# US 2017/0256399 A9 · High Temperature Atomic Layer Deposition Of Silicon Oxide Thin Films

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 2017/0256399 A9
- Document ID: US20170256399A9
- Status: Published application
- Kind: A9
- Application number: 15/248,214
- Filed: 2016-08-26
- Published: 2017-09-07
- Earliest claimed: 2012-04-12
- Assignees: Air Products and Chemicals, Inc.
- Applicants: Air Products and Chemicals, Inc.
- Inventors: Haripin Chandra; Meiliang Wang; Manchao Xiao; Xinjian Lei; Ronald Martin Pearlstein; Mark Leonard O'Neill; Bing Han
- Web page: https://patentgrep.com/patent/US20170256399A9

## CPC

- H10P 14/69215: {the material being a silicon oxide, e.g. SiO2}
- C07F 7/10: containing nitrogen {having a Si-N linkage}
- C23C 16/402: {Silicon dioxide}
- C23C 16/45527: {characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations}
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- H10P 14/6336: {in the presence of a plasma [PECVD]}
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- 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

Atomic layer deposition (ALD) process formation of silicon oxide with temperature >500° C. is disclosed. Silicon precursors used have a formula of: R1R2mSi(NR3R4)nXp I. wherein R1, R2, and R3 are each independently selected from hydrogen, a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group; R4 is selected from, a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group. a C3 to C10 alkylsilyl group; wherein R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure; X is a halide selected from the group consisting of Cl, Br and I; m is 0 to 3; n is 0, 1 or 2; and p is 0, 1 or 2 and m+n+p=3; and R1R2mSi(OR3)n(OR4)qXp II. wherein R1 and R2 areeach independently selected from hydrogen, a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group; R3 and R4 are each independently selected from a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group; wherein R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure; X is a halide atom selected from the group consisting of Cl, Br and I; m is 0 to 3; n is 0 to 2; q is 0 to 2; p is 0 to 2; and m+n+q+p=3.

## Claims

### Claim 1

A process to deposit a silicon oxide film onto a substrated comprises steps of:
a. providing a substrate in a reactor;
b. introducing into the reactor at least one silicon precursor;
c. purging reactor with purge gas;
d. introducing an oxygen source into the reactor; and
e. purging reactor with purge gas; and
wherein steps b through g are repeated until a desired thickness of silicon oxide is deposited,
wherein the process in conducted at one or more temperatures ranging from 500 to 800° C. and one or more pressures ranging from 50 miliTorr (mT) to 760 Torr, wherein the at least one silicon precursor having a formula selected from the group consisting of:
R1R2mSi(NR3R4)nXp I.
wherein R1, R2, and R3 are each independently selected from hydrogen, a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group; R4 is selected from, a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group, a C3 to C10 alkylsilyl group; wherein R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure; X is a halide selected from the group consisting of Cl, Br and I; m is 0 to 3; n is 0, 1 or 2; and p is 0, 1 or 2 and m+n+p=3; and
R1R2mSi(OR3)n(OR4)qXp II.
wherein R1 and R2 are each independently selected from hydrogen, a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group; R3 and R4 are each independently selected from a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group; wherein R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure; X is a halide atom selected from the group consisting of Cl, Br and I; m is 0 to 3; n is 0 to 2; q is 0 to 2; p is 0 to 2; and m+n+q+p=3.

### Claim 2 (depends on 1)

The process of claim 1, wherein the at least one silicon precursor is selected from the group consisting of ethylmethylaminodimethylsilane, t-butylaminodimethylsilane, iso-propylaminodimethylsilane, di-isopropylaminodimethylsilane, pyrrolidinodimethylsilane, diethylaminodiethylsilane, dimethylaminodiethylsilane, ethylmethylaminodiethylsilane, t-butylaminodiethylsilane, iso-propylaminodiethylsilane, di-isopropylaminodiethylsilane, pyrrolidonodiethylsilane, dipyrrolidinodimethylsilane, dipyrrolidinodiethylsilane, dipyrrolidino methylvinylsilane, 2,6-dimethylpiperidinomethylsilane, 2,6-dimethylpiperidinodimethylsilane, tris(dimethylamino)chlorosilane, and mixtures thereof.

### Claim 3 (depends on 1)

The process of claim 1, wherein the at least one silicon precursor is selected from the group consisting of methoxytrimethylsilane, ethoxytrimethylsilane, iso-propoxytrimethylsilane, tert-butoxytrimethylsilane, tert-pentoxytrimethylsilane, phenoxytrimethylsilane, acetoxytrimethylsilane, methoxytriethylsilane, ethoxytriethylsilane, iso-propoxytriethylsilane, tert-butoxytriethylsilane, tert-pentoxytriethylsilane, phenoxytriethylsilane, acetoxytriethylsilane, methoxydimethylsilane, ethoxydimethylsilane, iso-propoxydimethylsilane, tert-butoxydimethylsilane, tert-pentoxydimethylsilane, phenoxydimethylsilane, acetoxydimethylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, iso-propoxydimethylphenylsilane, tert-butoxydimethylphenylsilane, tert-pentoxydimethylphenylsilane, phenoxydimethylphenylsilane, acetoxydimethylphenylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, di-isopropoxydimethylsilane, di-t-butoxydimethylsilane, diacytoxydimethylsilane, dimethoxydiethylsilane, diethoxydiethyisilane, di-isopropoxydiethylsilane, di-t-butoxydiethylsilane, diacytoxydiethylsilane, dimethoxydi-isopropylsilane, diethoxydi-isopropylsilane, di-isopropoxydi-isopropylsilane, di-t-butoxydi-isopropylsilane, diacytoxydi-isopropylsilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, di-isopropoxymethylvinylsilane, di-t-butoxymethylvinylsilane, diacytoxymethylvinylsilane, 1,1,3,4-tetramethyl-1-sila-2,5-dioxacyclopentane, 1,1,3,3,4,4-hexamethyl-1-sila-2,5-dioxacyclopentane, and mixtures thereof.

