# US 9,005,719 B2 · Organoaminosilane precursors and methods for making and using same

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- Number: US 9,005,719 B2
- Document ID: US9005719B2
- Status: Granted
- Kind: B2
- Application number: 14/291,818
- Filed: 2014-05-30
- Published: 2014-09-18
- Granted: 2015-04-14
- Earliest claimed: 2011-05-24
- Assignees: Air Products and Chemicals, Inc.
- Applicants: Manchao Xiao; Xinjian Lei; Bing Han; Mark Leonard O'Neill; Ronald Martin Pearlstein; Richard Ho; Haripin Chandra; Agnes Derecskei-Kovacs
- Inventors: Manchao Xiao; Xinjian Lei; Bing Han; Mark Leonard O'Neill; Ronald Martin Pearlstein; Richard Ho; Haripin Chandra; Agnes Derecskei-Kovacs
- Web page: https://patentgrep.com/patent/US9005719B2

## CPC

- C23C 16/24: Deposition of silicon only
- C07F 7/025: {without C-silicon linkages}
- C07F 7/10: containing nitrogen {having a Si-N linkage}
- C23C 16/308: {Oxynitrides}
- C23C 16/32: Carbides
- C23C 16/345: {Silicon nitride}
- C23C 16/347: {Carbon nitride}
- C23C 16/401: {containing silicon}
- C23C 16/402: {Silicon dioxide}
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P 14/6687: {the compound comprising silicon and nitrogen}
- H10P 14/69215: {the material being a silicon oxide, e.g. SiO2}
- H10P 14/6922: {the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC}
- 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

Described herein are organoaminosilane precursors which can be used to deposit silicon containing films which contain silicon and methods for making these precursors. Also disclosed herein are deposition methods for making silicon-containing films or silicon containing films using the organoaminosilane precursors described herein. Also disclosed herein are the vessels that comprise the organoaminosilane precursors or a composition thereof that can be used, for example, to deliver the precursor to a reactor in order to deposit a silicon-containing film.

## Claims

### Claim 1

A method for forming a silicon-containing film on at least one surface of a substrate comprising:
providing the at least one surface of the substrate in a reaction chamber; and
forming the silicon-containing film on the at least one surface by a deposition process chosen from a chemical vapor deposition process and an atomic layer deposition process from an at least one organoaminosilane having Formula A, B, and C or mixtures thereof is employed as at least one of the silicon containing precursors:
wherein R is independently selected from a C1 to C10 linear or branched alkyl group; a C3 to C10 cyclic alkyl group; a C5 to C10 aromatic group; a C3 to C10 saturated or unsaturated heterocyclic group; a linear or a branched C2 to C10 alkenyl group; a C1 to C10 alkoxy group; a C1 to C10 alkylamino group; or a silyl group in formula C with or without substituents; R1 is independently selected from a C3-C10 linear or branched alkyl group; a C3 to C10 cyclic alkyl group; a C5 to C10 aromatic group; a C3 to C10 saturated or unsaturated heterocyclic group; a hydrogen atom; a linear or a branched C2 to C10 alkenyl group; a C1 to C10 alkoxy group; a C1 to C10 alkylamino group; or a silyl group with substituents; and R2 represents a single bond; a saturated or unsaturated, linear or branched, substituted or unsubstituted, hydrocarbon chain wherein the number of carbon atoms ranges from 1 to 10; a saturated or unsaturated, carbocyclic or heterocyclic ring; SiR2; or SiH2, and wherein R and R1 in Formula A are also combinable to form a cyclic group wherein the organoaminosilane is one selected from the group consisting of: 1-silyl-7-azaindole, N-silyl-2,5-dimethylpyrrole, N-(4-methoxyphenyl)disilazane, N-(3-methoxyphenyl)disilazane, N-(2-methoxyphenyl)disilazane, N-(4-chlorophenyl)disilazane, N-(2-chlorophenyl)disilazane, N-(2-ethylphenyl)disilazane, N-(2,6-diethylphenyl)disilazane, N-(2-propylphenyl)disilazane, N-(4-t-butylphenyl)disilazane, N-(4-iso-propylphenyl)disilazane, N-(2-iso-propylphenyl)disilazane, N-(3-ethylphenyl)disilazane, N-(4-sec-butylphenyl)disilazane, N-(4-vinylphenyl)disilazane, N-(3-methylphenyl)disilazane, N-(4-methylphenyl)disilazane, N-(2,4,6-trimethylphenyl)disilazane, N-(2,6-di-isopropylphenyl)disilazane, 1-N-(2-pyridyl)disilazane, N,N-disilyl-2-aminopyrimidine, N-(4-methyl-2-pyridyl)disilazane, N-(6-methyl-2-pyridyl)disilazane, N-(3-methyl-2-pyridyl)disilazane, N-(5-methyl-2-pyridyl)disilazane, and N-[2-disilyl-2-(4-methylpyrimidino)amino]disilazane, N-(2-dimethylamino-1-methylethyl)disilazane, N-(2-dimethylaminoethyl)disilazane, N-(1-cyclohexylethyl)disilazane, N,N-disilylcumylamine, N-[3,3-dimethylbutyl-2]disilazane, N,N-disilyl-2-picolylamine, N,N-disilyl-2-(2-pyridyl)ethylamine, and N,N-disilyl-1-(4-methylphenyl)ethylamine, N-propyl-isopropylaminosilane, N-methylcyclohexylaminosilane, N-ethylcyclohexylaminosilane, allylphenylaminosilane, N-isopropylcyclohexylaminosilane, allylcyclopentylaminosilane, phenylcyclohexylaminosilane, and 2-(N-silylmethylamino)pyridine.

