# US 11,028,473 B2 · Method of manufacturing semiconductor device, substrate processing apparatus, and recording medium > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,028,473 B2 - Document ID: US11028473B2 - Status: Granted - Kind: B2 - Application number: 15/175,389 - Filed: 2016-06-07 - Published: 2016-12-15 - Granted: 2021-06-08 - Earliest claimed: 2015-06-10 - Assignees: Kokusai Electric Corporation - Applicants: Hitachi Kokusai Electric Inc. - Inventors: Ryuji Yamamoto; Yoshiro Hirose - Web page: https://patentgrep.com/patent/US11028473B2 ## CPC - C23C 16/02: Pretreatment of the material to be coated (C23C16/04 takes precedence) - C23C 16/24: Deposition of silicon only - C23C 16/45542: {Plasma being used non-continuously during the ALD reactions} - C23C 16/45546: {specially adapted for a substrate stack in the ALD reactor} - C23C 16/45557: {Pulsed pressure or control pressure} - H10P 14/24: using chemical vapour deposition [CVD] - H10P 14/3211: {Silicon, silicon germanium or germanium} - H10P 14/3238: {being insulating materials} - H10P 14/3411: {Silicon, silicon germanium or germanium} - 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) - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract A method of manufacturing a semiconductor device includes forming a seed layer containing a predetermined element on a substrate by performing a process a predetermined number of times, and supplying a second precursor containing the predetermined element and not containing the ligand to the substrate to form a film containing the predetermined element on the seed layer. The process includes alternately performing: supplying a first precursor to the substrate to form an adsorption layer of the first precursor, the first precursor containing the predetermined element and a ligand which is coordinated to the predetermined element and which contains at least one of carbon or nitrogen, and supplying a ligand desorption material to the substrate to desorb the ligand from the adsorption layer of the first precursor. ## Claims ### Claim 1 A method of manufacturing a semiconductor device, comprising: (a) forming a seed layer containing a predetermined element on a substrate by performing a process multiple times, the process including performing: (a-1) supplying a first precursor to the substrate to form an adsorption layer of the first precursor, the first precursor containing the predetermined element and a ligand which is coordinated to the predetermined element and which contains at least one of carbon or nitrogen, and (a-2) supplying a ligand desorption material to the substrate to desorb the ligand from the adsorption layer of the first precursor, thereby lowering concentration of the at least one of carbon or nitrogen from the adsorption layer; and (b) supplying a second precursor containing the predetermined element and not containing the ligand to the substrate to form a film containing the predetermined element on the seed layer, wherein (a-1) and (a-2) are alternately performed in (a), and wherein a pressure at a space where the substrate is located in (a-1) is set higher than a pressure at a space where the substrate is located in (a-2). ### Claim 2 (depends on 1) The method of claim 1, wherein a pressure at a space where the substrate is located in (a-1) is set higher than a pressure at a space where the substrate is located in (b). ### Claim 3 (depends on 1) The method of claim 1, wherein a supply flow rate of the first precursor in (a-1) is set higher than an exhaust flow rate of the first precursor exhausted from a space where the substrate is located in (a-1). ### Claim 4 (depends on 1) The method of claim 1, wherein in (a-1), the first precursor is exhausted from a space where the substrate is located while supplying the first precursor into the space, and at this time, a supply flow rate of the first precursor supplied into the space is set higher than an exhaust flow rate of the first precursor exhausted from the space. ### Claim 5 (depends on 1) The method of claim 1, wherein in (a-1), an exhaust of the first precursor from a space where the substrate is located is stopped. ### Claim 6 (depends on 1) The method of claim 1, wherein the ligand desorption material includes a reducing gas. ### Claim 7 (depends on 1) The method of claim 1, wherein the ligand desorption material includes a plasma-excited reducing gas. ### Claim 8 (depends on 1) The method of claim 1, wherein the ligand desorption material includes a non-plasma-excited reducing gas. ### Claim 9 (depends on 1) The method of claim 1, wherein the ligand desorption material includes a plasma-excited gas. ### Claim 10 (depends on 1) The method of claim 1, wherein the ligand desorption material includes a plasma-excited hydrogen-containing gas. ### Claim 11 (depends on 1) The method of claim 1, wherein the ligand desorption material includes a plasma-excited inert gas. ### Claim 12 (depends on 1) The method of claim 1, wherein the ligand desorption material includes a plasma-excited inert gas and a non-plasma-excited reducing gas. ### Claim 13 (depends on 1) The method of claim 1, wherein the ligand desorption material includes a halogen-element-containing gas. ### Claim 14 (depends on 1) The method of claim 1, wherein (a-1) is performed under a condition in which the first precursor is not pyrolyzed, and (b) is performed under a condition in which the second precursor is pyrolyzed. ### Claim 15 (depends on 1) The method of claim 1, wherein an insulation film is formed on a surface of the substrate, and the seed layer is formed on the insulation film.