# US 2019/0376178 A1 · Compositions and Methods Using Same for Deposition of Silicon-Containing Film

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- Number: US 2019/0376178 A1
- Document ID: US20190376178A1
- Status: Published application
- Kind: A1
- Application number: 16/433,585
- Filed: 2019-06-06
- Published: 2019-12-12
- Earliest claimed: 2018-06-11
- Assignees: Versum Materials US, LLC
- Applicants: Versum Materials US, LLC
- Inventors: Robert G. Ridgeway; Raymond N. Vrtis; Madhukar B. Rao
- Web page: https://patentgrep.com/patent/US20190376178A1

## CPC

- C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates}
- C23C 16/325: {Silicon carbide}
- C23C 16/30: Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C 16/308: {Oxynitrides}
- C23C 16/345: {Silicon nitride}
- C23C 16/36: Carbonitrides
- C23C 16/401: {containing silicon}
- C23C 16/50: using electric discharges {(generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34)}
- C23C 16/513: using plasma jets
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- 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

Described herein are compositions and methods using same for forming a silicon-containing film such as without limitation a silicon carbide, silicon nitride, silicon oxide, silicon oxynitride, a carbon-doped silicon nitride, a carbon-doped silicon oxide, or a carbon doped silicon oxynitride film on at least a surface of a substrate having a surface feature. In one aspect, the silicon-containing films are deposited using a compound comprising a carbon-carbon double or carbon-carbon triple bond. The plasma source employed comprises both a remote plasma source and an in-situ plasma source operating in combination.

## Claims

### Claim 1

A method for depositing a silicon-containing film in a flowable chemical vapor deposition process, the method comprising:
placing a substrate comprising a surface feature into a reactor which is at one or more temperatures ranging from −20° C. to about 100° C.;
introducing into the reactor a composition comprising at least one compound having the formula RnSiR14-n wherein R is selected from a linear or branched C2 to C6 alkenyl group, a linear or branched C2 to C6 alkynyl group; R1 is selected from hydrogen, methane and a linear or branched C2 to C10 alkyl group; and n is a number selected from 0, 1, 2, and 3;
providing a plasma source into the reactor to at least partially react the at least one compound to form a flowable liquid oligomer, wherein the flowable liquid oligomer at least partially fills at least a portion of the surface feature, and wherein the plasma source comprises both a remote plasma source and an in-situ plasma source operating in combination.

### Claim 2 (depends on 1)

The method of claim 1 wherein at least one of the remote plasma source and the in-situ plasma source comprises a plasma source selected from the group consisting of nitrogen plasma, a plasma comprising nitrogen and hydrogen, a plasma comprising nitrogen and helium, a plasma comprising nitrogen and argon, ammonia plasma, a plasma comprising ammonia and helium, a plasma comprising ammonia and argon, a plasma comprising ammonia and nitrogen, NF3, NF3 plasma, organic amine plasma, and mixtures thereof.

### Claim 3 (depends on 1)

The method of claim 1 wherein at least one of the remote plasma source and the in-situ plasma source comprises a plasma source selected from the group consisting of a carbon source plasma, including a hydrocarbon plasma, a plasma comprising hydrocarbon and helium, a plasma comprising hydrocarbon and argon, carbon dioxide plasma, carbon monoxide plasma, a plasma comprising hydrocarbon and hydrogen, a plasma comprising hydrocarbon and a nitrogen source, a plasma comprising hydrocarbon and an oxygen source, and mixture thereof.

### Claim 4 (depends on 1)

The method of claim 1 wherein at least one of the remote plasma source and the in-situ plasma source is selected from but not limited to hydrogen plasma, helium plasma, argon plasma, xenon plasma, and mixture thereof.

### Claim 5 (depends on 1)

The method of claim 1 wherein at least one of the remote plasma source and the in-situ plasma source comprises a plasma source comprising oxygen is selected from the group consisting of water (H2O) plasma, oxygen plasma, ozone (O3) plasma, NO plasma, N2O plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma and combinations thereof.

### Claim 6 (depends on 1)

The method of claim 1 further comprising treating the flowable liquid at one or more temperatures ranging from about 100° C. to about 1000° C. to cure the oligomer and form a hardened film.

### Claim 7 (depends on 1)

The method of claim 1 wherein a pressure of the reactor is maintained at 100 torr or less.

### Claim 8 (depends on 1)

The method of claim 1 wherein the silicon-containing film is selected from the group consisting of silicon carbide, silicon nitride, silicon oxide, carbon doped silicon nitride, carbon doped silicon oxide, silicon oxynitride, and carbon doped silicon oxynitride film.

### Claim 9 (depends on 1)

The method of claim 1 wherein the compound is selected from the group consisting of

### Claim 10 (depends on 9)

The method of claim 9 wherein the at least one compound comprises tetravinylsilane.

### Claim 11 (depends on 1)

A film obtained by the method of claim 1.

### Claim 12 (depends on 6)

The method of claim 6 wherein the film has at least one of the following characteristics i) a film tensile stress ranging from about 150 to about 190 MPa after a UV cure, and ii) a density ranging from about 1.35 to about 2.10 g/cm3.