### Claim 2 (depends on 1)

The method of claim 1 wherein the silicon containing film is at least one selected from the group consisting of: a silicon oxide film, a silicon oxycarbide film, a silicon nitride film, a silicon oxynitride film, a silicon oxycarbonitride film, a silicon carbonitride, and an amorphous silicon film.

### Claim 3

A method of forming a silicon oxide or a silicon oxycarbide film via an atomic layer deposition or plasma enhanced atomic layer deposition process, the method comprising the steps of:
a. providing a substrate in a reactor;
b. introducing into the reactor an at least one silicon precursor selected from an at least one organoaminosilane having Formula A, B, and C or mixtures thereof is employed as at least one of the silicon containing precursors:
wherein R is independently selected from a C1 to C10 linear or branched alkyl group; a C3 to C10 cyclic alkyl group; a C5 to C10 aromatic group; a C3 to C10 saturated or unsaturated heterocyclic group; a linear or a branched C2 to C10 alkenyl group; a C1 to C10 alkoxy group; a C1 to C10 alkylamino group; or a silyl group in formula C with or without substituents; R1 is independently selected from a C3-C10 linear or branched alkyl group; a C3 to C10 cyclic alkyl group; a C5 to C10 aromatic group; a C3 to C10 saturated or unsaturated heterocyclic group; a hydrogen atom; a linear or a branched C2 to C10 alkenyl group; a C1 to C10 alkoxy group; a C1 to C10 alkylamino group; or a silyl group with substituents; and R2 represents a single bond; a saturated or unsaturated, linear or branched, substituted or unsubstituted, hydrocarbon chain wherein the number of carbon atoms ranges from 1 to 10; a saturated or unsaturated, carbocyclic or heterocyclic ring; SiR2; or SiH2, and wherein R and R1 in Formula A are also combinable to form a cyclic group;
c. purging the reactor with a purge gas;
d. introducing an oxygen source into the reactor;
e. purging the reactor with a purge gas; and
the steps b through e are repeated until a desired thickness of the film is obtained wherein the organoaminosilane is one selected from the group consisting of: 1-silyl-7-azaindole, N-silyl-2,5-dimethylpyrrole, N-(4-methoxyphenyl)disilazane, N-(3-methoxyphenyl)disilazane, N-(2-methoxyphenyl)disilazane, N-(4-chlorophenyl)disilazane, N-(2-chlorophenyl)disilazane, N-(2-ethylphenyl)disilazane, N-(2,6-diethylphenyl)disilazane, N-(2-propylphenyl)disilazane, N-(4-t-butylphenyl)disilazane, N-(4-iso-propylphenyl)disilazane, N-(2-iso-propylphenyl)disilazane, N-(3-ethylphenyl)disilazane, N-(4-sec-butylphenyl)disilazane, N-(4-vinylphenyl)disilazane, N-(3-methylphenyl)disilazane, N-(4-methylphenyl)disilazane, N-(2,4,6-trimethylphenyl)disilazane, N-(2,6-di-isopropylphenyl)disilazane, 1-N-(2-pyridyl)disilazane, N,N-disilyl-2-aminopyrimidine, N-(4-methyl-2-pyridyl)disilazane, N-(6-methyl-2-pyridyl)disilazane, N-(3-methyl-2-pyridyl)disilazane, N-(5-methyl-2-pyridyl)disilazane, and N-[2-(4-methylpyrimidino)amino]disilazane, N-(2-dimethylamino-1-methylethyl)disilazane, N-(2-dimethylaminoethyl)disilazane, N-(1-cyclohexylethyl)disilazane, N,N-disilylcumylamine, N-[3,3-dimethylbutyl-2]disilazane, N,N-disilyl-2-picolylamine, N,N-disilyl-2-(2-pyridyl)ethylamine, and N,N-disilyl-1-(4-methylphenyl)ethylamine, N-propyl-isopropylaminosilane, N-methylcyclohexylaminosilane, N-ethylcyclohexylaminosilane, allylphenylaminosilane, N-isopropylcyclohexylaminosilane, allylcyclopentylaminosilane, phenylcyclohexylaminosilane, and 2-(N-silylmethylamino)pyridine.

