Composition and method for low temperature deposition of silicon-containing films such as films including silicon nitride, silicon dioxide and/or silicon-oxynitride
View Patent ↗Silicon precursors for forming silicon-containing films in the manufacture of semiconductor devices, such as low dielectric constant (k) thin films, high k gate silicates, low temperature silicon epitaxial films, and films containing silicon nitride (Si 3 N 4 ), siliconoxynitride (SiO x N y ) and/or silicon dioxide (SiO 2 ). The precursors of the invention are amenable to use in low temperature (e.g., <500° C.) chemical vapor deposition processes, for fabrication of ULSI devices and device structures.
1. A silicon compound of the formula
[SiX n (NR 1 R 2 ) 3-n ] 2 (1)
wherein:
R 1 and R 2 may be the same as or different from one another and each is independently selected from the group consisting of H, C 1 -C 5 , alkyl, and C 3 -C 6 cycloalkyl;
X is selected from the group consisting of halogen, hydrogen and deuterium; and
0<n≦2, with the proviso that when R 1 =R 2 =ethyl or methyl, X≠Cl, when R 1 =R 2 =ethyl and n=1 or 2, X≠H, when R 1 =R 2 =isopropyl and n=2, X≠Cl or H, and when R 1 =R 2 =isopropyl and n=1, X≠H.
2. A silicon compound having the formula (Bu t NH) 2 ClSi—SiCl (HNBu t ) 2 .
3. A silicon compound of the formula:
wherein:
R 1 and R 2 may be the same as or different from one another and each is independently selected from the group consisting of H, C 1 -C 5 alkyl, and C 3 -C 6 cycloalkyl, with the proviso that R 1 and R 2 cannot simultaneously be ethyl or methyl.
4. A method of forming a silicon-containing film on a substrate, comprising contacting a substrate under chemical vapor deposition conditions including temperature below 600° C. with a vapor of a silicon compound as claimed in claim 1 .
5. The method of claim 4 , X is chlorine, R 1 is H and R 2 is tertiary butyl.
6. The method of claim 4 , wherein the silicon-containing film comprises a material selected from the group consisting of silicon oxide, silicon oxynitride and silicon and said temperature is <500° C.
7. The method of claim 6 , wherein the silicon compound has the formula (Bu t NH) 2 ClSi—SiCl(HNBu t ) 2 .
8. The method of claim 6 , wherein the silicon compound comprises a compound of the formula:
with the proviso that R 1 and R 2 cannot simultaneously be ethyl or methyl.
9. The method of claim 4 , wherein each R 1 and R 2 are the same as one another.
10. The method of claim 4 , wherein each R 1 and R 2 are different from one another.
11. The method of claim 4 , wherein each R 1 and R 2 is independently selected from C 1 -C 5 alkyl.
12. The method of claim 4 , wherein said silicon-containing film comprises a film selected from the group consisting of films, comprising silicon, silicon nitride (Si 3 N 4 ), siliconoxynitride (SiO x N y ), silicon dioxide (SiO 2 ), low dielectric constant (k) thin silicon-containing films, high k gate silicate films and low temperature silicon epitaxial films.
13. The method of claim 4 , wherein said chemical vapor deposition conditions comprise temperature of from about 400 to about 625° C., pressure of from about 10 to about 100 torr, and the presence of ammonia.
14. The method of claim 4 , wherein said chemical vapor deposition conditions comprise temperature of from about 525 to about 625° C., pressure of from about 0.1 to about 10 torr.
15. The method of claim 4 , comprising depositing oxynitride deposition of silicon.
16. The method of claim 4 , comprising depositing oxynitride deposition of silicate.
17. The method of claim 4 , wherein the silicon-containing film comprises silicon nitride.
18. The method of claim 4 , wherein said temperature is <500° C.
19. A method of making a compound of the formula:
[SiX n (NR 1 R 2 ) 3-n ] 2 (1)
wherein:
R 1 and R 2 may be the same as or different from one another and each is independently selected from the group consisting of H, C 1 -C 5 alkyl, and C 3 -C 6 cycloalkyl;
X is selected from the group consisting of halogen, hydrogen and deuterium; and
0<n≦2, with the proviso that when R 1 =R 2 =ethyl or methyl, X≠Cl, when R 1 =R 2 =ethyl and n=1 or 2, X≠H, when R 1 =R 2 =isopropyl and n=2, X≠Cl or H, and when R 1 =R 2 =isopropyl and n=1, X≠H,
said method comprising reacting a disilane compound of the formula X 3 Si—SiX 3 with an amine (R 1 R 2 NH) or lithium amide ((R 1 R 2 N)Li compound, wherein X, R 1 and R 2 are as set out above, according to a reaction selected from the group consisting of the following reactions:
wherein each of the R substituents may be the same as or different from the other and each is independently selected from the group consisting of H, C 1 -C 4 alkyl, and C 3 - C 6 cycloalkyl.
20. The method of claim 4 , wherein the silicon compound comprises a precursor that is reacted with a co-reactant in a reaction scheme selected from the group consisting of those of reaction scheme (C) below:
wherein A is selected from the group consisting of R 3 Si—N 3 , R—N═NR′ and R—N═N + =NR′, wherein each R is independently selected from the group consisting of C 1 -C 3 alkyl and R′ is R or H.
21. A silicon compound of the formula
[SiX n (NR 1 R 2 ) 3-n ] 2 (1)
wherein:
R 1 and R 2 may be the same as or different from one another and each is independently selected from the group consisting of H, C 3 alkyl, C 5 alkyl, and C 3 -C 6 cycloalkyl;
X is selected from the group consisting of halogen, hydrogen and deuterium; and
0<n≦2.
22. A composition for delivery of a silicon compound to a substrate, said composition comprising
a) a silicon compound of the formula
[SiX n (NR 1 R 2 ) 3-n ] 2 (1)
wherein:
R 1 and R 2 may be the same as or different from one another and each is independently selected from the group consisting of H, C 1 -C 5 alkyl, and C 3 -C 6 cycloalkyl;
X is selected from the group consisting of halogen, hydrogen and deuterium; and
0<n≦2, with the proviso that when R 1 =R 2 =ethyl or methyl, X≠Cl, when R 1 =R 2 =ethyl and n=1 or 2, X≠H, when R 1 =R 2 =isopropyl and n=2, X≠Cl or H, and when R 1 =R 2 =isopropyl and n=1, X≠H; and
b) one or more hydrocarbon solvents.