Composition and method for low temperature deposition of silicon-containing films such as films including silicon, 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 method of forming a silicon-containing film on a substrate, comprising contacting the substrate under vapor deposition conditions with a precursor of the formula [SiX n (NR 1 R 2 ) 3-n ] 2 selected from the group consisting of:
(i) precursors of said formula wherein:
R 1 =R 2 =C 3 -C 6 cycloalkyl;
X is selected from the group consisting of halogen, hydrogen and deuterium; and
0<n<2;
(ii) precursors of said formula wherein:
at least one of R 1 and R 2 is H, and the other is 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;
(iii) precursors of said formula wherein:
one of R 1 and R 2 is H, and the other is C 1 -C 5 alkyl;
X is selected from the group consisting of halogen, hydrogen and deuterium; and
0<n<2; and
(iv) precursors of said formula wherein:
one of R 1 and R 2 is H, and the other is ethyl or butyl;
X is chlorine; and
n is 0 or 1.
2. The method of claim 1 , wherein the precursor is selected from (i) precursors of said formula wherein:
R 1 =R 2 =C 3 -C 6 cycloalkyl;
X is selected from the group consisting of halogen, hydrogen and deuterium; and
0<n<2.
3. The method of claim 1 , wherein the precursor is selected from (ii) precursors of said formula wherein:
at least one of R 1 and R 2 is H, and the other is 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.
4. The method of claim 1 , wherein the precursor is selected from (iii) precursors of said formula wherein:
one of R 1 and R 2 is H, and the other is C 1 -C 5 alkyl;
X is selected from the group consisting of halogen, hydrogen and deuterium; and
0<n<2.
5. The method of claim 1 , wherein the precursor is selected from (iv) precursors of said formula wherein:
one of R 1 and R 2 is H, and the other is ethyl or butyl;
X is chlorine; and
n is 0 or 1.
6. The method of claim 1 , wherein the precursor is selected from the group consisting of:
(EtNH) 3 Si—Si(HNEt) 3 ;
(Bu t NH) 2 ClSi—SiCl(HNBu t ) 2 ; and
(EtNH) 2 HSi—SiH(NHEt) 2 .
7. The method of claim 1 , wherein the precursor is (EtNH) 3 Si—Si(HNEt) 3 .
8. The method of claim 1 , wherein the precursor is (Bu t NH) 2 ClSi—SiCl(HNBu t ) 2 .
9. The method of claim 1 , wherein the precursor is (EtNH) 2 HSi—SiH(NHEt) 2 .
10. The method of claim 1 , wherein the vapor deposition conditions comprise temperature below 600° C.
11. The method of claim 1 , wherein the vapor deposition conditions comprise temperature below 550° C.
12. The method of claim 1 , wherein the vapor deposition conditions comprise temperature below 500° C.
13. The method of claim 1 , wherein the vapor deposition conditions comprise temperature in a range of from 350° C. to 500° C.
14. The method of claim 1 , wherein the vapor deposition conditions comprise temperature in a range of from 100° C. to 350° C.
15. The method of claim 1 , wherein the substrate is contacted in said contacting with a co-reactant selected from the group consisting of:
oxygen;
ozone;
CO 2 ;
nitrogen;
ammonia;
compounds of the formula R 3 Si—N 3 wherein each R is independently selected from C 1 -C 3 alkyl;
compounds of the formula R—N═NR′ wherein each R is independently selected from C 1 -C 3 alkyl and R′ is R or H;
compounds of the formula R—N═N + ═NR′ wherein each R is independently selected from C 1 -C 3 alkyl and R′ is R or H;
dinitrogen oxide;
hydrogen;
silane;
disilane;
hafnium sources; and
zirconium sources.
16. The method of claim 1 , wherein the contacting is carried out in a low pressure chemical vapor deposition process wherein said vapor deposition conditions comprise pressure in a range of from 100 millitorr to 1000 torr.
17. The method of claim 1 , wherein the silicon-containing film comprises a low k dielectric film.
18. The method of claim 1 , wherein the silicon-containing film comprises a high k gate silicate film.
19. The method of claim 1 , wherein the silicon-containing film comprises a silicon nitride film.
20. The method of claim 1 , wherein the silicon-containing film comprises a silicon oxynitride film.