# US 8,785,333 B2 · Method of manufacturing semiconductor device, substrate processing apparatus, and recording medium

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- Number: US 8,785,333 B2
- Document ID: US8785333B2
- Status: Granted
- Kind: B2
- Application number: 13/973,714
- Filed: 2013-08-22
- Published: 2014-02-27
- Granted: 2014-07-22
- Earliest claimed: 2012-08-23
- Assignees: Hitachi Kokusai Electric Inc.
- Applicants: Hitachi Kokusai Electric Inc.
- Inventors: Yoshitomo Hashimoto; Yoshiro Hirose; Satoshi Shimamoto; Atsushi Sano
- Web page: https://patentgrep.com/patent/US8785333B2

## CPC

- H10P 14/6927: {the material being a silicon oxynitride, e.g. SiON or SiON:H}
- 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}
- H10P 14/6336: {in the presence of a plasma [PECVD]}
- 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 14/6687: {the compound comprising silicon and nitrogen}
- H10P 14/6905: {being a silicon carbide or silicon carbonitride and not containing oxygen, e.g. SiC or SiC:H}
- H10P 14/69433: {the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz}
- H10P 72/0402: {Apparatus for fluid treatment (H10P72/0441, H10P72/0448 take precedence)}
- H10P 72/0434: {mainly by convection}
- 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 includes forming a thin film containing a predetermined element, carbon, nitrogen and a borazine ring skeleton on a substrate by performing a cycle for a first predetermined number of times. The cycle includes forming a first layer containing the predetermined element, a halogen group, carbon and nitrogen by supplying a first precursor gas containing the predetermined element and the halogen group and a second precursor gas containing the predetermined element and an amino group to the substrate, for a second predetermined number of times; and forming a second layer containing the predetermined element, carbon, nitrogen and the borazine ring skeleton by supplying a reaction gas containing a borazine compound to the substrate and allowing the first layer to react with the borazine compound to modify the first layer under a condition where the borazine ring skeleton in the borazine compound is maintained.

## Claims

### Claim 1

A method of manufacturing a semiconductor device, the method comprising forming a thin film containing a predetermined element, carbon, nitrogen and a borazine ring skeleton on a substrate by performing a cycle for a first predetermined number of times, the cycle comprising:
forming a first layer containing the predetermined element, a halogen group, carbon and nitrogen by performing supplying a first precursor gas containing the predetermined element and the halogen group to the substrate and supplying a second precursor gas containing the predetermined element and an amino group to the substrate, for a second predetermined number of times; and
forming a second layer containing the predetermined element, carbon, nitrogen and the borazine ring skeleton by supplying a reaction gas containing a borazine compound to the substrate and allowing the first layer to react with the borazine compound to modify the first layer under a condition in which the borazine ring skeleton in the borazine compound is maintained.

### Claim 2 (depends on 1)

The method of claim 1, wherein in the act of forming the second layer, the halogen group contained in the first layer is reacted with a ligand contained in the borazine compound.

### Claim 3 (depends on 1)

The method of claim 1, wherein in the act of forming the second layer, the halogen group contained in the first layer is reacted with a ligand contained in the borazine compound to separate the halogen group reacted with the ligand from the first layer and separate the ligand reacted with the halogen group from the borazine compound.

### Claim 4 (depends on 1)

The method of claim 1, wherein in the act of forming the second layer, the halogen group contained in the first layer is reacted with a ligand contained in the borazine compound to separate the halogen group reacted with the ligand from the first layer and separate the ligand reacted with the halogen group from the borazine compound, thereby bonding the borazine compound with the ligand separated therefrom and the predetermined element contained in the first layer.

### Claim 5 (depends on 1)

The method of claim 1, wherein in the act of forming the second layer, the halogen group contained in the first layer is reacted with a ligand contained in the borazine compound to separate the halogen group reacted with the ligand from the first layer and separate the ligand reacted with the halogen group from the borazine compound, thereby bonding a portion of a borazine ring of the borazine compound with the ligand separated therefrom and the predetermined element contained in the first layer.

### Claim 6 (depends on 1)

The method of claim 1, wherein in the act of forming the second layer, the halogen group contained in the first layer is reacted with a ligand contained in the borazine compound to separate the halogen group reacted with the ligand from the first layer and separate the ligand reacted with the halogen group from the borazine compound, thereby bonding nitrogen constituting a borazine ring of the borazine compound with the ligand separated therefrom and the predetermined element contained in the first layer.

