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 precursor having the following formula: R 1 n Si(NR 2 R 3 ) m H 4-m-n wherein R 1 is independently selected from a linear C 1 to C 6 alkyl group, a branched C 2 to C 6 alkyl group, a C 3 to C 6 cyclic alkyl group, a C 2 to C 6 alkenyl group, a C 3 to C 6 alkynyl group, and a C 4 to C 10 aryl group; wherein R 2 and R 3 are each independently selected from hydrogen, a C 1 to C 6 linear alkyl group, a branched C 2 to C 6 alkyl group, a C 3 to C 6 cyclic alkyl group, a C 2 to C 6 alkenyl group, a C 3 to C 6 alkynyl group, and a C 4 to C 10 aryl group, wherein R 2 and R 3 are linked or, are not linked, to form a cyclic ring structure; n=1, 2, 3; and m=1, 2.
1 . A method to deposit a film comprising silicon and oxide onto a substrate comprises steps of:
a) providing a substrate in a reactor;
b) introducing into the reactor at least one silicon precursor comprising a compound having the following formula A:
R 1 n Si(NR 2 R 3 ) m H 4-m-n A
wherein R 1 is independently selected from a linear C 1 to C 6 alkyl group, a branched C 3 to C 6 alkyl group, a C 3 to C 6 cyclic alkyl group, a C 2 to C 6 alkenyl group, a C 3 to C 6 alkynyl group, a C 4 to C 10 aryl group; wherein R 2 and R 3 are each independently selected from the group consisting of hydrogen, a C 1 to C 6 linear alkyl group, a branched C 3 to C 6 alkyl group, a C 3 to C 6 cyclic alkyl group, a C 2 to C 6 alkenyl group, a C 3 to C 6 alkynyl group, a C 4 to C 10 aryl group, wherein R 2 and R 3 in Formula A are selected from R 2 and R 3 are linked to form a cyclic ring structure and R 2 and R 3 are not linked to form a cyclic ring structure; n=1, 2, 3; and m=1, 2;
c) purging the reactor with purge gas;
d) introducing an oxygen-containing source into the reactor; and
e) purging the reactor with purge gas; and
wherein steps b through e are repeated until a desired thickness of film is deposited; and
wherein the method is conducted at one or more temperatures ranging from about 25° C. to 300° C.
2 . The method of claim 1 , wherein the compound is selected from the group consisting of dimethylaminotrimethylsilane, dimethylaminotrimethylsilane, di-iso-propylaminotrimethylsilane, piperidinotrimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, di-sec-butylaminotrimethylsilane, iso-propyl-sec-butylaminotrimethylsilane, tert-butylaminotrimethylsilane, iso-propylaminotrimethylsilane, diethylaminodimethylsilane, dimethylaminodimethylsilane, di-iso-propylaminodimethylsilane, piperidinodimethylsilane, 2,6-dimethylpiperidinodimethylsilane, di-sec-butylaminodimethylsilane, iso-propyl-sec-butylaminodimethylsilane, tert-butylaminodimethylsilane, Iso-propylaminodimethylsilane, tert-pentylaminodimethylaminosilane, dimethylaminomethylsilane, di-iso-propylaminomethylsilane, iso-propyl-sec-butylaminomethylsilane, 2,6-dimethylpiperidinomethylsilane, di-sec-butylaminomethylsilane, bis(dimethylamino)methylsilane, bis(diethylamino)methylsilane, bis(di-iso-propylamino)methylsilane, bis(iso-propyl-sec-butylamino)methylsilane, bis(2,6-dimethylpiperidino)methylsilane, bis(iso-propylamino)methylsilane, bis(tert-butylamino)methylsilane, bis(sec-butylamino)methylsilane, bis(tert-pentylamino)methylsilane, bis(cyclohexylamino)methylsilane, bis(iso-propylamino)dimethylsilane, bis(iso-butylamino)dimethylsilane, bis(sec-butylamino)dimethylsilane, bis(tert-butylamino)dimethylsilane, bis(tert-pentylamino)dimethylsilane, bis(cyclohexylamino)dimethylsilane, and combinations.
3 . The method of claim 1 , wherein the oxygen-containing source is selected from the group consisting of an ozone, 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, 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 a density of the film is 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 a density of the film is 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 . A method to deposit a film selected from a silicon oxide film and a carbon doped silicon oxide film onto a substrate, the method comprising steps of:
a. providing the substrate in a reactor;
b. introducing into the reactor at least one silicon precursor comprising a compound having the following formula:
R 1 n Si(NR 2 R 3 ) m H 4-m-n
wherein R 1 is independently selected from a linear C 1 to C 2 alkyl group, R 2 is selected from a C 1 to C 6 linear alkyl group, a branched C 3 to C 6 alkyl group; R 3 is hydrogen; n=1 or 2; and m=2;
c. purging the reactor with a purge gas;
d. introducing an oxygen-containing source into the reactor; and
e. purging reactor with purge gas; and
wherein steps b through e are repeated until a desired thickness of film is deposited; and
wherein the method is conducted at one or more temperatures ranging from about 25° C. to about 300° C.
12 . The method of claim 11 , wherein the at least one silicon precursor is selected from the group consisting of bis(iso-propylamino)methylsilane, bis(iso-butylamino)methylsilane, bis(sec-butylamino)methylsilane, bis(tert-butylamino)methylsilane, bis(tert-pentylamino)methylsilane, bis(cyclohexylamino)methylsilane, bis(iso-propylamino)dimethylsilane, bis(iso-butylamino)dimethylsilane, bis(sec-butylamino)dimethylsilane, bis(tert-butylamino)dimethylsilane, bis(tert-pentylamino)dimethylsilane, and bis(cyclohexylamino)dimethylsilane.
13 . The method of claim 11 , wherein the oxygen-containing source is selected from the group consisting of an ozone, 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, and combinations thereof.
14 . The method of claim 11 wherein the oxygen-containing source comprises plasma.
15 . The method of claim 14 wherein the density of the film is about 2.1 g/cc or greater.
16 . The method of claim 14 , wherein the plasma is generated in situ.
17 . The method of claim 14 , wherein the plasma is generated remotely.
18 . A composition for depositing a film selected from a silicon oxide or a carbon doped silicon oxide film using a vapor deposition process, the composition comprising: a compound having the following formula B:
R 1 n Si(NR 2 H) m H 4-m-n B
wherein R 1 is independently selected from a linear C 1 to C 2 alkyl group, R 2 is independently selected from a C 1 to C 6 linear alkyl group and a branched C 3 to C 6 alkyl group; n=1 or 2; and m=2.
19 . The composition of claim 18 , wherein the compound is selected from the group consisting of bis(iso-propylamino)methylsilane, bis(iso-butylamino)methylsilane, bis(sec-butylamino)methylsilane, bis(tert-butylamino)methylsilane, bis(tert-pentylamino)methylsilane, bis(cyclohexylamino)methylsilane, bis(iso-propylamino)dimethylsilane, bis(iso-butylamino)dimethylsilane, bis(sec-butylamino)dimethylsilane, bis(tert-butylamino)dimethylsilane, bis(tert-pentylamino)dimethylsilane, bis(cyclohexylamino)dimethylsilane, and combinations thereof.
20 . A silicon precursor for depositing a film comprising silicon and oxide, the silicon precursor comprising at least one selected from the group consisting of bis(sec-butylamino)methylsilane, bis(tert-butylamino)methylsilane, and bis(cyclohexylamino)methylsilane.