# US 10,770,287 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 10,770,287 B2 - Document ID: US10770287B2 - Status: Granted - Kind: B2 - Application number: 16/286,292 - Filed: 2019-02-26 - Published: 2019-08-29 - Granted: 2020-09-08 - Earliest claimed: 2018-02-28 - Assignees: Kokusai Electric Corporation - Applicants: Kokusai Electric Corporation - Inventors: Katsuyoshi Harada; Tatsuru Matsuoka; Yoshitomo Hashimoto - Web page: https://patentgrep.com/patent/US10770287B2 ## CPC - H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD} - C23C 16/345: {Silicon nitride} - C23C 16/45525: {Atomic layer deposition [ALD]} - C23C 16/45546: {specially adapted for a substrate stack in the ALD reactor} - C23C 16/45553: {characterized by the use of precursors specially adapted for ALD} - C23C 16/45578: {Elongated nozzles, tubes with holes} - H10P 14/6682: {the compound being a silane, e.g. disilane, methylsilane or chlorosilane} - H10P 14/69433: {the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz} - 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) ## Abstract There is provided a technique, including: (a) forming NH termination on a surface of a substrate by supplying a first reactant containing N and H to the substrate; (b) forming a first SiN layer having SiCl termination formed on its surface by supplying SiCl4 as a precursor to the substrate to react the NH termination formed on the surface of the substrate with the SiCl4; (c) forming a second SiN layer having NH termination formed on its surface by supplying a second reactant containing N and H to the substrate to react the SiCl termination formed on the surface of the first SiN layer with the second reactant; and (d) forming a SiN film on the substrate by performing a cycle a predetermined number of times under a condition where the SiCl4 is not gas-phase decomposed after performing (a), the cycle including non-simultaneously performing (b) and (c). ## Claims ### Claim 1 A method of manufacturing a semiconductor device, comprising: (a) forming NH termination on a surface of a substrate by supplying a first reactant containing N and H to the substrate; (b) forming a first SiN layer having SiCl termination formed on its surface by supplying SiCl4 as a precursor to the substrate to react the NH termination formed on the surface of the substrate with the SiCl4; (c) forming a second SiN layer having NH termination formed on its surface by supplying a second reactant containing N and H to the substrate to react the SiCl termination formed on the surface of the first SiN layer with the second reactant; and (d) forming a SiN film on the substrate by performing a cycle a predetermined number of times under a condition where the SiCl4 is not gas-phase decomposed after performing (a), the cycle including non-simultaneously performing (b) and (c). ### Claim 2 (depends on 1) The method according to claim 1, wherein the cycle is performed the predetermined number of times under a condition in which the SiCl4 is not pyrolyzed. ### Claim 3 (depends on 1) The method according to claim 1, wherein the cycle is performed the predetermined number of times under a condition in which the SiCl4 does not generate an intermediate. ### Claim 4 (depends on 1) The method according to claim 1, wherein the cycle is performed the predetermined number of times under a condition in which no gas-phase reaction occurs. ### Claim 5 (depends on 1) The method according to claim 1, wherein (b) is performed under a condition in which an adsorptive substitution reaction occurs between the NH termination formed on the surface of the substrate and the SiCl4, and wherein (c) is performed under a condition in which an adsorptive substitution reaction occurs between the SiCl termination formed on the surface of the first SiN layer and the second reactant. ### Claim 6 (depends on 1) The method according to claim 1, wherein (b) is performed under a condition in which Si—N bonds are formed by bonding of Si constituting the SiCl4 and N constituting the NH termination formed on the surface of the substrate, and at that time, Si—Cl bonds which are not converted into the Si—N bonds among Si—Cl bonds contained in the SiCl4 are held without being broken. ### Claim 7 (depends on 1) The method according to claim 1, wherein (b) is performed under a condition in which at least a portion of Si—Cl bonds in the SiCl4 and at least a portion of N—H bonds in the NH termination formed on the surface of the substrate are broken, and Si—N bonds are formed by bonding of Si after the at least a portion of Si—Cl bonds in the SiCl4 are broken and N after the at least a portion of N—H bonds in the NH termination formed on the surface of the substrate are broken, and at that time, Si—Cl bonds which are not converted into the Si—N bonds among the Si—Cl bonds in the SiCl4 are held without being broken. ### Claim 8 (depends on 1) The method according to claim 1, wherein (b) is performed under a condition in which Si constituting the SiCl4 is bonded to N constituting