Organoaminosilanes and methods for making same

Patent metadata

Field	Value
Publication number	US-9758534-B2
Application number	US-201514956748-A
Country	US
Kind code	B2
Filing date	Dec 2, 2015
Priority date	Feb 28, 2014
Publication date	Sep 12, 2017
Grant date	Sep 12, 2017

Abstract

Organoaminosilanes, such as without limitation di-iso-propylaminosilane (DIPAS), are precursors for the deposition of silicon containing films such as silicon-oxide and silicon-nitride films. Described herein are methods to make organoaminosilane compounds, or other compounds such as organoaminodisilanes and organoaminocarbosilanes, via the catalytic hydrosilylation of an imine by a silicon source comprising a hydridosilane.

First claim

The invention claimed is:

1. A method for preparing a compound selected from a group consisting of organoaminosilane, an organoaminodisilane, and an organoaminocarbosilane, the method comprising the steps of:
reacting at least one imine having a formula R—N═CR′R″ wherein R, R′ and R″ are each independently selected from hydrogen, a C 1-10 linear alkyl group, a C 3-10 branched alkyl, a C 3-10 cyclic alkyl group, a C 2-10 alkenyl group, a C 4-10 aromatic group, a C 4-10 heterocyclic group, a C 1-10 linear organoamino group, a C 2-10 branched organoamino group, a silyl group, a C 1-10 linear carbosilyl group, and a C 2-10 branched carbosilyl group, wherein at least one of R′ and R″ or R and R′, or none of R′ and R″ or R and R′ are be linked to form a substituted or unsubstituted cyclic ring and a silicon source selected from the group consisting of silane, disilane, methylsilane, ethylsilane, diethylsilane, phenylsilane, 1,4-disilabutane, 1,3-disilapropane, 2-methyl-1,3-disilapropane, 1-silacyclopentane, 1-methyl-1-silacyclopentane, 1-silacyclobutane, and 1,3-disilacyclobutane, in the presence of a catalyst, wherein the catalyst is not a calcium hydride complex under reaction conditions sufficient for the imine and silicon source to react and provide the compound.

2. The method of claim 1 wherein the compound is the organoaminosilane and is selected from the group consisting of: N,N-di-iso-propylaminosilane, N-sec-butyl-N-iso-propylaminosilane, N,N-di-sec-butyl-aminosilane, N-methyl-N-cyclopentylaminosilane, N-cyclopentyl-N-n-propylaminosilane, N-cyclopentyl-N-iso-propylaminosilane, N-cyclohexyl-N-methylaminosilane, N-ethyl-N-cyclohexylaminosilane, and N-cyclohexyl-N-iso-propylaminosilane.

3. The method of claim 1 wherein the compound is the organoaminodisilane and is selected from the group consisting of: N,N-di-iso-propylaminodisilane, N-sec-butyl-N-iso-propylaminodisilane, N,N-di-sec-butyl-aminodisilane, N-ethyl-N-cyclopentylaminodisilane, N-cyclopentyl-N-n-propylaminodisilane, N-cyclopentyl-N-iso-propylaminodisilane, N-sec-butyl-N-cyclopentylaminodisilane, N-cyclohexyl-N-methylaminodisilane, N-ethyl-N-cyclohexylaminodisilane, and N-cyclohexyl-N-iso-propylaminodisilane.

4. The method of claim 1 wherein the compound is the organoaminocarbosilane and is selected from the group consisting of: 1-(N,N-di-iso-propylamino)-1,4-disilabutane, 1-(N,N-di-iso-propylamino)-1,3-disilapropane, 1-(N,N-di-iso-propylamino)-2-methyl-1,3-disilapropane, 1-(N,N-di-iso-propylamino)-1-silacyclopentane, 1-(N,N-di-iso-propylamino)-1,3-disilacyclobutane, N,N-di-iso-propylamino-methylsilane, N-n-propyl-N-iso-propylamino-methylsilane, N-sec-butyl-N-iso-propylamino-methylsilane, and N-cyclohexyl-N-iso-propylaminomethylsilane.

