601048B2 - Status: Granted - Kind: B2 - Application number: 18/032,264 - Filed: 2021-10-08 - Published: 2023-12-14 - Granted: 2026-04-14 - Earliest claimed: 2020-10-19 - Assignees: Tokyo Electron Limited - Applicants: Tokyo Electron Limited - Inventors: Yoshihiro Kato; Junya Suzuki; Toshio Hasegawa; Kouji Shimomura - Web page: https://patentgrep.com/patent/US12601048B2 ## CPC - C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates} - C23C 16/36: Carbonitrides - C23C 16/45531: {specially adapted for making ternary or higher compositions} - C23C 16/45536: {Use of plasma, radiation or electromagnetic fields} - C23C 16/505: using radio frequency discharges - C23C 16/56: After-treatment - H01J 37/32174: {Circuits specially adapted for controlling the RF discharge} - H01J 37/32449: {Gas control, e.g. control of the gas flow} - H10P 14/60: of insulating materials - H10P 14/6336: {in the presence of a plasma [PECVD]} - H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD} - H10P 14/6682: {the compound being a silane, e.g. disilane, methylsilane or chlorosilane} - H10P 14/6922: {the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC} - H10P 14/6927: {the material being a silicon oxynitride, e.g. SiON or SiON:H} - H01J 2237/332: Coating - 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) - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract A film forming method according to an aspect of the present disclosure is a film forming method of embedding a film in a recess formed in a surface of a substrate, and includes a first processing including (a) adsorbing a raw material gas into the recess, (b) forming a film by reacting a reaction gas with the raw material gas, and (c) activating a plasma generation gas including a hydrogen gas and a noble gas by plasma and supplying the gas into the recess to shrink the film. A plurality of cycles each including (a) and (b) are executed, and at least a part of the plurality of cycles includes (c). ## Claims ### Claim 1 A film forming method of embedding a film in a recess formed in a surface of a substrate, the method comprising: a first processing comprising: (a) adsorbing a raw material gas into the recess; (b) forming the film by reacting a first reaction gas with the raw material gas; and (c) activating a plasma generation gas including a hydrogen gas and a noble gas by plasma and supplying the plasma generation gas into the recess to shrink the film, wherein a plurality of cycles each including (a) and (b) are executed, and at least a part of the plurality of cycles includes (c). ### Claim 2 (depends on 1) The film forming method of claim 1, wherein the raw material gas includes at least one selected from a group including silicon (Si) and a metal, and wherein the first reaction gas includes at least one selected from a group including oxygen (O), nitrogen (N), and carbon (C). ### Claim 3 (depends on 1) The film forming method of claim 1, further comprising (d) forming a film by reacting a second reaction gas with the raw material gas, the second reaction gas being different from the first reaction gas, wherein a plurality of cycles each including (a), (b), and (d) are executed, and at least a part of the plurality of cycles includes (c). ### Claim 4 (depends on 1) The film forming method of claim 1, wherein the recess is a trench or a hole. ### Claim 5 (depends on 1) The film forming method of claim 1, comprising (e) forming a liner film in the recess, (e) being performed before the first processing. ### Claim 6 (depends on 1) The film forming method of claim 1, comprising a second processing of forming a film covering the film formed in the first processing after the first processing, the film of the second processing having higher ashing resistance and higher etching resistance than the film of the first processing. ### Claim 7 (depends on 1) The film forming method of claim 1, wherein an influence of the plasma on the film is gradually reduced. ### Claim 8 (depends on 7) The film forming method of claim 7, wherein the influence of the plasma includes power for generating the plasma in (c). ### Claim 9 (depends on 7) The film forming method of claim 7, wherein the influence of the plasma includes a time during which the plasma is generated in (c). ### Claim 10 (depends on 7) The film forming method of claim 7, wherein the influence of the plasma includes a frequency of (c) included in the plurality of cycles. ### Claim 11 (depends on 10) The film forming method of claim 10, wherein the influence of the plasma includes power for generating the plasma in (c). ### Claim 12 (depends on 11) The film forming method of claim 11, wherein the influence of the plasma includes a time during which the plasma is generated in (c). ### Claim 13 (depends on 12) The film forming method of claim 12, wherein the raw material gas includes at least one selected from a group including silicon (Si) and a metal, and wherein the first reaction gas includes at least one selected from a group including oxygen (O), nitrogen (N), and carbon (C). ### Claim 14 (depends on 13) The film forming method of claim 13, further comprising (d) forming a film by reacting a second reaction gas with the raw material gas, the second reaction gas being different from the first reaction gas, wherein a plurality of cycles each including (a), (b), and (d) are executed, and at least a part of the plurality of cycles includes (c). ### Claim 15 (depends on 14) The film forming method of claim 14, wherein the raw material gas includes at least one selected from a group including silicon (Si) and a metal, wherein the first reaction gas includes at least one selected from a group including oxygen (O), nitrogen (N), and carbon (C), and wherein the second reaction gas includes an element different from the first reaction gas among oxygen (O), nitrogen (N), and carbon (C). ### Claim 16 (depends on 15) The film forming method of claim 15, wherein the recess is a trench or a hole. ### Claim 17 (depends on 16) The film forming method of claim 16, comprising (e) forming a liner film in the recess, (e) being performed before the first processing. ### Claim 18 (depends on 17) The film forming method of claim 17, comprising alternately repeating the first processing and a third processing of forming a film having higher ashing resistance and higher etching resistance than the film formed in the first processing. ### Claim 19 (depends on 17) The film forming method of claim 17, comprising a second processing of forming a film covering the film formed in the first processing after the first processing, the film of the second processing having higher ashing resistance and higher etching resistance than the film of the first processing. ### Claim 20 A film forming apparatus comprising: a processing container configured to accommodate a substrate having a recess formed in a surface thereof; a gas supplier configured to supply a raw material gas, a reaction gas, and a plasma generation gas into the processing container; an RF power supplier configured to generate plasma; and a controller, wherein the plasma generation gas includes a hydrogen gas and a noble gas, and wherein the controller is configured to control the gas supplier and the RF power supplier so as to execute: (a) adsorbing the raw material gas into the recess; (b) forming a film by reacting the reaction gas with the raw material gas; and (c) activating the plasma generation gas by plasma and supplying the plasma generation gas into the recess to shrink the film, and wherein the controller is configured to control the gas supplier and the RF power supplier so that a plurality of cycles each including (a) and (b) are executed and at least a part of the plurality of cycles includes (c).