# US 10,864,548 B2 · Film forming method and film forming apparatus

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- Number: US 10,864,548 B2
- Document ID: US10864548B2
- Status: Granted
- Kind: B2
- Application number: 15/960,885
- Filed: 2018-04-24
- Published: 2018-11-01
- Granted: 2020-12-15
- Earliest claimed: 2017-05-01
- Assignees: Tokyo Electron Limited
- Applicants: Tokyo Electron Limited
- Inventors: Hiroaki Ashizawa; Yasushi Fujii; Tsuyoshi Takahashi; Seokhyoung Hong; Kazuyoshi Yamazaki; Hideo Nakamura; Yu Nunoshige; Takashi Kamio
- Web page: https://patentgrep.com/patent/US10864548B2

## CPC

- B05D 1/34: Applying different liquids or other fluent materials simultaneously
- B05D 1/38: with intermediate treatment (intermediate treatment per se B05D3/00)
- B05D 3/007: {After-treatment}
- C23C 16/34: Nitrides {(C23C16/303 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 16/45544: {characterized by the apparatus}
- C23C 16/45561: {Gas plumbing upstream of the reaction chamber}
- H10P 14/432: {using selective deposition}
- H10W 20/033: {in openings in dielectrics}
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10

## Abstract

A step of constantly supplying first and second carrier gases into a processing container having a substrate therein through first and second carrier gas flow paths, respectively, and supplying a source gas into the processing container through a source gas flow path, a step of purging the source gas by supplying a purge gas into the processing container through a purge gas flow path provided separately from the carrier gas, a step of supplying a reactant gas into the processing container through a reactant gas flow path, and a step of purging the reactant gas by supplying a purge gas into the processing container through the purge gas flow path are performed in a predetermined cycle. An additive gas having a predetermined function is supplied as at least a part of the purge gas in at least one of the purging steps.

## Claims

### Claim 1

A film forming method for forming a predetermined film, the film forming method comprising:
providing a film forming apparatus including:
a processing container configured to accommodate therein a substrate to be processed;
a gas supply configured to supply a source gas and a reactant gas for forming the predetermined film on the substrate to be processed, carrier gases for carrying the source gas and the reactant gas to the processing container and a purge gas for purging an interior of the processing container, respectively; and
a gas discharge configured to discharge gases in the processing container and maintain a vacuum atmosphere in the processing container,
wherein the gas supply includes a source gas flow path configured to supply the source gas into the processing container, a reactant gas flow path configured to supply the reactant gas into the processing container, a first carrier gas flow path and a second carrier gas flow path connected to the source gas flow path and the reactant gas flow path, respectively, and configured to supply the carrier gases for the source gas and the reactant gas, a purge gas flow path including a first purge gas flow path connected to the first carrier gas flow path and a second purge gas flow path connected to the second carrier gas flow path, and
wherein the purge gas flow path is configured to supply the purge gas for purging the interior of the processing container into the processing container by controlling a flow rate of the purge gas separately from the first carrier gas and the second carrier gas, an additive gas flow path configured to supply an additive gas having a predetermined function to the predetermined film, and opening/closing valves configured to independently open and close the source gas flow path, the reactant gas flow path, the first and second carrier gas flow paths, the purge gas flow path, and the additive gas flow path, respectively;
a first process of constantly supplying the carrier gases into the processing container through the first carrier gas flow path and the second carrier gas flow path in a state in which the substrate to be processed is disposed in the processing container;
a second process of causing the source gas to be adsorbed to a surface of the substrate to be processed by supplying the source gas into the processing container through the source gas flow path;
a third process of purging the source gas by stopping the supply of the source gas and supplying the purge gas into the processing container through the purge gas flow path;
a fourth process of causing the source gas and the reactant gas to react with each other by supplying the reactant gas into the processing container through the reactant gas flow path; and,
a fifth process of purging the reactant gas by stopping the supply of the reactant gas and supplying the purge gas into the processing container through the purge gas flow path,
wherein the purge gas is supplied into the processing container through the first and second purge gas flow paths at a flow rate which is higher than the flow rate of the first carrier gas and the second carrier gas, while not increasing the flow rate of the first and second carrier gases,
wherein the second to fifth processes are performed in a predetermined cycle, and
wherein the additive gas having the predetermined function is supplied through the additive gas flow path as at least a part of the purge gas in one or both of the third process of purging the source gas and the fifth process of purging the reactant gas.

### Claim 2 (depends on 1)

The film forming method according to claim 1, wherein the purge gas flow path has a gas storage configured to store the purge gas therein, and the purge gas is stored in the gas storage and then supplied into the processing container when pressure in the gas storage is increased and the valve provided in the purge gas flow path is opened.

### Claim 3 (depends on 1)

The film forming method according to claim 1, wherein the first purge gas flow path is further connected to the source gas flow path and the second purge gas flow path is further connected to the reactant gas flow path, and supplies the purge gas through the first purge gas flow path and the second purge gas flow path in the third process of purging the source gas and the fifth process of purging the reactant gas.

### Claim 4 (depends on 1)

The film forming method according to claim 1, wherein the source gas is TiCl4 gas, the reactant gas is NH3 gas, and the predetermined film is a TiN film.

### Claim 5 (depends on 4)

The film forming method according to claim 4, wherein the additive gas is H2 gas.

### Claim 6 (depends on 5)

The film forming method according to claim 5, wherein a temperature during film forming is 400 to 750° C., H2 gas is supplied as the additive gas in the fifth process of purging the reactant gas, and the H2 gas serves to decrease specific resistance of the TiN film.

### Claim 7 (depends on 6)

The film forming method according to claim 6, wherein the second and fifth processes are repeated in multiple cycles, and time of the fifth process for a final cycle is prolonged and wherein the time is 60 seconds or less.

### Claim 8 (depends on 6)

The film forming method according to claim 6, wherein the second and fifth processes are repeated in multiple cycles, and the fifth process is periodically prolonged.

### Claim 9 (depends on 5)

The film forming method according to claim 5, wherein a temperature during film forming is 400 to 500° C., H2 gas is supplied as the additive gas in both of the third process of purging the source gas and the fifth process of purging the reactant gas, and the H2 gas serves to improve continuity of the TiN film.

### Claim 10 (depends on 5)

The film forming method according to claim 5, wherein H2 gas is supplied as the additive gas only in the fifth process of purging the reactant gas or in both of the third process of purging the source gas and the fifth process of purging the reactant gas, and the H2 gas serves to inhibit an etching action of TiCl4.

### Claim 11 (depends on 10)

The film forming method according to claim 10, wherein a temperature during film forming is within a range of 625 to 740° C.

### Claim 12 (depends on 10)

The film forming method according to claim 10, wherein a flow rate of the TiCl4 gas is within a range of 50 to 270 sccm.

### Claim 13 (depends on 11)

The film forming method according to claim 11, wherein a flow rate of the TiCl4 gas is within a range of 50 to 270 sccm.