# US 9,039,838 B2 · Method of manufacturing semiconductor device and substrate processing apparatus

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- Number: US 9,039,838 B2
- Document ID: US9039838B2
- Status: Granted
- Kind: B2
- Application number: 13/553,968
- Filed: 2012-07-20
- Published: 2013-01-24
- Granted: 2015-05-26
- Earliest claimed: 2009-11-20
- Assignees: Hitachi Kokusai Electric Inc.
- Applicants: Ryota Sasajima; Yoshiro Hirose; Yosuke Ota; Naonori Akae; Kojiro Yokozawa
- Inventors: Ryota Sasajima; Yoshiro Hirose; Yosuke Ota; Naonori Akae; Kojiro Yokozawa
- Web page: https://patentgrep.com/patent/US9039838B2

## CPC

- H10P 14/6304: {Formation by oxidation, e.g. oxidation of the substrate}
- C23C 16/402: {Silicon dioxide}
- C23C 16/45546: {specially adapted for a substrate stack in the ALD reactor}
- C23C 16/54: Apparatus specially adapted for continuous coating
- C23C 16/56: After-treatment
- H10P 14/412: {Deposition of metallic or metal-silicide materials}
- H10P 14/6309: {of silicon in uncombined form, i.e. pure silicon}
- H10P 14/6314: {of a metallic layer}
- H10P 14/6529: {by exposure to a gas or vapour}
- H10P 14/69394: {the material containing titanium, e.g. TiO2}
- H10P 95/00: Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass
- 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 14/662: {Laminate layers, e.g. stacks of alternating high-k metal oxides (adhesion layers or buffer layers H10P14/6508, H10P14/6548)}
- H10P 14/6682: {the compound being a silane, e.g. disilane, methylsilane or chlorosilane}
- H10P 14/69215: {the material being a silicon oxide, e.g. SiO2}
- H10P 14/69391: {the material containing aluminium, e.g. Al2O3}
- H10P 14/69392: {the material containing hafnium, e.g. HfO2}
- H10P 14/69395: {the material containing zirconium, e.g. ZrO2}
- H10P 14/69397: {the material containing two or more metal elements}
- 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

Provided is a substrate processing apparatus. The apparatus includes: a process vessel, a heater, a source gas supply system, an oxygen-containing gas supply system, a hydrogen-containing gas supply system, a pressure regulator, and a controller. The controller is configured to control the parts so as to perform: (a) forming an oxide film on a substrate by alternately repeating: (a-1) forming a layer by supplying a source gas into the process vessel accommodating the substrate; and (a-2) changing the layer into an oxide layer by supplying an oxygen-containing gas and an hydrogen-containing gas into the process vessel, the inside of the process vessel being under a heated atmosphere having a low pressure; and (b) modifying the oxide film formed on the substrate by supplying the oxygen-containing gas and the hydrogen-containing gas into the process vessel, the inside of the process vessel being under the heated atmosphere having the low pressure.

## Claims

### Claim 1

A substrate processing apparatus comprising:
a process vessel configured to accommodate a substrate;
a heater configured to heat a substrate in the process vessel;
a source gas supply system configured to supply a source gas containing a predetermined element into the process vessel;
an oxygen-containing gas supply system configured to supply an oxygen-containing gas into the process vessel;
a hydrogen-containing gas supply system configured to supply a hydrogen-containing gas into the process vessel;
a pressure regulator configured to control a pressure of an inside of the process vessel; and
a controller configured to control the heater, the source gas supply system, the oxygen-containing gas supply system, the hydrogen-containing gas supply system, and the pressure regulator so as to perform: (a) forming an oxide film on the substrate by alternately repeating: (a-1) forming a layer containing the predetermined element by supplying the source gas into the process vessel accommodating the substrate; and (a-2) changing the layer containing the predetermined element into an oxide layer by supplying the oxygen-containing gas and the hydrogen-containing gas into the process vessel, the inside of the process vessel being under a heated atmosphere having a pressure lower than an atmospheric pressure; and (b) modifying the oxide film formed on the substrate by supplying the oxygen-containing gas and the hydrogen-containing gas into the process vessel, the inside of the process vessel being under the heated atmosphere having the pressure lower than the atmospheric pressure.