### Claim 4 (depends on 3)

The method of claim 3 wherein the oxygen source is selected from groups consisting of oxygen (O2), oxygen plasma, water plasma, ozone (O3), NO, N2O, NO2, carbon monoxide (CO), carbon dioxide (CO2), CO2 plasma, and combinations thereof.

### Claim 5

A method of forming a silicon nitride or a silicon carbonitride film via an atomic layer deposition or plasma enhanced atomic layer deposition process, the method comprising the steps of:
a. providing a substrate in a reactor;
b. introducing into the reactor at least one organoaminosilane having Formula A, B, and C or mixtures thereof is employed as at least one of the silicon containing precursors:
wherein R is independently selected from a C1 to C10 linear or branched alkyl group; a C3 to C10 cyclic alkyl group; a C5 to C10 aromatic group; a C3 to C10 saturated or unsaturated heterocyclic group; a linear or a branched C2 to C10 alkenyl group; a C1 to C10 alkoxy group; a C1 to C10 alkylamino group; or a silyl group in formula C with or without substituents; R1 is independently selected from a C3-C10 linear or branched alkyl group; a C3 to C10 cyclic alkyl group; a C5 to C10 aromatic group; a C3 to C10 saturated or unsaturated heterocyclic group; a hydrogen atom; a linear or a branched C2 to C10 alkenyl group; a C1 to C10 alkoxy group; a C1 to C10 alkylamino group; or a silyl group with substituents; and R2 represents a single bond; a saturated or unsaturated, linear or branched, substituted or unsubstituted, hydrocarbon chain wherein the number of carbon atoms ranges from 1 to 10; a saturated or unsaturated, carbocyclic or heterocyclic ring; SiR2; or SiH2, and wherein R and R1 in Formula A are also combinable to form a cyclic group;
c. purging the reactor with a purge gas;
d. introducing a nitrogen-containing source into the reactor;
e. purging the reactor with a purge gas; and
The steps b through e are repeated until a desired thickness of the silicon nitride film is obtained wherein the organoaminosilane is one selected from the group consisting of 1-silyl-7-azaindole, N-silyl-2,5-dimethylpyrrole, N-(4-methoxyphenyl)disilazane, N-(3-methoxyphenyl)disilazane, N-(2-methoxyphenyl)disilazane, N-(4-chlorophenyl)disilazane, N-(2-chlorophenyl)disilazane, N-(2-ethylphenyl)disilazane, N-(2,6-diethylphenyl)disilazane, N-(2-propylphenyl)disilazane, N-(4-t-butylphenyl)disilazane, N-(4-iso-propylphenyl)disilazane, N-(2-iso-propylphenyl)disilazane, N-(3-ethylphenyl)disilazane, N-(4-sec-butylphenyl)disilazane, N-(4-vinylphenyl)disilazane, N-(3-methylphenyl)disilazane, N-(4-methylphenyl)disilazane, N-(2,4,6-trimethylphenyl)disilazane, N-(2,6-di-isopropylphenyl)disilazane, 1-N-(2-pyridyl)disilazane, N,N-disilyl-2-aminopyrimidine, N-(4-methyl-2-pyridyl)disilazane, N-(6-methyl-2-pyridyl)disilazane, N-(3-methyl-2-pyridyl)disilazane, N-(5-methyl-2-pyridyl)disilazane, and N-[2-(4-methylpyrimidino)amino]disilazane, N-(2-dimethylamino-1-methylethyl)disilazane, N-(2-dimethylaminoethyl)disilazane, N-(1-cyclohexylethyl)disilazane, N,N-disilylcumylamine, N-[3,3-dimethylbutyl-2]disilazane, N,N-disilyl-2-picolylamine, N,N-disilyl-2-(2-pyridyl)ethylamine, and N,N-disilyl-1-(4-methylphenyl)ethylamine, N-propyl-isopropylaminosilane, N-methylcyclohexylaminosilane, N-ethylcyclohexylaminosilane, allylphenylaminosilane, N-isopropylcyclohexylaminosilane, allylcyclopentylaminosilane, phenylcyclohexylaminosilane, and 2-(N-silylmethylamino)pyridine.

