# US 9,437,422 B2 · Method of manufacturing semiconductor device and substrate processing method

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 9,437,422 B2
- Document ID: US9437422B2
- Status: Granted
- Kind: B2
- Application number: 14/706,223
- Filed: 2015-05-07
- Published: 2015-08-20
- Granted: 2016-09-06
- Earliest claimed: 2011-12-09
- Assignees: Hitachi Kokusai Electric Inc.
- Applicants: Hitachi Kokusai Electric Inc.
- Inventors: Yoshiro Hirose; Atsushi Sano
- Web page: https://patentgrep.com/patent/US9437422B2

## CPC

- H10P 14/6334: {using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition (deposition by physical ablation of a target H10P14/6329)}
- C23C 16/30: Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C 16/45531: {specially adapted for making ternary or higher compositions}
- C23C 16/45546: {specially adapted for a substrate stack in the ALD reactor}
- 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}
- H10P 14/69433: {the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz}
- H10P 14/69391: {the material containing aluminium, e.g. Al2O3}
- H10P 14/69392: {the material containing hafnium, e.g. HfO2}
- H10P 14/69393: {the material containing tantalum, e.g. Ta2O5}
- H10P 14/69394: {the material containing titanium, e.g. TiO2}
- H10P 14/69395: {the material containing zirconium, e.g. ZrO2}
- 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

A method of manufacturing a semiconductor device is provided. The method includes: forming a film containing a predetermined element, oxygen, carbon and nitrogen on a substrate by repeating a cycle. The cycle includes: (a) supplying a source gas containing the predetermined element and a halogen element to the substrate; (b) supplying a first reactive gas containing three elements including carbon, nitrogen and hydrogen to the substrate; (c) supplying a nitriding gas as a second reactive gas to the substrate; (d) supplying an oxidizing gas as a third reactive gas to the substrate; and (e) supplying an hydrogen-containing gas as a fourth reactive gas to the substrate, wherein (a) through (e) are non-simultanelously performed.

## Claims

### Claim 1

A method of manufacturing a semiconductor device, comprising:
forming a film containing a predetermined element, oxygen, carbon and nitrogen on a substrate by repeating a cycle, the cycle comprising:
(a) supplying a source gas containing the predetermined element and a halogen element to the substrate;
(b) supplying a first reactive gas containing three elements including carbon, nitrogen and hydrogen to the substrate;
(c) supplying a nitriding gas as a second reactive gas to the substrate;
(d) supplying an oxidizing gas as a third reactive gas to the substrate; and
(e) supplying an hydrogen-containing gas as a fourth reactive gas to the substrate,
wherein (a) through (e) are non-simultaneously performed.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the first reactive gas comprises at least one selected from the group consisting of amine and organic hydrazine.

### Claim 3 (depends on 2)

The method according to claim 2, wherein the second reactive gas comprises at least one selected from the group consisting of NH3 gas, N2H2 gas, N2H4 gas and N3H8 gas.

### Claim 4 (depends on 3)

The method according to claim 3, wherein the third reactive gas comprises at least one selected from the group consisting of O2 gas, N2O gas, NO gas, NO2 gas, O3 gas, H2 gas+O2 gas, H2 gas+O3 gas, H2O gas, CO gas and CO2 gas.

### Claim 5 (depends on 4)

The method according to claim 4, wherein the fourth reactive gas comprises H2 gas.

### Claim 6 (depends on 1)

The method according to claim 1, wherein the predetermined element comprises silicon or a metal, and the halogen element comprises chlorine or fluorine.

### Claim 7 (depends on 1)

The method according to claim 1, wherein each of the first reactive gas, the second reactive gas, the third reactive gas and the fourth reactive gas is thermally activated under non-plasma condition and supplied to the substrate.

### Claim 8 (depends on 1)

The method according to claim 1, wherein the forming of the film is performed with the substrate accommodated in a process chamber, and
wherein an inner pressure of the process chamber when performing (b) is higher than those of the process chamber when performing (a) and (d).

### Claim 9 (depends on 1)

The method according to claim 1, wherein the forming of the film is performed with the substrate accommodated in a process chamber, and
wherein an inner pressure of the process chamber when performing (b) is higher than that of the process chamber when performing (d), and the inner pressure of the process chamber when performing (d) is higher than that of the process chamber when performing (a).

### Claim 10

A substrate processing method comprising:
forming a film containing a predetermined element, oxygen, carbon and nitrogen on a substrate by repeating a cycle, the cycle comprising:
(a) supplying a source gas containing the predetermined element and a halogen element to the substrate;
(b) supplying a first reactive gas containing three elements including carbon, nitrogen and hydrogen to the substrate;
(c) supplying a nitriding gas as a second reactive gas to the substrate;
(d) supplying an oxidizing gas as a third reactive gas to the substrate; and
(e) supplying an hydrogen-containing gas as a fourth reactive gas to the substrate,
wherein (a) through (e) are non-simultaneously performed.

### Claim 11

A method of manufacturing a semiconductor device, comprising:
forming a film containing a predetermined element, oxygen, carbon and nitrogen on a substrate by repeating a cycle, the cycle comprising:
(a) forming a first layer including the predetermined element, nitrogen and carbon by alternately performing, a predetermined number of times, supplying a source gas containing the predetermined element and a halogen element to the substrate; and supplying a first reactive gas containing three elements including carbon, nitrogen and hydrogen to the substrate;
(b) forming a second layer by supplying a nitriding gas as a second reactive gas to the substrate to nitride the first layer;
(c) forming a third layer by supplying an oxidizing gas as a third reactive gas to the substrate to oxidize the second layer; and
(d) forming a fourth layer by supplying an hydrogen-containing gas as a fourth reactive gas to the substrate to modify a surface of the third layer,
wherein (a) through (d) are non-simultaneously performed.

### Claim 12 (depends on 11)

The method according to claim 11, wherein the surface of the third layer modified in (d) to include more OH group than that of the third layer before modification.