Silyl substituted organoamines as precursors for high growth rate silicon-containing films
Described herein are novel silyl-substituted hydrazine and silyl-substituted diamine precursor compounds and compositions and methods comprising same to deposit a silicon-containing film such as, without limitation, silicon oxide, silicon nitride, silicon oxynitride, silicon carbonitride, silicon oxycarbonitride, or carbon-doped silicon oxide via a thermal atomic layer deposition (ALD) or plasma enhanced atomic layer deposition (PEALD) process, or a combination thereof.
1. A silicon precursor compound according to one of Formulae A to C:
wherein R 1-3 and X 1-16 are each independently selected from the group consisting of hydrogen; a halide atom selected from F, Cl, Br, and I; a silyl group (—SiH 3 ); a methylsilyl group (—SiH 2 Me); a dimethylsilyl group (—SiHMe 2 ); a trimethylsilyl group (—SiMe 3 ); a C 1-10 linear alkyl group; a C 3-10 branched alkyl group; a C 3-10 cyclic alkyl group; a C 2-10 alkenyl group; a C 4-10 aryl group; and a C 4-10 heterocyclic group,
provided that (a) if R 1 and R 2 are both hydrogen, then X 1-16 cannot all be methyl groups, and (b) if X 7 and X 8 are both F, then X 1-6 and X 9-16 cannot all be methyl groups, and wherein two or more of substituents R 1 , R 2 , and R 3 may be linked to form a substituted or unsubstituted, saturated or unsaturated, cyclic group.
2. A composition comprising at least one silicon precursor compound of claim 1 .
3. The composition of claim 2 , wherein the at least one silicon precursor compound is selected from the group consisting of 1-(2,2-dimethylhydrazinyl)-N,N-disilylsilanamine, 1-(2-(tert-butyl)hydrazinyl)-N,N-disilylsilanamine, N-((2,2-dimethylhydrazinyl) silyl)-N-(dimethylsilyl)-1,1-dimethylsilanamine, N-((2-(tert-butyl)hydrazinyl)silyl)-N-(dimethylsilyl)-1,1-dimethylsilanamine, N-((2,2-dimethylhydrazinyl)silyl)-1,1,1-trimethyl-N-(trimethylsilyl)silanamine, N-((2-(tert-butyl)hydrazinyl)silyl)-1,1,1-trimethyl-N-(trimethylsilyl)silanamine, 1-(1,2,2-trimethylhydrazinyl)-N,N-disilylsilanamine, 1-(1-iso-propyl-2,2-dimethylhydrazinyl)-N,N-disilylsilanamine, 1-(1-trimethylsilyl-2,2-dimethylhydrazinyl)-N,N-disilylsilanamine, 1-(1-dimethylsilyl-2,2-dimethylhydrazinyl)-N,N-disilylsilanamine, N-((2,2-dimethylhydrazinyl)silyl)-N,N′,N′-trisilylsilanediamine, 1,1′-(2,2-dimethylhydrazine-1,1-diyl)bis(N,N-disilylsilanamine).
4. A method of depositing a silicon-containing film onto a substrate, the method comprising the steps of:
a) providing a substrate in a reactor;
b) introducing into the reactor the at least one silicon precursor compound, of claim 1 ;
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 film is deposited, and
wherein the method is conducted at one or more temperatures ranging from about 25° C. to 600° C.
5. The method of claim 4 , 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.
6. The method of claim 4 wherein a density of the film is about 2.1 g/cc or greater.
7. The method of claim 4 wherein the film further comprises carbon at a concentration of 0.5 atomic weight percent (at. %) as measured by x-ray photospectroscopy or greater.
8. The method of claim 7 wherein a density of the film is about 1.8 g/cc or greater.
9. A silicon precursor compound according to one of Formulae D to F:
wherein R 1-4 and X 1-16 are each independently selected from the group consisting of hydrogen; a halide atom selected from F, Cl, Br, and I; a silyl group (—SiH 3 ); a methylsilyl group (—SiH 2 Me); a dimethylsilyl group (—SiHMe 2 ); a trimethylsilyl group (—SiMe 3 ); a C 1-10 linear alkyl group; a C 3-10 branched alkyl group; a C 3-10 cyclic alkyl group; a C 2-10 alkenyl group; a C 4-10 aryl group; and a C 4-10 heterocyclic group, provided that (a) X 1 , X 2 and X 3 cannot all be methyl groups, and (b) R 1 and R 2 cannot both be trimethylsilyl groups, and wherein two or more of substituents R 1 , R 2 , R 3 , and R 4 may be linked to form a substituted or unsubstituted, saturated or unsaturated, cyclic group.
