# US 12,009,201 B2 · Method of processing substrate, method of manufacturing semiconductor device, substrate processing apparatus, and recording medium

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- Number: US 12,009,201 B2
- Document ID: US12009201B2
- Status: Granted
- Kind: B2
- Application number: 18/189,609
- Filed: 2023-03-24
- Published: 2023-08-10
- Granted: 2024-06-11
- 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/US12009201B2

## 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 processing a substrate, comprising:
forming a Si- and N-containing film on a surface of the substrate by performing a cycle a predetermined number of times, the cycle including:
forming a first Si- and N-containing layer having Cl termination on its surface by supplying SiCl4 to the substrate to cause NH termination on the surface of the substrate to react with the SiCl4 under a condition where self-limitation occurs in a reaction of the NH termination and the SiCl4; and
forming a second Si- and N-containing layer having NH termination on its surface by supplying a reactant containing N and H to the substrate to cause the Cl termination on the surface of the first Si- and N-containing layer to react with the reactant.

### Claim 2 (depends on 1)

The method according to claim 1, wherein a supply time of the SiCl4 in the act of forming the first Si- and N-containing layer is set longer than a supply time of the reactant in the act of forming the second Si- and N-containing layer.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the act of forming the first Si- and N-containing layer is performed under a condition where an adsorptive substitution reaction occurs between the NH termination and the SiCl4.

### Claim 4 (depends on 3)

The method according to claim 3, wherein the act of forming the first Si- and N-containing layer is performed under a condition where self-limitation occurs in the adsorptive substitution reaction.

### Claim 5 (depends on 1)

The method according to claim 1, wherein the SiCl4 is supplied to the substrate under a condition where the SiCl4 is not gas-phase decomposed.

### Claim 6 (depends on 1)

The method according to claim 1, wherein the act of forming the first Si- and N-containing layer is performed under a condition where the SiCl4 is not pyrolyzed.

### Claim 7 (depends on 1)

The method according to claim 1, wherein the act of forming the first Si- and N-containing layer is performed under a condition where the SiCl4 does not generate an intermediate.

### Claim 8 (depends on 1)

The method according to claim 1, wherein the act of forming the first Si- and N-containing layer is performed under a condition in which no gas-phase reaction occurs.

### Claim 9 (depends on 3)

The method according to claim 3, wherein the act of forming the second Si- and N-containing layer is performed under a condition where an adsorptive substitution reaction occurs between the Cl termination on the surface of the first Si- and N-containing layer and the reactant.

### Claim 10 (depends on 1)

The method according to claim 1, wherein the act of forming the first Si- and N-containing layer is performed under a condition where Si—N bonds are formed by bonding of Si constituting the SiCl4 and N constituting the NH termination 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 11 (depends on 1)

The method according to claim 1, wherein the act of forming the first Si- and N-containing layer is performed under a condition where at least a portion of Si—Cl bonds in the SiCl4 and at least a portion of N—H bonds in the NH termination 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 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 12 (depends on 1)

The method according to claim 1, wherein the act of forming the first Si- and N-containing layer is performed under a condition where Si constituting the SiCl4 is bonded to N constituting the NH termination 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 13 (depends on 1)

The method according to claim 1, wherein the act of forming the first Si- and N-containing layer is performed under a condition where 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 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 14 (depends on 1)

The method according to claim 1, further comprising forming the NH termination on the surface of the substrate by supplying a reactant containing N and H to the substrate before the act of forming the first Si- and N-containing layer is performed.

### Claim 15 (depends on 14)

The method according to claim 14, wherein a supply time of the reactant in the act of forming the NH termination on the surface of the substrate is set longer than the supply time of the reactant in the act of forming the second Si- and N-containing layer.

### Claim 16 (depends on 14)

The method according to claim 14, wherein a supply time of the reactant in the act of forming the NH termination on the surface of the substrate is set longer than the supply time of the SiCl4 in the act of forming the first Si- and N-containing layer.

### Claim 17 (depends on 1)

The method according to claim 1, wherein the supply time of the SiCl4 in the act of forming the first Si- and N-containing layer is set to be within a range of 60 to 180 seconds.

### Claim 18 (depends on 1)

The method according to claim 1, wherein in the act of forming the first Si- and N-containing layer, the SiCl4 is supplied to the substrate from a side of the substrate, and
wherein in the act of forming the second Si- and N-containing layer, the reactant is supplied to the substrate from a side of the substrate.

### Claim 19 (depends on 14)

The method according to claim 14, wherein in the act of forming the NH termination on the surface of the substrate, the reactant is supplied to the substrate from a side of the substrate,
wherein in the act of forming the first Si- and N-containing layer, the SiCl4 is supplied to the substrate from a side of the substrate, and
wherein in the act of forming the second Si- and N-containing layer, the reactant is supplied to the substrate from a side of the substrate.

### Claim 20 (depends on 1)

A non-transitory computer-readable recording medium storing a program that causes, by a computer, a substrate processing apparatus to perform a process comprising the method of claim 1.

### Claim 21

A method of manufacturing a semiconductor device, comprising:
forming a Si- and N-containing film on a surface of a substrate by performing a cycle a predetermined number of times, the cycle including:
forming a first Si- and N-containing layer having Cl termination on its surface by supplying SiCl4 to the substrate to cause NH termination on the surface of the substrate to react with the SiCl4 under a condition where self-limitation occurs in the reaction of the NH termination and the SiCl4; and
forming a second Si- and N-containing layer having NH termination on its surface by supplying a reactant containing N and H to the substrate to cause the Cl termination on the surface of the first Si- and N-containing layer to react with the reactant.

### Claim 22

A substrate processing apparatus, comprising:
a reactant supply system configured to supply a reactant containing N and H to a substrate;
a SiCl4 supply system configured to supply SiCl4 to the substrate;
a heater configured to heat the substrate; and
a controller configured to be capable of controlling the reactant supply system, the SiCl4 supply system, and the heater so as to perform a process comprising:
forming a Si- and N-containing film on a surface of the substrate by performing a cycle a predetermined number of times, the cycle including:
forming a first Si- and N-containing layer having Cl termination on its surface by supplying the SiCl4 to the substrate to cause NH termination on the surface of the substrate to react with the SiCl4 under a condition where self-limitation occurs in the reaction of the NH termination and the SiCl4; and
forming a second Si- and N-containing layer having NH termination on its surface by supplying the reactant to the substrate to cause the Cl termination on the surface of the first Si- and N-containing layer to react with the reactant.