# US 10,319,585 B2 · Film forming method

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- Number: US 10,319,585 B2
- Document ID: US10319585B2
- Status: Granted
- Kind: B2
- Application number: 15/722,343
- Filed: 2017-10-02
- Published: 2018-04-12
- Granted: 2019-06-11
- Earliest claimed: 2016-10-07
- Assignees: Tokyo Electron Limited
- Applicants: Tokyo Electron Limited
- Inventors: Kohichi Satoh; Shinya Okabe; Nagayasu Hiramatsu; Motoko Nakagomi; Yuji Kobayashi
- Web page: https://patentgrep.com/patent/US10319585B2

## CPC

- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- C23C 16/0281: {of metallic sub-layers (C23C16/029 takes precedence)}
- C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates}
- C23C 16/06: characterised by the deposition of metallic material
- C23C 16/45512: {Premixing before introduction in the reaction chamber}
- C23C 16/45536: {Use of plasma, radiation or electromagnetic fields}
- C23C 16/45574: {Nozzles for more than one gas}
- C23C 16/5096: {Flat-bed apparatus}
- H01J 37/32: Gas-filled discharge tubes (heating by discharge H05B)
- H10P 14/432: {using selective deposition}
- H10P 14/6336: {in the presence of a plasma [PECVD]}
- H10W 20/033: {in openings in dielectrics}
- H01J 37/26: Electron or ion microscopes; Electron or ion diffraction tubes
- H01J 2237/3321: CVD [Chemical Vapor Deposition]
- 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)
- H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H)
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10

## Abstract

A film forming method of forming a film containing a metal element on a substrate using a source gas containing the metal element and a reactant gas that reacts with the source gas, which includes: forming a lower layer film containing the metal element on a surface of the substrate through a plasma CVD process by supplying the source gas into a process container and plasmarizing the source gas; and subsequently, laminating an upper layer film containing the metal element on the lower layer film by a plasma ALD process which alternately performs an adsorption step of supplying the source gas into the process container to adsorb the source gas onto the surface of the substrate with the lower layer film formed thereon, and a reaction step of supplying the reactant gas into the process container and plasmarizing the reactant gas.

## Claims

### Claim 1

A film forming method of forming a film containing a metal element on a substrate using a source gas containing the metal element and a reactant gas that reacts with the source gas, the method comprising:
forming a lower layer film containing the metal element on a surface of the substrate through a chemical vapor deposition process (plasma CVD process) by supplying the source gas and the reactant gas into a process container and plasmarizing a mixture gas of the source gas and the reactant gas, the substrate on which a film is to be formed being disposed inside the process container; and
subsequently, laminating an upper layer film containing the metal element on the lower layer film by an atomic layer deposition process (plasma ALD process) which alternately performs an adsorption step of supplying the source gas into the process container to adsorb the source gas onto the surface of the substrate with the lower layer film formed thereon, and a reaction step of supplying the reactant gas into the process container and plasmarizing the reactant gas so that the plasmarized reactant gas reacts with the source gas adsorbed onto the surface of the substrate.

### Claim 2 (depends on 1)

The film forming method of claim 1, wherein the act of forming the lower layer film is performed until the lower layer film has a predetermined thickness of 3 nm or less and subsequently, the act of laminating the upper layer film is performed.

### Claim 3 (depends on 1)

The film forming method of claim 1, wherein the lower layer film and the upper layer film are metal films.

### Claim 4 (depends on 1)

The film forming method of claim 1, wherein the source gas contains TiCl4, and the reactant gas contains H2.

### Claim 5 (depends on 4)

The film forming method of claim 4, wherein the upper layer film and the lower layer film contain Ti.