Method of forming a silicon nitride film using Si—N containing precursors

• US 10,544,506 B2
• Filed: 03/30/2016
• Issued: 01/28/2020
• 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: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Inventors: Kerrigan, Sean, Sanchez, Antonio
• Primary Examiner(s): Chen, Bret P
• Application Number:
  US15/560,635
• Publication Number:
  US 20180087150A1
• Time in Patent Office: 1,399 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

Methods for forming a SiN-containing film are disclosed. The methods use film-forming compositions 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 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 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 method of claim 1, 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.

3. The method of claim 1, further comprising the step of delivering into the reactor a reactant.

4. The method of claim 1, wherein the substrate is selected from the group consisting of a silicon wafer, a glass substrate, and a plastic substrate.

5. The method of claim 1, wherein the Si—

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

6. The method of claim 1, wherein the Si—

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

)₂, having the formula;

7. 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,

8. The process of claim 7, 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.

9. The process of claim 7, wherein the catalyst is a metal supported on carbon.

10. The process of claim 7, wherein the Si—

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

11. The process of claim 7, wherein the Si—

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

12. The process of claim 7, wherein the Si—

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

)₂, having the formula;