# US 2015/0147484 A1 · Atomic Layer Deposition Of Films Comprising Silicon, Carbon And Nitrogen Using Halogenated Silicon Precursors

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- Number: US 2015/0147484 A1
- Document ID: US20150147484A1
- Status: Published application
- Kind: A1
- Application number: 14/533,496
- Filed: 2014-11-05
- Published: 2015-05-28
- Earliest claimed: 2013-11-22
- Assignees: Applied Materials, Inc.
- Applicants: Applied Materials, Inc.
- Inventors: Victor Nguyen; Ning Li; Mihaela Balseanu; Li-Qun Xia; Mark Saly; David Thompson
- Web page: https://patentgrep.com/patent/US20150147484A1

## CPC

- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- C23C 16/345: {Silicon nitride}
- C23C 16/36: Carbonitrides
- C23C 16/45536: {Use of plasma, radiation or electromagnetic fields}
- 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: 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 are methods for the deposition of films comprising SiCN. Certain methods involve exposing a substrate surface to a silicon precursor, wherein the silicon precursor is halogenated with Cl, Br or I, and the silicon precursor comprises a halogenated silane, a halogenated carbosilane, an halogenated aminosilane or a halogenated carbo-sillyl amine. Then, the substrate surface can be exposed to a nitrogen-containing plasma or a nitrogen precursor and densification plasma.

## Claims

### Claim 1

A method of depositing a film comprising Si, C and N, the method comprising:
a. exposing a substrate surface to a silicon precursor, wherein the silicon precursor is halogenated with Cl, Br or I, and the silicon precursor comprises a halogenated silane, a halogenated carbosilane, an halogenated aminosilane or a halogenated carbo-sillyl amine; and
b. exposing the substrate to a nitrogen-containing plasma, with the proviso that if the halogenated silicon precursor comprises the halogenated aminosilane or the halogenated silane, then the nitrogen-containing plasma also comprises carbon.

### Claim 2 (depends on 1)

The method of claim 1, wherein the silicon precursor comprises a halogenated bis(silyl) methane-based precursor.

### Claim 3 (depends on 2)

The method of claim 2, wherein the halogenated bis(silyl) methane-based precursor has a structure represented by:
wherein
each R, R1, R2, R3 and R4 is independently H, Cl or (CH2)nCHyNAy,
n=0-6,
y=0-1,
A=C1-6 linear, branched or cyclic alkyl or aryl group or hydrogen.

### Claim 4 (depends on 1)

The method of claim 1, wherein the silicon precursor comprises a halogenated cyclotrisilazane-based precursor.

### Claim 5 (depends on 4)

The method of claim 4, wherein the halogenated cyclotrisilazane-based precursor has a structure represented by:
wherein
each R is independently is H or (CH2)nCHyNAy;
each R1, and R2 are independently H, Br, Cl, I or (CH2)—CHyNAy, with the proviso that at least one R1 or R2 is Br, Cl or I;
n=0-6;
y=0-1;
A=C1-6 linear, branched or cyclic alkyl or aryl group or hydrogen.

### Claim 6 (depends on 1)

The method of claim 1, wherein the silicon precursor comprises a halogenated trisilacyclohexane-based precursor.

### Claim 7 (depends on 6)

The method of claim 6, wherein the halogenated trisilacyclohexane-based precursor has a structure represented by:
wherein
each R, R1, R2, R3 and R4 is independently H, Br, Cl, I or (CH2)—CHyNAy;
n=0-6;
y=0-1;
A=C1-6 linear, branched or cyclic alkyl or aryl group or hydrogen.

### Claim 8 (depends on 1)

The method of claim 1, wherein the nitrogen-containing plasma comprises ammonia, an amine or carbonitride.

### Claim 9

A method of depositing a film comprising Si, C and N, the method comprising:
a. exposing a substrate surface to a silicon precursor, wherein the silicon precursor is halogenated with Cl, Br or I, and the silicon precursor comprises a halogenated silane, a halogenated carbosilane, an halogenated aminosilane or a halogenated carbo-sillyl amine;
b. exposing the substrate surface to a nitrogen precursor to provide a film; and
c. exposing the film to a densification plasma, with the proviso that if the halogenated silicon precursor comprises the halogenated aminosilane or the halogenated silane, then the nitrogen precursor also contains carbon.

### Claim 10 (depends on 9)

The method of claim 9, wherein the silicon precursor comprises a halogenated silane and the nitrogen precursor comprises ammonia.

### Claim 11 (depends on 9)

The method of claim 9, wherein the silicon precursor comprises a halogenated carbosilane and the nitrogen precursor comprises an alkyl amine.

### Claim 12 (depends on 9)

The method of claim 9, wherein the silicon precursor comprises a halogenated bis(silyl) methane precursor.

### Claim 13 (depends on 9)

The method of claim 9, wherein the halogenated bis(silyl) methane-based precursor has a structure represented by:
wherein
each R, R1, R2, R3 and R4 is independently H, Cl or (CH2)nCHyNAy,
n=0-6,
y=0-1,
A=C1-6 linear, branched or cyclic alkyl or aryl group or hydrogen.

### Claim 14 (depends on 9)

The method of claim 9, wherein the silicon precursor comprises a halogenated cyclotrisilazane-based precursor.

### Claim 15 (depends on 14)

The method of claim 14, wherein the halogenated cyclotrisilazane-based precursor has a structure represented by:
wherein
each R is independently H or (CH2)nCHyNAy;
each R1, and R2 are independently H, Br, Cl, I or (CH2)nCHyNAy, with the proviso that at least one R1 or R2 is Br, Cl or I;
n=0-6,
y=0-1,
A=C1-6 linear, branched or cyclic alkyl or aryl group or hydrogen.

### Claim 16 (depends on 9)

The method of claim 9, wherein the silicon precursor comprises a halogenated trisilacyclohexane-based precursor.

### Claim 17 (depends on 16)

The method of claim 16, wherein the halogenated trisilacyclohexane-based precursor has a structure represented by:
wherein
each R, R1, R2, R3 and R4 is independently H, Br, Cl, I or (CH2)nCHyNAy;
n=0-6,
y=0-1,
A=C1-6 linear, branched or cyclic alkyl or aryl group or hydrogen.

### Claim 18 (depends on 17)

The method of claim 17, further comprising exposing the film comprising Si and N to a carbon source.

### Claim 19 (depends on 18)

The method of claim 18, wherein the carbon source comprises exposing the film to a compound with a C═C bond.

### Claim 20

A method of depositing a film comprising Si, C and N, the method comprising
a. exposing a substrate surface to a silicon precursor, wherein the silicon precursor is halogenated with Cl, Br or I, and the silicon precursor comprises a halogenated bis(silyl) methane-based precursor, a halogenated cyclotrisilazane-based precursor or a halogenated trisilacyclohexane-based precursor; and
b. exposing the substrate to a nitrogen-containing plasma or a nitrogen precursor.