Compositions and methods for the deposition of silicon oxide films
Described herein are compositions and methods for forming silicon oxide films. In one aspect, the film is deposited from at least one silicon precursor compound, wherein the at least one silicon precursor compound is selected from the following Formulae A and B: as defined herein.
1. A method of depositing a film comprising silicon and oxygen onto a substrate, the method comprising the 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
R 1 is independently selected from the group consisting of a linear C 1 to C 10 alkyl group, a branched C 3 to C 10 alkyl group, a C 3 to C 10 cyclic alkyl group, a C 3 to C 10 heterocyclic group, a C 3 to C 10 alkenyl group, a C 3 to C 10 alkynyl group, and a C 4 to C 10 aryl group;
R 2 is selected from the group consisting of hydrogen, a C 1 to C 10 linear alkyl group, a branched C 3 to C 10 alkyl group, a C 3 to C 10 cyclic alkyl group, a C 3 to C 10 heterocyclic group, a C 3 to C 10 alkenyl group, a C 3 to C 10 alkynyl group, and a C 4 to C 10 aryl group, wherein R 1 and R 2 in Formula A or B are either linked to form a cyclic ring structure or are not linked to form a cyclic ring structure;
R 3-8 are each independently selected from the group consisting of hydrogen, a linear C 1 to C 10 alkyl group, a branched C 3 to C 10 alkyl group, a C 3 to C 10 cyclic alkyl group, a C 2 to C 10 alkenyl group, a C 2 to C 10 alkynyl group, and a C 4 to C 10 aryl group;
X is selected from the group consisting of hydrogen, a linear C 1 to C 10 alkyl group, a branched C 3 to C 10 alkyl group, a C 3 to C 10 cyclic alkyl group, a C 2 to C 10 alkenyl group, a C 2 to C 10 alkynyl group, and a C 4 to C 10 aryl group, wherein R 1 and R 9 are either linked to form a cyclic ring or are not linked to form a cyclic ring, and wherein both of R 3 and R 4 are not hydrogen;
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 the film is deposited, and
wherein the method is conducted at one or more temperatures ranging from about 600° C. to about 800° C.
2. The method of claim 1 , wherein the at least one silicon precursor compound is at least one selected from the group consisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1-diethylamino-1,1,3,3,3-pentamethyldisiloxane, 1-di-iso-propylamino-1,1,3,3,3-pentamethyldisiloxane, 1-di-sec-butylamino-1,1,3,3,3-pentamethyldisiloxane, 1-pyrrolyl-1,1,3,3,3-pentamethyldisiloxane, 1-pyrrolidino-1,1,3,3,3-pentamethyldisiloxane, 1-piperidino-1,1,3,3,3-pentamethyldisiloxane, 1-(2,6-dimethylpiperidino)-3,3,3-pentamethyldisiloxane, 1-dimethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-diethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-di-iso-propylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-sec-butylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-cyclohexylmethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-cyclohexylethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-piperidino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-(2,6-dimethylpiperidino)-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-pyrrolyl-1,1,3,3,5,5,5-heptamethyltrisiloxane, and 1-pyrrolidino-1,1,3,3,5,5,5-heptamethyltrisiloxane.
3. The method of claim 1 , wherein the oxygen-containing source is selected from the group consisting of 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, a carbon monoxide plasma, and combinations thereof.
4. The method of claim 1 wherein the oxygen-containing source comprises plasma.
5. The method of claim 4 wherein the plasma is generated in situ.
6. The method of claim 4 wherein the plasma is generated remotely.
7. The method of claim 4 wherein the film has a density of about 2.1 g/cc or greater.
8. The method of claim 1 wherein the film further comprises carbon.
9. The method of claim 8 wherein the film has a density of about 1.8 g/cc or greater.
10. The method of claim 8 wherein a carbon content of the film is 0.5 atomic weight percent (at. %) as measured by x-ray photospectroscopy or greater.
11. The method of claim 1 wherein the at least one silicon precursor compound is selected from the group consisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1-diethylamino-1,1,3,3,3-pentamethyldisiloxane, and 1-pyrrolidino-1,1,3,3,3-pentamethyldisiloxane.
12. The method of claim 11 wherein the at least one silicon precursor compound is 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane.
13. The method of claim 1 wherein the at least one silicon precursor compound is substantially free of halide ions.
14. The method of claim 13 wherein the at least one silicon precursor compound comprises less than 5 ppm of halide ions.
15. The method of claim 14 wherein the at least one silicon precursor compound comprises less than 3 ppm of halide ions.
16. The method of claim 15 wherein the at least one silicon precursor compound comprises less than 1 ppm of halide ions.
17. The method of claim 16 wherein the at least one silicon precursor compound is free of halide ions.
18. A method of depositing 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
R 1 is independently selected from the group consisting of a linear C 1 to C 10 alkyl group, a branched C 3 to C 10 alkyl group, a C 3 to C 10 cyclic alkyl group, a C 3 to C 10 heterocyclic group, a C 3 to C 10 alkenyl group, a C 3 to C 10 alkynyl group, and a C 4 to C 10 aryl group;
R 2 is selected from the group consisting of hydrogen, a C 1 to C 10 linear alkyl group, a branched C 3 to C 10 alkyl group, a C 3 to C 10 cyclic alkyl group, a C 3 to C 10 heterocyclic group, a C 3 to C 10 alkenyl group, a C 3 to C 10 alkynyl group, and a C 4 to C 10 aryl group, wherein R 1 and R 2 in Formula A or B are either linked to form a cyclic ring structure or are not linked to form a cyclic ring structure; and
R 3-8 and X are methyl;
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 the film is deposited, and
wherein the method is conducted at one or more temperatures ranging from about 600° C. to about 800° C.
19. The method of claim 18 , wherein the at least one silicon precursor compound is at least one selected from the group consisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1-diethylamino-1,1,3,3,3-pentamethyldisiloxane, 1-di-iso-propylamino-1,1,3,3,3-pentamethyldisiloxane, 1-di-sec-butylamino-1,1,3,3,3-pentamethyldisiloxane, 1-pyrrolyl-1,1,3,3,3-pentamethyldisiloxane, 1-pyrrolidino-1,1,3,3,3-pentamethyldisiloxane, 1-piperidino-1,1,3,3,3-pentamethyldisiloxane, 1-(2,6-dimethylpiperidino)-3,3,3-pentamethyldisiloxane, 1-dimethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-diethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-di-iso-propylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-sec-butylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-cyclohexylmethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-cyclohexylethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-piperidino-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-(2,6-dimethylpiperidino)-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-pyrrolyl-1,1,3,3,5,5,5-heptamethyltrisiloxane, and 1-pyrrolidino-1,1,3,3,5,5,5-heptamethyltrisiloxane.
20. The method of claim 18 , wherein the at least one silicon precursor compound is at least one selected from the group consisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane, 1-diethylamino-1,1,3,3,3-pentamethyldisiloxane, and 1-pyrrolidino-1,1,3,3,3-pentamethyldisiloxane.
21. The method of claim 20 wherein the at least one silicon precursor compound is 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane.
22. The method of claim 18 wherein the at least one silicon precursor compound is substantially free of halide ions.
23. The method of claim 22 wherein the at least one silicon precursor compound comprises less than 5 ppm of halide ions.
24. The method of claim 23 wherein the at least one silicon precursor compound comprises less than 3 ppm of halide ions.
25. The method of claim 24 wherein the at least one silicon precursor compound comprises less than 1 ppm of halide ions.
26. The method of claim 25 wherein the at least one silicon precursor compound is free of halide ions.