High temperature atomic layer deposition of silicon-containing films
View Patent ↗A method and composition for depositing a silicon oxide film in an atomic layer deposition process at one or more temperatures of 650° C. or greater is provided. In one aspect, there is provided a method to deposit a silicon oxide film or material comprising the steps of: providing a substrate in a reactor; introducing into the reactor at least one halidosiloxane precursor selected from the group of compounds having formulae I and II described herein; purging the reactor with a purge gas; introducing an oxygen source into the reactor; and purging reactor with purge gas; and wherein the steps are repeated until a desired thickness of silicon oxide is deposited and the process is conducted at one or more temperatures ranging from about 650 to 1000° C.
1. A method to deposit a silicon oxide film onto at least a surface of a substrate, the method comprising the steps of:
a. providing the substrate in a reactor;
b. introducing into the reactor at least one halidosiloxane precursor selected from the group of compounds having the following formulae I and II:
R 3-n X n Si—O—SiX n R 3-n I
R 3-n X n Si—O—SiX m R 1 p R 2-m-p —O—SiX n R 3-n II
wherein X=Cl, Br, or I; R and R 1 are each independently selected from a hydrogen atom, a C 1 to C 3 alkyl group; n=1, 2, or 3; m=0, 1, or 2; and p=0 or 1;
c. purging the reactor with a purge gas;
d. introducing an oxygen source into the reactor; and
e. purging reactor with the purge gas; and
wherein steps b through e are repeated until a desired thickness of the silicon oxide film is deposited; and
wherein the method is conducted at one or more temperatures ranging from about 700 to 800° C.
2. The method of claim 1 , wherein the at least one halidosiloxane precursor is selected from the group consisting of 1,1,1,3,3,3-hexachlorodisiloxane, 1,1,3,3-tetrachlorodisiloxane, 1,1,3,3-tetrachloro-1,3-dimethyldisiloxane, 1,3-dichloro-1,1,3,3-tetramethyldisiloxane, 1,1,1,3,3,5,5,5-octachlorotrisiloxane, 1,1,3,5,5-pentachloro-1,3,5-trimethyltrisiloxane, 1,5-dichloro-1,1,3,3,5,5-hexamethyltrisiloxane, 1,5-pentachloro-1,3,5-trimethyltrisiloxane, and mixtures thereof.
3. The method of claim 1 , wherein the purge gas is selected from the group consisting of nitrogen, helium, argon and combinations thereof.
4. The method of claim 1 , wherein the oxygen source comprises at least one member selected from the group consisting of oxygen, peroxide, oxygen plasma, carbon dioxide plasma, carbon monoxide plasma, a composition comprising hydrogen and oxygen, a composition comprising hydrogen and ozone, a composition comprising carbon dioxide and oxygen, a composition comprising water and oxygen, a composition comprising nitrogen and oxygen, water vapor, water vapor plasma, a composition comprising water and ozone, hydrogen peroxide, ozone source, and combinations thereof.
5. The method of claim 1 , further comprising:
f. introducing a hydroxyl containing source into the reactor; and
g. purging reactor with the purge gas, and wherein steps b through g are repeated until a desired thickness of silicon oxide is deposited.
6. A method to deposit a silicon oxide film comprising the steps of:
a. providing a substrate in a reactor;
b. introducing into the reactor at least one halidosiloxane precursor selected from the group of compounds having the following formulae I and II:
R 3-n X n Si—O—SiX n R 3-n I
R 3-n X n Si—O—SiX m R 1 p R 2-m-p —O—SiX n R 3-n II
wherein X=Cl, Br, or I; R and R 1 are each independently selected from a hydrogen atom, a C 1 to C 3 alkyl group; n=1, 2, or 3; m=0, 1, or 2; and p=0 or 1;
c. purging reactor with a purge gas;
d. introducing an oxygen source into the reactor;
e. purging reactor with the purge gas;
f. introducing a hydroxyl containing source into the reactor;
g. purging reactor with the purge gas; and
wherein steps b through g are repeated until a desired thickness of the silicon oxide film is deposited;
wherein a process temperature ranges from 700 to 800° C. and a pressure ranges from 50 miliTorr (mT) to 760 Torr.
7. The method of claim 6 , wherein the at least one halidosiloxane precursor is selected from the group consisting of 1,1,1,3,3,3-hexachlorodisiloxane, 1,1,3,3-tetrachlorodisiloxane, 1,1,3,3-tetrachloro-1,3-dimethyldisiloxane, 1,3-dichloro-1,1,3,3-tetramethyldisiloxane, 1,1,1,3,3,5,5,5-octachlorotrisiloxane, 1,1,3,5,5-pentachloro-1,3,5-trimethyltrisiloxane, 1,5-dichloro-1,1,3,3,5,5-hexamethyltrisiloxane, 1,5-pentachloro-1,3,5-trimethyltrisiloxane, and mixtures thereof.
8. The method of claim 6 , wherein the purge gas is selected from the group consisting of nitrogen, helium, argon and combinations thereof.
9. The method of claim 6 , wherein the oxygen source comprises at least one member selected from the group consisting of oxygen, peroxide, oxygen plasma, carbon dioxide plasma, carbon monoxide plasma, a composition comprising hydrogen and oxygen, a composition comprising hydrogen and ozone, a composition comprising carbon dioxide and oxygen, a composition comprising water and oxygen, a composition comprising nitrogen and oxygen , water vapor, water vapor plasma, a composition comprising water and ozone, hydrogen peroxide, ozone source, and combinations thereof.
10. A method to deposit a silicon oxide film comprising the steps of:
a. providing a substrate in a reactor;
b. introducing into the reactor at least one halidosiloxane precursor selected from the group of compounds having the following formulae I and II:
R 3-n X n Si—O—SiX n R 3-n I
R 3-n X n Si—O—SiX m R 1 p R 2-m-p —O—SiX n R 3-n II
wherein X=Cl, Br, or I; R and R 1 are each independently selected from a hydrogen atom, a C 1 to C 3 alkyl group; n=1, 2, or 3; m=0, 1, or 2; and p=0 or 1;
c. purging reactor with a purge gas;
d. introducing an oxygen source into the reactor;
e. purging reactor with the purge gas,
wherein steps b through e are repeated until desired thickness is deposited, and
wherein a method temperature ranges from 700 to 800° C. and a pressure ranges from 50 miliTorr (mTorr) to 760 Torr and the halidosiloxane precursor comprises at least one anchoring functionality and a passivating functionality comprising a Si-Me or Si—Cl group.
11. The method of claim 10 , wherein the oxygen source comprises at least one member selected from the group consisting of oxygen, peroxide, oxygen plasma, carbon dioxide plasma, carbon monoxide plasma, a composition comprising hydrogen and oxygen, a composition comprising hydrogen and ozone, a composition comprising carbon dioxide and oxygen, a composition comprising water and oxygen, a composition comprising nitrogen and oxygen, water vapor, water vapor plasma, a composition comprising water and ozone, hydrogen peroxide, ozone source, and combinations thereof.
12. The method of claim 10 , wherein the pressure ranges from 50 miliTorr (mTorr) to 100 Torr.
13. A silicon containing film formed by the method of claim 10 .