5. The method of claim 1 wherein the catalyst comprises a halide-free catalyst and wherein the compound contains less than 5 ppm (by weight) halide.

6. A method for preparing a compound selected from the group consisting of an organoaminosilane, an organoaminodisilane, and an organoaminocarbosilane, in the presence of a catalyst comprising an alkaline earth metal complex, the method comprising the steps of: reacting at least one imine having a formula R—N═CR′R″ wherein R, R′ and R″ are each independently selected from the group consisting of hydrogen, a C 1-10 linear alkyl group, a C 3-10 branched alkyl, a C 3-10 cyclic alkyl group, a C 2-10 alkenyl group, a C 4-10 aromatic group, a C 4-10 heterocyclic group, a C 1-10 linear organoamino group, a C 2-10 branched organoamino group, a silyl group, a C 1-10 linear carbosilyl group, and a C 2-10 branched carbosilyl group, wherein at least one of R′ and R″ or R and R′, or none of R′ and R″ or R and R′ are be linked to form a substituted or unsubstituted cyclic ring and a silicon source comprising at least one hydridosilane wherein the hydridosilane has a formula R 1 R 2 R 3 SiH wherein R 1 and R 2 are each independently selected from the group consisting of, a C 1-10 linear alkyl group, a C 3-10 branched alkyl group, a C 4-10 cyclic alkyl group, a C 2-10 alkenyl group, a C 4-10 aromatic group, a C 4-10 heterocyclic group, a C 1-10 linear organoamino group, a C 2-10 branched organoamino group, a silyl group, a C 1-10 linear carbosilyl group, and a C 2-10 branched carbosilyl group, R 3 is hydrogen and wherein at least one of R 1 and R 2 , R 1 and R 3 , R 2 and R 3 or none of R 1 and R 2 , R 1 and R 3 , or R 2 and R 3 are linked to form a substituted or unsubstituted cyclic ring.

7. A method of preparing an organoamine having a formula HN(R)(CHR′R″) wherein R, R′ and R″ are independently selected from the group consisting of hydrogen, a C 1-10 linear alkyl group, a C 3-10 branched alkyl group, a C 3-10 cyclic alkyl group, a C 2-10 alkenyl group, a C 4-10 aromatic group, a C 4-10 heterocyclic group, a C 1-10 linear organoamino group, a C 2-10 branched organoamino group, a C 1-10 linear carbosilyl group, and a C 2-10 branched carbosilyl groups wherein at least one of R′ and R″ or R and R′ or none of R′ and R″ or R and R′ are linked to form a substituted or an unsubstituted cyclic ring, the method comprising the steps of:
reacting an imine having a formula R—N═CR′R″ wherein R, R′ and R″ are each independently selected from the group consisting of, hydrogen, a C 1-10 linear alkyl group, a C 3-10 branched alkyl group, a C 3-10 cyclic alkyl group, a C 2-10 alkenyl group, a C 4-10 aromatic group, a C 4-10 heterocyclic group, a C 1-10 linear organoamino group, a C 2-10 branched organoamino groups, a silyl group, a C 1-10 linear carbosilyl group, and a C 2-10 branched carbosilyl group wherein at least one of R′ and R″ or R and R′ or none of R′ and R″ or R and R′ are linked to form a substituted or unsubstituted cyclic ring and a silicon source comprising a hydridosilane in the presence of an alkaline earth metal catalyst under conditions sufficient for the imine and silicon source to react and provide a compound selected from an organoaminosilane, an organoaminodisilane, and an organoaminocarbosilane;
reacting the compound with a proton source under conditions sufficient to provide the organoamine.

8. The method described in claim 7 wherein the proton source is selected from the group consisting of water, alcohol, and Brønsted acid.

Assignees

• Air Prod & Chem
• Versum Mat Us Llc

Inventors

• Xiao Manchao
• Macdonald Matthew R
• Ho Richard
• Lei Xinjian

Classifications

• C07F7/12

  Organo silicon halides · CPC title

• C07F7/10 Primary

  containing nitrogen {having a Si-N linkage} · CPC title

• C07F7/0801

  General processes · CPC title

• C07F7/025 Primary

  without C-silicon linkages · CPC title