### Claim 7 (depends on 1)

The method of claim 1, wherein the cycle further comprises modifying the second layer and adjusting nitrogen and carbon components of the second layer by supplying a nitriding gas to the substrate and nitriding the second layer under a condition in which the borazine ring skeleton in the second layer is maintained.

### Claim 8 (depends on 1)

The method of claim 1, wherein the cycle further comprises modifying the second layer and adjusting nitrogen and carbon components of the second layer by supplying a reaction gas containing carbon and nitrogen to the substrate under a condition in which the borazine ring skeleton in the second layer is maintained.

### Claim 9 (depends on 1)

The method of claim 1, wherein the cycle further comprises forming a third layer containing the predetermined element, nitrogen and the borazine ring skeleton, or a third layer containing the predetermined element, carbon, nitrogen and the borazine ring skeleton by supplying a nitriding gas to the substrate and nitriding the second layer to modify the second layer under a condition in which the borazine ring skeleton in the second layer is maintained,
wherein in the act of forming the thin film, a thin film containing the predetermined element, nitrogen and the borazine ring skeleton, or a thin film containing the predetermined element, carbon, nitrogen and the borazine ring skeleton is formed on the substrate.

### Claim 10 (depends on 9)

The method of claim 9, wherein in the act of forming the third layer, carbon contained in the second layer is at least partially separated from the second layer.

### Claim 11 (depends on 1)

The method of claim 1, wherein in the act of forming the first layer, the act of supplying the first precursor gas and the act of supplying the second precursor gas are alternately performed for the second predetermined number of times.

### Claim 12 (depends on 1)

The method of claim 1, wherein in the act of forming the first layer, the act of supplying the first precursor gas and the act of supplying the second precursor gas are set as one set and the set is performed for the second predetermined number of times.

### Claim 13 (depends on 1)

The method of claim 1, wherein in the act of forming the first layer, the act of supplying the first precursor gas and the act of supplying the second precursor gas are simultaneously performed for the second predetermined number of times.

### Claim 14 (depends on 1)

The method of claim 1, wherein the predetermined element comprises a semiconductor element or a metal element.

### Claim 15 (depends on 1)

The method of claim 1, wherein the predetermined element comprises a silicon element.

### Claim 16

A substrate processing apparatus, comprising:
a process chamber configured to accommodate a substrate;
a heater configured to heat the substrate in the process chamber;
a first precursor gas supply system configured to supply a first precursor gas containing a predetermined element and a halogen group to the substrate in the process chamber;
a second precursor gas supply system configured to supply a second precursor gas containing the predetermined element and an amino group to the substrate in the process chamber;
a reaction gas supply system configured to supply a reaction gas containing a borazine compound to the substrate in the process chamber;
a pressure adjusting unit configured to adjust an internal pressure of the process chamber; and
a control unit configured to control the first precursor gas supply system, the second precursor gas supply system, the reaction gas supply system, the heater and the pressure adjusting unit such that a thin film containing the predetermined element, carbon, nitrogen and a borazine ring skeleton is formed on the substrate by performing a cycle for a first predetermined number of times, the cycle comprising:
forming a first layer containing the predetermined element, the halogen group, carbon and nitrogen by performing supplying the first precursor gas to the substrate in the process chamber and supplying the second precursor gas to the substrate in the process chamber, for a second predetermined number of times; and
forming a second layer containing the predetermined element, carbon, nitrogen and the borazine ring skeleton by supplying the reaction gas to the substrate in the process chamber and allowing the first layer to react with the borazine compound to modify the first layer under a condition in which the borazine ring skeleton in the borazine compound is maintained.

### Claim 17

A non-transitory computer-readable recording medium storing a program that causes a computer to perform a process of forming a thin film containing a predetermined element, carbon, nitrogen and a borazine ring skeleton on a substrate in a process chamber of a substrate processing apparatus by performing a cycle for a first predetermined number of times, the cycle comprising:
forming a first layer containing the predetermined element, a halogen group, carbon and nitrogen by performing supplying a first precursor gas containing the predetermined element and the halogen group to the substrate in the process chamber and supplying a second precursor gas containing the predetermined element and an amino group to the substrate in the process chamber, for a second predetermined number of times; and
forming a second layer containing the predetermined element, carbon, nitrogen and the borazine ring skeleton by supplying a reaction gas containing a borazine compound to the substrate in the process chamber and allowing the first layer to react with the borazine compound to modify the first layer under a condition in which the borazine ring skeleton in the borazine compound is maintained.