CATALYTIC DEHYDROGENATIVE COUPLING OF CARBOSILANES WITH AMMONIA, AMINES AND AMIDINES

• US 20180087150A1
• Filed: 03/30/2016
• Published: 03/29/2018
• Est. Priority Date: 03/30/2015
• Status: Active Grant

• Current Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Original Assignee: Air Liquide Advanced Materials LLC (L'Air Liquide SA)
• Inventors: KERRIGAN, Sean, SANCHEZ, Antonio
• Granted Patent: US 10,544,506 B2
• Time in Patent Office: Days
• CPC Class Codes: C23C 16/345 Silicon nitride
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: C23C 16/50 using electric discharges generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34
• CPC Class Codes: H01L 21/0217 the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz H01L21/02126 and H01L21/0214 take precedence
• CPC Class Codes: H01L 21/02222 the compound being a silazane
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD

Abstract

Si-containing film forming compositions are disclosed comprising Si—N containing precursors. Also disclosed are methods of synthesizing the same and methods of using the same for vapor deposition. In particular, a catalytic dehydrogenative coupling of carbosilanes with ammonia, amines and amidines produces the Si—N containing precursors.

Claims

1. A Si-containing film forming composition comprising a Si—

N containing precursor having the formula H₃Si(CH₂)_nSiH₂N(R)C(Me)=NR, RN═

C(Me)N(R)SiH₂(CH₂)_nSiH₂N(R)C(Me)=NR,

2. The Si-containing film forming composition of claim 1, wherein the Si—

N containing precursor is NH(SiH₂(CH₂)_nSiH₃)₂, having the formula;

3. The Si-containing film forming composition of claim 1, wherein the Si—

N containing precursor is N(SiH₂(CH₂)_nSiH₃)₃, having the formula;

7. The Si-containing film forming composition of claim 1, wherein the Si—

N containing precursor is H₃Si(CH₂)_nSiH(NRR′

)₂, having the formula;

8. The Si-containing film forming composition of claim 1, wherein the Si—

N containing precursor is H₃Si(CH₂)_nSiH₂N(R)C(Me)=NR.

9. The Si-containing film forming composition of claim 1, wherein the Si—

N containing precursor is RN═

C(Me)N(R)SiH₂(CH₂)_nSiH₂N(R)C(Me)=NR.

10. A method for forming a SiN-containing film, the method comprising the steps of:

delivering into a reactor containing a substrate a vapor including a Si-containing film forming composition of claim 1; and

depositing at least part of the Si—

N containing precursor onto the substrate to form the silicon-containing film on the substrate using a vapor deposition process.

11. The method of claim 10, wherein the vapor deposition process is selected from the group consisting of low pressure chemical vapor deposition (LPCVD), sub-atmospheric chemical vapor deposition (SACVD), plasma enhanced chemical vapor deposition (PECVD), flowable chemical vapor deposition (Flowable CVD), atomic layer deposition (ALD), plasma enhanced atomic layer deposition (PEALD), ultraviolet (UV) assisted ALD, catalyzed ALD, spatial isolation ALD.

12. The method of claim 10, further comprising the step of delivering into the reactor a reactant.

13. The method of claim 10, wherein the substrate is selected from the group consisting of a silicon wafer, a glass substrate, and a plastic substrate.

14. The method of claim 10, wherein the substrate is coated with patterned or unpatterned organic or inorganic films.

18. The method of claim 10, wherein the Si—

N containing precursor is NH(SiH₂(CH₂)_nSiH₃)₂, having the formula;

19. The method of claim 10, wherein the Si—

N containing precursor is N(SiH₂(CH₂)_nSiH₃)₃, having the formula;

20. The method of claim 10, wherein the Si—

N containing precursor is H₃Si(CH₂)_nSiH(NRR′

)₂, having the formula;

4-6. -6. (canceled)

15. A process for forming a Si—

N containing compound having the formula having the formula H₃Si(CH₂)_nSiH₂N(R)C(Me)=NR, RN═

C(Me)N(R)SiH₂(CH₂)_nSiH₂N(R)C(Me)=NR,

16. The process of claim 15, wherein the second reactant is selected from the group consisting of NH₃, RNH₂, R₂NH, and an amidine, wherein R may each independently be H, a C₁ to C₆ alkyl group, or a C₃-C₂₀ aryl, heterocycle or cycloalkyl group, preferably ammonia or amidine.

17. The process of claim 15, wherein the catalyst is a metal supported on carbon.

21. The process of claim 15, wherein the Si—

N containing compound is NH(SiH₂(CH₂)_nSiH₃)₂, having the formula;

22. The process of claim 15, wherein the Si—

N containing compound is N(SiH₂(CH₂)_nSiH₃)₃, having the formula;

23. The process of claim 15, wherein the Si—

N containing compound is H₃Si(CH₂)_nSiH(NRR′

)₂, having the formula;