10. A composition comprising at least one silicon precursor compound of claim 9 .
11. The composition of claim 10 , wherein the at least one silicon precursor compound is selected from the group consisting of N,N-disilyl-1,3,2-diazasilolidin-2-amine, 1,3-dimethyl-N,N-disilyl-1,3,2-diazasilolidin-2-amine, N,N-disilyloctahydro-1H-benzo[d][1,3,2]diazasilol-2-amine, 3-silyl-1,3,5,2,4-triazadisilepane, 1,5-dimethyl-3-silyl-1,3,5,2,4-triazadisilepane, 3-silyldecahydro-1H-benzo[f][1,3,5,2,4] triazadisilepine, N,N′-(ethane-1,2-diyl)bis(N,N-disilylsilanediamine), N,N′-(ethane-1,2-diyl)bis(N-methyl-N,N-disilylsilanediamine), N,N′-(cyclohexane-1,2-diyl)bis(N,N-disilylsilanediamine).
12. A method of depositing a silicon-containing film onto a substrate, the method comprising the steps of:
a) providing a substrate in a reactor;
b) introducing into the reactor the at least one silicon precursor compound of claim 9 ;
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 film is deposited, and
wherein the method is conducted at one or more temperatures ranging from about 25° C. to 600° C.
13. The method of claim 12 , 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 12 wherein a density of the film is about 2.1 g/cc or greater.
15. The method of claim 12 wherein the film further comprises carbon at a concentration of 0.5 atomic weight percent (at. %) as measured by x-ray photospectroscopy or greater.
16. The method of claim 15 wherein a density of the film is about 1.8 g/cc or greater.
17. A method to deposit a film comprising silicon and nitrogen 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 Formula A to C:
wherein R 1-3 and X 1-16 are each independently selected from the group consisting of hydrogen; a halide atom selected from F, Cl, Br, and I; a silyl group (—SiH 3 ); a methylsilyl group (—SiH 2 Me); a dimethylsilyl group (—SiHMe 2 ); a trimethylsilyl group (—SiMe 3 ); a C 1-10 linear alkyl group; a C 3-10 branched alkyl group; a C 3-10 cyclic alkyl group; a C 2-10 alkenyl group; a C 4-10 aryl group; and a C 4-10 heterocyclic group,
provided that (a) if R 1 and R 2 are both hydrogen, then X 1-16 cannot all be methyl groups, and (b) if X 7 and X 8 are both F, then X 1-6 and X 9-16 cannot all be methyl groups, and wherein two or more of substituents R 1 , R 2 , and R 3 may be linked to form a substituted or unsubstituted, saturated or unsaturated, cyclic group,
c) purging the reactor with purge gas;
d) introducing an nitrogen-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 film is deposited, and
wherein the method is conducted at one or more temperatures ranging from about 25° C. to 600° C.
18. The method of claim 17 , wherein the compound is selected from the group consisting of 1-(2,2-dimethylhydrazinyl)-N,N-disilylsilanamine, 1-(2-(tert-butyl)hydrazinyl)-N,N-disilylsilanamine, N-((2,2-dimethylhydrazinyl)silyl)-N-(dimethylsilyl)-1,1-dimethylsilanamine, N-((2-(tert-butyl)hydrazinyl)silyl)-N-(dimethylsilyl)-1,1-dimethylsilanamine, N-((2,2-dimethylhydrazinyl)silyl)-1,1,1-trimethyl-N-(trimethylsilyl)silanamine, N-((2-(tert-butyl)hydrazinyl)silyl)-1,1,1-trimethyl-N-(trimethylsilyl)silanamine, 1-(1,2,2-trimethylhydrazinyl)-N,N-disilylsilanamine, 1-(1-iso-propyl-2,2-dimethylhydrazinyl)-N,N-disilylsilanamine, 1-(1-trimethylsilyl-2,2-dimethylhydrazinyl)-N,N-disilylsilanamine, 1-(1-dimethylsilyl-2,2-dimethylhydrazinyl)-N,N-disilylsilanamine, N-((2,2-dimethylhydrazinyl)silyl)-N,N′,N′-trisilylsilanediamine, 1,1′-(2,2-dimethylhydrazine-1,1-diyl)bis(N,N-disilylsilanamine).
19. The method of claim 17 , wherein the nitrogen-containing source is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, nitrogen/argon plasma, nitrogen/helium plasma, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, tert-butylamine, dimethylamine, diethylamine, isopropylamine, diethylamine plasma, dimethylamine plasma, trimethylamine plasma, ethylenediamine plasma, ethanolamine plasma, and mixtures thereof.
20. The method of claim 17 wherein the film further comprises carbon at a concentration of 0.5 atomic weight percent (at. %) as measured by x-ray photospectroscopy or greater.