### Claim 6 (depends on 5)

The method of claim 5 wherein the nitrogen-containing source is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, nitrogen/helium plasma, nitrogen/argon plasma, helium plasma, argon plasma, hydrogen plasma, and mixtures thereof.

### Claim 7

A method of forming a silicon nitride film onto at least a surface of a substrate using a chemical vapor deposition or plasma enhanced chemical vapor deposition process comprising:
a. providing a substrate in a reactor;
b. introducing into the reactor at least one organoaminosilane having Formula A, B, and C or mixtures thereof is employed as at least one of the silicon containing precursors:
wherein R is independently selected from a C1 to C10 linear or branched alkyl group; a C3 to C10 cyclic alkyl group; a C5 to C10 aromatic group; a C3 to C10 saturated or unsaturated heterocyclic group; a linear or a branched C2 to C10 alkenyl group; a C1 to C10 alkoxy group; a C1 to C10 alkylamino group; or a silyl group in formula C with or without substituents; R1 is independently selected from a C3-C10 linear or branched alkyl group; a C3 to C10 cyclic alkyl group; a C5 to C10 aromatic group; a C3 to C10 saturated or unsaturated heterocyclic group; a hydrogen atom; a linear or a branched C2 to C10 alkenyl group; a C1 to C10 alkoxy group; a C1 to C10 alkylamino group; or a silyl group with substituents; and R2 represents a single bond; a saturated or unsaturated, linear or branched, substituted or unsubstituted, hydrocarbon chain wherein the number of carbon atoms ranges from 1 to 10; a saturated or unsaturated, carbocyclic or heterocyclic ring; SiR2; or SiH2, and wherein R and R1 in Formula A are also combinable to form a cyclic group;
c. providing a nitrogen-containing source wherein the at least one organoaminosilane precursors and the nitrogen-containing source react to deposit the film comprising both silicon and nitrogen onto the at least one surface wherein the organoaminosilane is one selected from the group consisting of 1-silyl-7-azaindole, N-silyl-2,5-dimethylpyrrole, N-(4-methoxyphenyl)disilazane, N-(3-methoxyphenyl)disilazane, N-(2-methoxyphenyl)disilazane, N-(4-chlorophenyl)disilazane, N-(2-chlorophenyl)disilazane, N-(2-ethylphenyl)disilazane, N-(2,6-diethylphenyl)disilazane, N-(2-propylphenyl)disilazane, N-(4-t-butylphenyl)disilazane, N-(4-iso-propylphenyl)disilazane, N-(2-iso-propylphenyl)disilazane, N-(3-ethylphenyl)disilazane, N-(4-sec-butylphenyl)disilazane, N-(4-vinylphenyl)disilazane, N-(3-methylphenyl)disilazane, N-(4-methylphenyl)disilazane, N-(2,4,6-trimethylphenyl)disilazane, N-(2,6-di-isopropylphenyl)disilazane, 1-N-(2-pyridyl)disilazane, N,N-disilyl-2-aminopyrimidine, N-(4-methyl-2-pyridyl)disilazane, N-(6-methyl-2-pyridyl)disilazane, N-(3-methyl-2-pyridyl)disilazane, N-(5-methyl-2-pyridyl)disilazane, and N-[2-(4-methylpyrimidino)amino]disilazane, N-(2-dimethylamino-1-methylethyl)disilazane, N-(2-dimethylaminoethyl)disilazane, N-(1-cyclohexylethyl)disilazane, N,N-disilylcumylamine, N-[3,3-dimethylbutyl-2]disilazane, N,N-disilyl-2-picolylamine, N,N-disilyl-2-(2-pyridyl)ethylamine, and N,N-disilyl-1-(4-methylphenyl)ethylamine, N-propyl-isopropylaminosilane, N-methylcyclohexylaminosilane, N-ethylcyclohexylaminosilane, allylphenylaminosilane, N-isopropylcyclohexylaminosilane, allylcyclopentylaminosilane, phenylcyclohexylaminosilane, and 2-(N-silylmethylamino)pyridine.