the NH termination formed on the surface of the substrate in a state in which Cl is bonded to each of three bonds among four bonds of Si constituting the SiCl4. ### Claim 9 (depends on 1) The method according to claim 1, wherein (b) is performed under a condition in which Si after at least a portion of Si—Cl bonds in the SiCl4 are broken is bonded to N after at least a portion of N—H bonds in the NH termination formed on the surface of the substrate are broken in a state in which Cl is bonded to each of three bonds among four bonds of Si constituting the SiCl4. ### Claim 10 (depends on 1) The method according to claim 1, wherein a supply time of the SiCl4 in (b) is set longer than a supply time of the second reactant in (c). ### Claim 11 (depends on 1) The method according to claim 1, wherein a supply time of the first reactant in (a) is set longer than a supply time of the second reactant in (c). ### Claim 12 (depends on 1) The method according to claim 1, wherein a supply time of the first reactant in (a) is set longer than a supply time of the SiCl4 in (b), and the supply time of the SiCl4 in (b) is set longer than a supply time of the second reactant in (c). ### Claim 13 (depends on 1) The method according to claim 1, wherein a supply time of the SiCl4 in (b) is set such that an amount of an adsorptive substitution reaction occurring between the NH termination formed on the surface of the substrate and the SiCl4 in a central portion of the substrate becomes substantially equal to an amount of an adsorptive substitution reaction occurring between the NH termination formed on the surface of the substrate and the SiCl4 in an outer peripheral portion of the substrate. ### Claim 14 (depends on 1) The method according to claim 1, wherein a supply time of the SiCl4 in (b) is set such that a thickness of the first SiN layer formed in a central portion of the substrate becomes substantially equal to a thickness of the first SiN layer formed in an outer peripheral portion of the substrate. ### Claim 15 (depends on 1) The method according to claim 1, wherein in (a), the first reactant is supplied to the substrate from a side of the substrate, and wherein, in (b), the SiCl4 is supplied to the substrate from the side of the substrate, and wherein, in (c), the second reactant is supplied to the substrate from the side of the substrate. ### Claim 16 (depends on 1) The method according to claim 1, wherein a pattern is formed on the surface of the substrate, the pattern including a recess, and wherein the recess is a trench or a hole. ### Claim 17 A substrate processing apparatus, comprising: a process chamber in which a substrate is processed; a reactant supply system configured to supply a first reactant containing N and H and a second reactant containing N and H to the substrate in the process chamber; a precursor supply system configured to supply SiCl4 as a precursor to the substrate in the process chamber; a heater configured to heat the substrate in the process chamber; and a controller configured to control the reactant supply system, the precursor supply system, and the heater so as to perform a process in the process chamber, the process comprising: (a) forming NH termination on a surface of the substrate by supplying the first reactant to the substrate; (b) forming a first SiN layer having SiCl termination formed on its surface by supplying the SiCl4 to the substrate to react the NH termination formed on the surface of the substrate with the SiCl4; (c) forming a second SiN layer having NH termination formed on its surface by supplying the second reactant to the substrate to react the SiCl termination formed on the surface of the first SiN layer with the second reactant; and (d) forming a SiN film on the substrate by performing a cycle a predetermined number of times under a condition where the SiCl4 is not gas-phase decomposed after performing (a), the cycle including non-simultaneously performing (b) and (c). ### Claim 18 A non-transitory computer-readable recording medium storing a program that causes, by a computer, a substrate processing apparatus to perform a process in a process chamber of the substrate processing apparatus, the process comprising: (a) forming NH termination on a surface of a substrate by supplying a first reactant containing N and H to the substrate; (b) forming a first SiN layer having SiCl termination formed on its surface by supplying SiCl4 as a precursor to the substrate to react the NH termination formed on the surface of the substrate with the SiCl4; (c) forming a second SiN layer having NH termination formed on its surface by supplying a second reactant containing N and H to the substrate to react the SiCl termination formed on the surface of the first SiN layer with the second reactant; and (d) forming a SiN film on the substrate by performing a cycle a predetermined number of times under a condition where the SiCl4 is not gas-phase decomposed after performing (a), the cycle including non-simultaneously performing (b) and (c).