Methods of using amino(bromo)silane precursors for ALD/CVD silicon-containing film applications

• US 10,053,775 B2
• Filed: 12/30/2015
• Issued: 08/21/2018
• Est. Priority Date: 12/30/2015
• Status: Active Grant

• Current Assignee: American Air Liquide Incorporated (L'Air Liquide SA), L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Original Assignee: American Air Liquide Incorporated (L'Air Liquide SA), L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Inventors: Kuchenbeiser, Glenn, Pallem, Venkateswara R., Blasco, Nicolas, Girard, Jean-Marc
• Primary Examiner(s): Chen, Bret P
• Application Number:
  US14/984,908
• Publication Number:
  US 20160108064A1
• Time in Patent Office: 965 Days
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD

Abstract

Methods of using Si-containing film forming compositions to deposit silicon-containing films using vapor deposition processes are disclosed. The disclosed Si-containing film forming composition comprises an amino(bromo)silane precursor having the formula:
SiH_xBr_y(NR¹R²)_4−x−y
wherein x=0, 1 or 2; y=1, 2 or 3; x+y<4; each R¹ and R² is independently selected from C₁-C₆ alkyl, aryl, or hetero group; and R¹ and R² may be joined to form a cyclic nitrogen-containing heterocycle. The disclosed Si-containing film forming compositions include an amino(bromo)silane precursor selected from the group consisting of SiH₂Br(NEt₂), SiH₂Br(N(iPr)₂), SiH₂Br(N(iBu)₂) and SiBr(NMe₂)₃.

Claims

1. A method for forming a silicon-containing layer on a substrate, the method comprising the steps of:

introducing into a reactor containing a substrate a vapor of an Si-containing film forming composition comprising an amino(bromo)silane precursor having the formula;

SiH_xBr_y(NR¹R²)<sub>4−

x−

y</sub>

wherein x=0, 1 or 2;

y=1, 2 or 3;

x+y<

4; and

each R¹ and R² is independently selected from a C₁-C₆ alkyl, aryl, or hetero group; and

depositing at least part of the amino(bromo)silane precursor onto the substrate to form the silicon-containing layer using a vapor deposition process.

2. The method of claim 1, further comprising the step of delivering into the reactor a second vapor of a second precursor.

3. The method of claim 2, wherein an element of the second precursor is selected from the group consisting of group 2, group 13, group 14, transition metals, lanthanides, and combinations thereof.

4. The method of claim 1, further comprising the step of delivering into the reactor a reactant, wherein the reactant is selected from the group consisting of O₂, O₃, H₂O, H₂O₂, NO, NO₂, a carboxylic acid, plasma treated oxygen, radicals thereof, and combinations thereof.

5. The method of claim 1, further comprising the step of delivering into the reactor a reactant, wherein the reactant is selected from the group consisting of H₂, NH₃, (SiH₃)₃N, hydridosilanes, chlorosilanes and chloropolysilanes, alkysilanes, hydrazines, organic amines, pyrazoline, pyridine, B-containing molecules, alkyl metals, radical species thereof, and mixtures thereof.

6. The method of claim 5, wherein the reactant is selected from the group consisting of SiH₄, Si₂H₆, Si₃H₈, Si₄H₁₀, Si₅H₁₀, Si₆H₁₂, radical species thereof, and mixtures thereof.

7. The method of claim 5, wherein the reactant is selected from the group consisting of SiHCl₃, SiH₂Cl₂, SiH₃Cl, Si₂Cl₆, Si₂HCl₅, Si₃Cl₈, Si₂H₂Cl₄, and cyclo-Si₆H₆Cl₆, radical species thereof, and mixtures thereof.

8. The method of claim 5, wherein the reactant is selected from the group consisting of Me₂SiH₂, Et₂SiH₂, MeSiH₃, EtSiH₃, radical species thereof, and mixtures thereof.

9. The method of claim 5, wherein the reactant is selected from the group consisting of N₂H₄, MeHNNH₂, MeHNNHMe, radical species thereof, and mixtures thereof.

10. The method of claim 5, wherein the reactant is selected from the group consisting of NMeH₂, NEtH₂, NMe₂H, NEt₂H, NMe₃, NEt₃, (SiMe₃)₂NH, radical species thereof, and mixtures thereof.

11. The method of claim 1, wherein the silicon-containing layer is a silicon oxide layer.

12. The method of claim 1, wherein the vapor deposition process is an atomic layer deposition (ALD) process or a chemical deposition process.

13. The method of claim 1, wherein the amino(bromo)silane precursor is SiH₂Br(NEt₂).

14. The method of claim 1, wherein the amino(bromo)silane precursor is SiH₂Br(N(iPr)₂).

15. The method of claim 1, wherein the amino(bromo)silane precursor is SiH₂Br(N(iBu)₂).

16. The method of claim 1, wherein the amino(bromo)silane precursor is SiBr(NMe₂)₃.

17. The method of claim 1, wherein the amino(bromo)silane precursor is selected from the group consisting of:

18. The method of claim 1, wherein the amino(bromo)silane precursor is selected from the group consisting of:

19. The method of claim 1, wherein the amino(bromo)silane precursor is selected from the group consisting of:

20. The method of claim 1, wherein the amino(bromo)silane precursor is SiH₂Br(NMe₂).