# US 11,078,569 B2 · Trisilylamine derivatives as precursors for high growth rate silicon-containing films

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- Number: US 11,078,569 B2
- Document ID: US11078569B2
- Status: Granted
- Kind: B2
- Application number: 16/134,108
- Filed: 2018-09-18
- Published: 2019-03-21
- Granted: 2021-08-03
- Earliest claimed: 2017-09-19
- Assignees: Versum Materials US, LLC
- Applicants: Versum Materials US, LLC
- Inventors: Xinjian Lei; Matthew R. MacDonald; Meiliang Wang
- Web page: https://patentgrep.com/patent/US11078569B2

## CPC

- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- C23C 16/345: {Silicon nitride}
- C23C 16/402: {Silicon dioxide}
- C23C 16/45542: {Plasma being used non-continuously during the ALD reactions}
- C07F 7/025: {without C-silicon linkages}
- C07F 7/10: containing nitrogen {having a Si-N linkage}
- 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)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

Described herein are compositions and methods for forming silicon and oxygen containing films. In one aspect, the film is deposited from at least one precursor, wherein the at least one precursor selected from the group consisting of Formulae A and B: wherein R, R1, and R2-8 are as defined herein.

## Claims

### Claim 1

A method to deposit a film comprising silicon and oxygen onto a substrate comprises steps of:
a) providing a substrate in a reactor;
b) introducing into the reactor at least one silicon precursor compound, wherein the at least one silicon precursor compound is selected from the group consisting of Formulae A and B:
wherein R1 is selected from a C3 to C10 cyclic alkyl group, a branched C4 to C10 cyclic alkyl group, a C3 to C10 cyclic alkenyl group, a branched C4 to C10 cyclic alkenyl group, a C3 to C6 cyclic alkynyl group, a branched C3 to C6 cyclic alkynyl group; R and R2-8 are each independently selected from the group consisting of hydrogen, a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C1 to C6 dialkylamino group, a C1 to C6 alkylamino group, a C3 to C10 cyclic alkyl group, a branched C4 to C10 cyclic alkyl group, a C3 to C10 cyclic alkenyl group, a branched C4 to C10 cyclic alkenyl group, a C3 to C6 cyclic alkynyl group, a branched C3 to C6 cyclic alkynyl group, and a C4 to C10 aryl group wherein the silicon precursor is substantially free of halide;
c) purging the reactor with purge gas;
d) introducing an oxygen-containing source into the reactor; and
e) purging the reactor with purge gas,
wherein steps b through e are repeated until a desired thickness of film is deposited, and
wherein the method is conducted at one or more temperatures ranging from about 25° C. to 600° C.

### Claim 2 (depends on 1)

The method of claim 1, wherein the compound is selected from the group consisting of N-cyclohexyl-N-methyl-N′,N′-disilyl-silanediamine, N-cyclohexyl-N-ethyl-N′,N′-disilyl-silanediamine, N-cyclohexyl-N-iso-propyl-N′,N′-disilyl-silanediamine, N,N-dicyclohexyl-N′,N′-disilyl-silanediamine, N-cyclohexyl-N′,N′-disilyl-silanediamine, N-cyclopentyl-N′,N′-disilyl-silanediamine, N-cyclohexyl-N-methyl-N′,N′-bis(trimethylsilyl)-silanediamine, N-cyclohexyl-N-ethyl-N′,N′-bis(trimethylsilyl)-silanediamine, N-cyclohexyl-N′,N′-bis(trimethylsilyl)-silanediamine, N-cyclopentyl-N′,N′-bis(trimethylsilyl)-silanediamine, N-cyclohexyl-N-methyl-N′,N′-bis(trimethylsilyl)-methylsilanediamine, N-cyclohexyl-N-ethyl-N′,N′-bis(trimethylsilyl)-methylsilanediamine, N-cyclohexyl-N′,N′-bis(trimethylsilyl)-methylsilanediamine, N-cyclopentyl-N′,N′-bis(trimethylsilyl)-methylsilanediamine, N-cyclohexyl-N-methyl-N′,N′-bis(dimethylsilyl)-silanediamine, N-cyclohexyl-N-ethyl-N′,N′-bis(dimethylsilyl)-silanediamine, N-cyclohexyl-N-iso-propyl-N′,N′-bis(dimethylsilyl)-silanediamine, N,N-dicyclohexyl-N′,N′-bis(dimethylsilyl)-silanediamine, N-cyclohexyl-N′,N′-bis(dimethylsilyl)-silanediamine, N-cyclopentyl-N′,N′-bis(dimethylsilyl)-silanediamine, N-cyclohexyl-N′,N′-bis(dimethylsilyl)-methylsilanediamine, N-cyclopentyl-N′,N-bis(dimethylsilyl)-methylsilanediamine, N-cyclohexylmethylaminosilyl-N,N′,N′-trisilyl-silanediamine, N-cyclohexylethylaminosilyl-N,N′,N′-trisilyl-silanediamine, N-cyclohexyl-iso-propylaminosilyl-N,N′,N′-trisilyl-silanediamine, cyclohexylaminosilyl-N, N′,N′-trisilyl-silanediamine, and cyclopentylaminosilyl-N,N′,N′-trisilyl-silanediamine.

