# US 10,872,764 B2 · Film forming method

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- Number: US 10,872,764 B2
- Document ID: US10872764B2
- Status: Granted
- Kind: B2
- Application number: 16/132,729
- Filed: 2018-09-17
- Published: 2019-03-21
- Granted: 2020-12-22
- Earliest claimed: 2017-09-19
- Assignees: Tokyo Electron Limited
- Applicants: Tokyo Electron Limited
- Inventors: Shinya Iwashita; Takamichi Kikuchi; Naotaka Noro; Toshio Hasegawa; Tsuyoshi Moriya
- Web page: https://patentgrep.com/patent/US10872764B2

## CPC

- H10P 14/6336: {in the presence of a plasma [PECVD]}
- C23C 16/26: Deposition of carbon only
- C23C 16/405: {of refractory metals or yttrium}
- 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 16/4554: {Plasma being used non-continuously in between ALD reactions (C23C16/56 takes precedence)}
- C23C 16/45542: {Plasma being used non-continuously during the ALD reactions}
- C23C 16/52: Controlling or regulating the coating process {(C23C16/45557, C23C16/279 take precedence)}
- 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 14/668: {the materials being characterised by the deposition precursor materials}
- H10P 14/69394: {the material containing titanium, e.g. TiO2}
- 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

Disclosed is a film forming method including forming a metal oxide film on a base film by alternately supplying a metal-containing gas and a plasmatized oxidizing gas. The metal-containing gas is changed from a first metal-containing gas having no halogen to a second metal-containing gas different from the first metal-containing gas during the film forming of the metal oxide film.

## Claims

### Claim 1

A film forming method comprising:
forming a first metal oxide film on a base film during a first period of time by alternately supplying a first metal-containing gas and a plasmatized oxidizing gas to the base film; and
forming a second metal oxide film on the first metal oxide film during a second period of time by alternately supplying a second metal-containing gas and the plasmatized oxidizing gas to the first metal oxide film,
wherein the first metal-containing gas does not include halogen and the second metal-containing gas is different from the first metal-containing gas, and
wherein the first metal-containing gas and the second metal-containing gas contain a same metal element.

### Claim 2 (depends on 1)

The film forming method of claim 1, wherein the metal oxide film formed using the first metal-containing gas has a thickness of 1 nm or less.

### Claim 3 (depends on 1)

The film forming method of claim 1, wherein the second metal-containing gas includes the halogen.

### Claim 4 (depends on 3)

The film forming method of claim 3, wherein the halogen is chlorine.

### Claim 5 (depends on 1)

The film forming method of claim 1, wherein the first metal-containing gas is tetrakis(dimethylamino)titanium (TDMAT).

### Claim 6 (depends on 1)

The film forming method of claim 1, wherein the second metal-containing gas is TiCl4.

### Claim 7 (depends on 1)

The film forming method of claim 1, wherein the base film is an amorphous carbon film having a predetermined pattern.

### Claim 8

A film forming method comprising:
forming a metal oxide film on a workpiece using a film forming apparatus including a placing table on which the workpiece is placed and an impedance adjustment circuit provided to adjust an impedance between the placing table and a ground,
wherein the metal oxide film is formed by:
forming a first metal oxide film on the workpiece during a first period of time by alternately supplying a first metal-containing gas and a plasmatized oxidizing gas to the workpiece; and
forming a second metal oxide film on the first metal oxide film during a second period of time by alternately supplying a second metal-containing gas and the plasmatized oxidizing gas to the first metal oxide film,
wherein the impedance adjustment circuit is adjusted such that the impedance changes from a first impedance to a second impedance lower than the first impedance during the film forming of the metal oxide film, and
wherein the first metal-containing gas and the second metal-containing gas contain a same metal element.