# US 10,121,654 B2 · Method for manufacturing semiconductor device, substrate-processing apparatus, and recording medium

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- Number: US 10,121,654 B2
- Document ID: US10121654B2
- Status: Granted
- Kind: B2
- Application number: 15/386,859
- Filed: 2016-12-21
- Published: 2017-04-13
- Granted: 2018-11-06
- Earliest claimed: 2014-06-25
- Assignees: Hitachi Kokusai Electric Inc.
- Applicants: Hitachi Kokusai Electric Inc.
- Inventors: Yoshinobu Nakamura; Kiyohiko Maeda; Yoshiro Hirose; Ryota Horiike; Yoshitomo Hashimoto
- Web page: https://patentgrep.com/patent/US10121654B2

## CPC

- H01L 21/0228
- C23C 16/02: Pretreatment of the material to be coated (C23C16/04 takes precedence)
- C23C 16/34: Nitrides {(C23C16/303 takes precedence)}
- C23C 16/4554: {Plasma being used non-continuously in between ALD reactions (C23C16/56 takes precedence)}
- C23C 16/45527: {characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations}
- C23C 16/45542: {Plasma being used non-continuously during the ALD reactions}
- C23C 16/45544: {characterized by the apparatus}
- C23C 16/52: Controlling or regulating the coating process {(C23C16/45557, C23C16/279 take precedence)}
- C23C 16/56: After-treatment
- H01L 21/0217
- H01L 21/0234
- H01L 21/02126
- H01L 21/02211
- H01L 21/02247
- H01L 21/02274
- H01L 21/02304
- H01L 21/02312
- H01L 21/02315
- H01L 21/02318
- H01L 21/02337
- H01L 21/3081
- H01L 21/3086
- H01L 21/30604
- H01L
- 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 method for manufacturing a semiconductor device, including: providing a substrate with an oxide film formed on a surface thereof; pre-processing a surface of the oxide film; and forming a nitride film containing carbon on the surface of the oxide film which has been pre-processed, by performing a cycle a predetermined number of times, the cycle including non-simultaneously performing: supplying a precursor gas to the substrate; supplying a carbon-containing gas to the substrate; and supplying a nitrogen-containing gas to the substrate, or by performing a cycle a predetermined number of times, the cycle including non-simultaneously performing: supplying a precursor gas to the substrate; and supplying a gas containing carbon and nitrogen to the substrate, or by performing a cycle a predetermined number of times, the cycle including non-simultaneously performing: supplying a precursor gas containing carbon to the substrate; and supplying a nitrogen-containing gas to the substrate.

## Claims

### Claim 1

A method for manufacturing a semiconductor device, comprising:
providing a substrate with an oxide film formed on a surface thereof;
pre-processing a surface of the oxide film;
forming a nitride film containing carbon on the surface of the oxide film which has been pre-processed; and
after forming the nitride film containing carbon, heat-processing the substrate under a temperature higher than a temperature of the substrate in the forming the nitride film containing carbon,
wherein the forming the nitride film containing carbon is performed by either:
(a) performing a cycle a predetermined number of times, the cycle including non-simultaneously performing:
supplying a precursor gas to the substrate;
supplying a carbon-containing gas to the substrate; and
supplying a nitrogen-containing gas to the substrate, or
(b) performing a cycle a predetermined number of times, the cycle including non-simultaneously performing:
supplying a precursor gas to the substrate; and
supplying a gas containing carbon and nitrogen to the substrate, or
(c) performing a cycle a predetermined number of times, the cycle including non-simultaneously performing:
supplying a precursor gas containing carbon to the substrate; and
supplying a nitrogen-containing gas to the substrate;
wherein a concave portion is formed in the surface of the substrate, and the oxide film is formed on an inner surface of the concave portion,
wherein, in the forming the nitride film containing carbon, the nitride film containing carbon is formed to fill an interior of the concave portion in which the oxide film is formed.

### Claim 2 (depends on 1)

The method of claim 1, wherein in the pre-processing the surface of the oxide film, a nitride layer containing oxygen and carbon or a nitride layer not containing oxygen and carbon is formed on the surface of the oxide film.

### Claim 3 (depends on 2)

The method of claim 2, wherein in the pre-processing the surface of the oxide film, includes either:
(a) a cycle including non-simultaneously performing:
supplying a precursor gas to the substrate;
supplying a carbon-containing gas to the substrate; and
supplying a nitrogen-containing gas to the substrate is performed a predetermined number of times, or
(b) a cycle including non-simultaneously performing:
supplying a precursor gas to the substrate; and
supplying a gas containing carbon and nitrogen to the substrate is performed a predetermined number of times, or
(c) a cycle including non-simultaneously performing:
supplying a precursor gas containing carbon to the substrate; and
supplying a nitrogen-containing gas to the substrate is performed a predetermined number of times, and
wherein the nitride layer containing oxygen and carbon is formed using the oxide film as an oxygen source.

### Claim 4 (depends on 2)

The method of claim 2, wherein in the pre-processing the surface of the oxide film, the nitride layer not containing oxygen and carbon is formed by:
performing a cycle a predetermined number of times, the cycle including non-simultaneously performing:
supplying a precursor gas to the substrate and
supplying a plasma-excited nitrogen-containing gas to the substrate.

### Claim 5 (depends on 2)

The method of claim 2, wherein in the pre-processing the surface of the oxide film, the nitride layer not containing oxygen and carbon is formed by:
supplying a plasma-excited nitrogen-containing gas to the substrate after performing a cycle a predetermined number of times, the cycle including non-simultaneously performing:
supplying a precursor gas to the substrate and
supplying a nitrogen-containing to the substrate.

### Claim 6 (depends on 2)

The method of claim 2, wherein in the pre-processing the surface of the oxide film, the nitride layer not containing oxygen and carbon is formed by:
performing a cycle a predetermined number of times, the cycle including non-simultaneously performing:
non-simultaneously performing, a predetermined number of times, a set which non-simultaneously performs
supplying a precursor gas to the substrate and supplying a nitrogen-containing to the substrate; and
supplying a plasma-excited nitrogen-containing gas to the substrate.

### Claim 7 (depends on 1)

The method of claim 1, wherein in the pre-processing the surface of the oxide film, the surface of the oxide film is modified by supplying a modification gas to the substrate.

### Claim 8 (depends on 1)

The method of claim 1, wherein the pre-processing the surface of the oxide film and the forming the nitride film containing carbon are performed in a state where the substrate is accommodated in a process chamber, and
wherein the method further comprises:
after performing the forming the nitride film containing carbon, forming a cap layer on a surface of the nitride film containing carbon within the process chamber.

### Claim 9 (depends on 1)

The method of claim 1, wherein a thickness of the nitride film containing carbon is set to fall within a range of 0.2 to 10 nm.

### Claim 10 (depends on 1)

The method of claim 1, wherein a concentration of carbon in the nitride film containing carbon is set to fall within a range of 3 to 10 atomic %.

### Claim 11 (depends on 1)

The method of claim 1, further comprising:
performing an etching process to the substrate on which the nitride film containing carbon is formed.