### Claim 3 (depends on 1)

The method of claim 1, wherein the oxygen-containing source is selected from the group consisting of an ozone, hydrogen peroxide, an oxygen plasma, a plasma comprising oxygen and argon, a plasma comprising oxygen and helium, an ozone plasma, a water plasma, a nitrous oxide plasma, a carbon dioxide plasma, and combinations thereof.

### Claim 4 (depends on 1)

The method of claim 1 wherein a density of the film is about 2.1 g/cc or greater.

### Claim 5 (depends on 1)

The method of claim 1 wherein the film further comprises carbon.

### Claim 6 (depends on 5)

The method of claim 5 wherein a density of the film is about 1.8 g/cc or greater.

### Claim 7 (depends on 5)

The method of claim 5 wherein a carbon content of the film is 0.5 atomic weight percent (at. %) as measured by x-ray photospectroscopy or greater.

### Claim 8 (depends on 1)

A composition for depositing a film selected from a silicon oxide or a carbon doped silicon oxide film using a vapor deposition process, the composition comprising: at least one silicon precursor compound selected from the group consisting of Formulae A and B as set forth in claim 1.

### Claim 9 (depends on 8)

The composition of claim 8, wherein the compound is selected from the group consisting of N-cyclohexyl-N-methyl-N′,N′-disilyl-silanediamine, N-cyclohexyl-N-ethyl-N′,N′-disilyl-silanediamine, N-cyclohexyl-N-iso-propyl-N′,N′-disilyl-silanediamine, N,N-dicyclohexyl-N′,N′-disilyl-silanediamine, N-cyclohexyl-N′,N′-disilyl-silanediamine, N-cyclopentyl-N′,N′-disilyl-silanediamine, N-cyclohexyl-N-methyl-N′,N′-bis(trimethylsilyl)-silanediamine, N-cyclohexyl-N-ethyl-N′,N′-bis(trimethylsilyl)-silanediamine, N-cyclohexyl-N′,N′-bis(trimethylsilyl)-silanediamine, N-cyclopentyl-N′,N′-bis(trimethylsilyl)-silanediamine, N-cyclohexyl-N-methyl-N′,N′-bis(trimethylsilyl)-methylsilanediamine, N-cyclohexyl-N-ethyl-N′,N′-bis(trimethylsilyl)-methylsilanediamine, N-cyclohexyl-N′,N′-bis(trimethylsilyl)-methylsilanediamine, N-cyclopentyl-N′,N′-bis(trimethylsilyl)-methylsilanediamine, N-cyclohexyl-N-methyl-N′,N′-bis(dimethylsilyl)-silanediamine, N-cyclohexyl-N-ethyl-N′,N′-bis(dimethylsilyl)-silanediamine, N-cyclohexyl-N-iso-propyl-N′,N′-bis(dimethylsilyl)-silanediamine, N,N-dicyclohexyl-N′,N′-bis(dimethylsilyl)-silanediamine, N-cyclohexyl-N′,N′-bis(dimethylsilyl)-silanediamine, N-cyclopentyl-N′,N′-bis(dimethylsilyl)-silanediamine, N-cyclohexyl-N′,N′-bis(dimethylsilyl)-methylsilanediamine, N-cyclopentyl-N′,N-bis(dimethylsilyl)-methylsilanediamine, N-cyclohexylmethylaminosilyl-N,N′,N′-trisilyl-silanediamine, N-cyclohexylethylaminosilyl-N,N′,N′-trisilyl-silanediamine, N-cyclohexyl-iso-propylaminosilyl-N,N′,N′-trisilyl-silanediamine, cyclohexylaminosilyl-N, N′,N′-trisilyl-silanediamine, and cyclopentylaminosilyl-N,N′,N′-trisilyl-silanediamine and combinations thereof.

### Claim 10 (depends on 8)

The composition of claim 8, wherein the halide ions are chloride ions and are included at a concentration of less than 5 ppm.