### Claim 2 (depends on 1)

The substrate processing apparatus according to claim 1, wherein the controller is configured to further control the heater, the oxygen-containing gas supply system, and the hydrogen-containing gas supply system so that a temperature of the substrate in the step (b) is higher than a temperature of the substrate in the step (a-2); or a gas supply time of each of the gases in the step (b) is longer than a gas supply time of each of the gases in the step (a-2).

### Claim 3 (depends on 1)

The substrate processing apparatus according to claim 1, wherein the controller is configured to further control the heater so that a temperature of the substrate in the step (b) is higher than a temperature of the substrate in the step (a).

### Claim 4 (depends on 1)

The substrate processing apparatus according to claim 1, wherein the controller is configured to further control the heater, the source gas supply system, the oxygen-containing gas supply system, the hydrogen-containing gas supply system, and the pressure regulator so that the step (a) and the step (b) are alternately repeated.

### Claim 5 (depends on 1)

The substrate processing apparatus according to claim 1, wherein the controller is configured to further control the heater, the source gas supply system, the oxygen-containing gas supply system, the hydrogen-containing gas supply system, and the pressure regulator so that the oxygen-containing gas is reacted with the hydrogen-containing gas under the heated atmosphere having the pressure lower than the atmospheric pressure to form an oxidizing species, and the layer containing the predetermined element is changed into the oxide layer by using the oxidizing species in the step (a-2), and the oxygen-containing gas is reacted with the hydrogen-containing gas under the heated atmosphere having the pressure lower than the atmospheric pressure to form the oxidizing species, and the oxide film is modified by using the oxidizing species in the step (b).

### Claim 6 (depends on 1)

The substrate processing apparatus according to claim 1, wherein the predetermined element comprises at least one of a semiconductor element and a metal element.

### Claim 7 (depends on 1)

The substrate processing apparatus according to claim 1, wherein the predetermined element comprises at least one of a silicon element and a metal element.

### Claim 8 (depends on 1)

The substrate processing apparatus according to claim 1, wherein the predetermined element comprises a silicon element.

### Claim 9

A substrate processing apparatus comprising:
a process vessel configured to accommodate a substrate;
a heater configured to heat a substrate in the process vessel;
a source gas supply system configured to supply a source gas containing a predetermined element into the process vessel;
an oxygen-containing gas supply system configured to supply an oxygen-containing gas into the process vessel;
a hydrogen-containing gas supply system configured to supply a hydrogen-containing gas into the process vessel;
a pressure regulator configured to control a pressure of an inside of the process vessel; and
a controller configured to control the heater, the source gas supply system, the oxygen-containing gas supply system, the hydrogen-containing gas supply system, and the pressure regulator so as to perform: (a) forming an oxide film on the substrate by alternately repeating: (a-1) supplying the source gas into the process vessel accommodating the substrate to form a layer containing the predetermined element; and (a-2) supplying the oxygen-containing gas and the hydrogen-containing gas into the process vessel to change the layer containing the predetermined element into an oxide layer, the inside of the process vessel being under a heated atmosphere having a pressure lower than an atmospheric pressure; and after that, (b) supplying the oxygen-containing gas and the hydrogen-containing gas into the process vessel, the inside of the process vessel being under the heated atmosphere having the pressure lower than the atmospheric pressure.

### Claim 10

A substrate processing apparatus comprising:
a process vessel configured to accommodate a substrate;
a heater configured to heat a substrate in the process vessel;
a source gas supply system configured to supply a source gas containing a predetermined element into the process vessel;
an oxygen-containing gas supply system configured to supply an oxygen-containing gas into the process vessel;
a hydrogen-containing gas supply system configured to supply a hydrogen-containing gas into the process vessel;
a pressure regulator configured to control a pressure of an inside of the process vessel; and
a controller configured to control the heater, the source gas supply system, the oxygen-containing gas supply system, the hydrogen-containing gas supply system, and the pressure regulator so as to perform: alternately repeating: (a-1) supplying the source gas into the process vessel accommodating the substrate; and (a-2) supplying the oxygen-containing gas and the hydrogen-containing gas into the process vessel, the inside of the process vessel being under a heated atmosphere having a pressure lower than an atmospheric pressure; and after that, (b) supplying the oxygen-containing gas and the hydrogen-containing gas into the process vessel, the inside of the process vessel being under the heated atmosphere having the pressure lower than the atmospheric pressure.