### Claim 4 (depends on 1)

The process of claim 1, wherein the at least one silicon precursor is selected from the group consisting of 1,1,1,3,3,3-hexamethyldisilazane, 1,1,1,3,3,3-hexaethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,1,3,3-tetraethyldisilazane, 1,1,1,2,3,3,3-heptamethyldisilazane, 1,1,1,3,3,3-hexaethyl-2-methyldisilazane, 1,1,2,3,3-pentamethyldisilazane, 1,1,3,3-tetraethyl-2-methyldisilazane, 1,1,1,3,3,3-hexamethyl-2-ethyldisilazane, 1,1,1,2,3,3,3-heptaethyldisilazane, 1,1,3,3-tetramethyl-2-ethyldisilazane, 1,1,2,3,3-pentaethyldisilazane, 1,1,1,3,3,3-hexamethyl-2-isopropyldisilazane, 1,1,1,3,3,3-hexaethyl-2-isopropyldisilazane, 1,1,3,3-tetramethyl-2-isopropyldisilazane, 1,1,3,3-tetraethyl-2-isopropyldisilazane, and mixtures thereof.

### Claim 5 (depends on 1)

The process of claim 1, wherein the purge gas is selected from the group consisting of nitrogen, helium and argon.

### Claim 6 (depends on 1)

The process of claim 1, wherein the oxygen source is selected from the group consisting of oxygen, peroxide, oxygen plasma, water vapor, water vapor plasma, hydrogen peroxide, and ozone source.

### Claim 7 (depends on 1)

The process of claim 1, further comprises steps f and g after step g:
f Introduce water vapor or hydroxyl source into the reactor;
g. Purging reactor with purge gas.

### Claim 8

A process to deposit silicon oxide comprises steps of:
a) providing a substrate in a reactor;
b) introducing into the reactor at least one silicon precursor;
c) purging reactor with purge gas;
d) introducing an oxygen source into the reactor;
e) purging reactor with purge gas; and
f) repeating steps b through e until desired thickness is deposited;
wherein process temperature ranges from 500 to 800° C. and pressure ranges from 50 miliTorr (mT) to 760 Torr and the silicon precursor comprises at least one anchoring functionality and a passivating functionality comprising a Si-Me group,
wherein the process in conducted at one or more temperatures ranging from 500 to 800° C. and one or more pressures ranging from 50 miliTorr (mT) to 760 Torr, wherein the at least one silicon precursor having a formula selected from the group consisting of:
R1R2mSi(NR3R4)nXp I.
wherein R1, R2, and R3 are each independently selected from hydrogen, a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group; R4 is selected from, a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group, a C3 to C10 alkylsilyl group; wherein R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure; X is a halide selected from the group consisting of Cl, Br and I; m is 0 to 3; n is 0 to 2; and p is 0, 1, or 2 and m+n+p=3; and
R1R2mSi(OR3)n(OR4)qXp II.
wherein R1 and R2 are each independently selected from hydrogen, a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group; R3 and R4 are each independently selected from a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group; wherein R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure; X is a halide atom selected from the group consisting of Cl, Br and I; m is 0 to 3; n is 0 to 2; q is 0 to 2 and p is 0 to 2 and m+n+q+p=3.

### Claim 9 (depends on 8)

The process of claim 8, wherein the oxygen source is selected from the group consisting of oxygen, peroxide, oxygen plasma, nitrous oxide, water vapor, water vapor plasma, hydrogen peroxide , and ozone source.

### Claim 10 (depends on 8)

The process of claim 8, wherein the process temperature ranges from 500° C. to 750° C.

### Claim 11 (depends on 8)

The process of claim 8, wherein the process temperature ranges from 600° C. to 750° C.

### Claim 12 (depends on 8)

The process of claim 8, wherein the pressure ranges from 50 miliTorr (mT) to 100 Torr.

### Claim 13 (depends on 8)

The process of claim 8, wherein the anchoring functionality is an amino group.

### Claim 14 (depends on 8)

The process of claim 8, wherein the anchoring functionality is a halide selected from group consisting of Cl, Br, and I.

### Claim 15 (depends on 8)

The process of claim 8, wherein the anchoring functionality is an alkoxy group.

### Claim 16 (depends on 8)

The process of claim 8, wherein the at least one silicon precursor is selected from the group consisting of 1,1,1,3,3,3-hexamethyldisilazane, methoxytrimethylsilane, ethoxytrimethylsilane, and chlorotrimethylsilane.