Precursors and processes for deposition of Si-containing films using ALD at temperature of 550° C. or higher

Patent metadata

Field	Value
Publication number	US-12368042-B2
Application number	US-201917416990-A
Country	US
Kind code	B2
Filing date	Dec 13, 2019
Priority date	Dec 21, 2018
Publication date	Jul 22, 2025
Grant date	Jul 22, 2025

Abstract

Methods for forming a Si-containing film on a substrate comprise heating the substrate to a temperature higher than S50° C., exposing the substrate to a vapor including a Si-containing film forming composition containing a Si-containing precursor having the formula: SiR 1 y R 2 4-x-y (NH—SiR′ 3 ) x , wherein x=2, 3, 4; y=0, 1, 2, R 1 and R 2 each are independently selected from H, a halogen (Cl, Br, I), an C 1 -C 4 alkyl, an isocyanate, a C 1 -C 4 alkoxide, or an —NR 3 R 4 group in which R 3 and R 4 each are independently selected from H, a C 1 -C 4 alkyl, provided that if R 3 ═H, R 4 >C 1 ; each R′ is independently selected from H, a halogen (Cl, Br, I), or a C 1 -C 4 alkyl, and depositing the Si-containing precursor onto the substrate to form the Si-containing film on the substrate through an ALD process. The Si-containing precursor may be selected from SiH 2 (NH—Si(CH 3 ) 3 ) 2 , SiHCl(NH—Si(CH 3 ) 3 ) 2 , SiCl 2 (NH—Si(CH 3 ) 3 ) 2 , SiH(NH—Si(CH 3 ) 3 ) 3 , SiCl(NH—Si(CH 3 ) 3 ) 3 , or Si(NH—Si(CH 3 ) 3 ) 4 .

First claim

What is claimed is:

1. A method for forming a Si-containing film on a substrate, the method comprising the steps of:
heating the substrate in a reactor to a temperature of 550° C. or higher;
exposing the substrate to a vapor including a Si-containing film forming composition that contains a Si-containing precursor selected from SiH(NH—Si(CH 3 ) 3 ) 3 , SiHCl(NH—Si(CH 3 ) 3 ) 2 , SiCl 2 (NH—Si(CH 3 ) 3 ) 2 , or Si(NH—Si(CH 3 ) 3 ) 4 ; and
depositing at least part of the Si-containing precursor onto the substrate to form the Si-containing film on the substrate through an atomic layer deposition (ALD) process.

2. The method of claim 1 , further comprising the step of exposing the substrate to a co-reactant.

3. The method of claim 2 , wherein the co-reactant is selected from O, O 2 , H 2 O, NO, N 2 O, NO 2 , H 2 O 2 , O radicals and combinations thereof.

4. The method of claim 2 , wherein the co-reactant is selected from NH 3 , NO, N 2 O, hydrazines, N 2 plasma, N 2/1 H 2 plasma, NH 3 plasma, amines and combinations thereof.

5. The method of claim 1 , further comprising the step of heating the substrate to a temperature greater than 550° C. to no more than 650° C.

6. The method of claim 1 , further comprising the step of heating the substrate to a temperature greater than 550° C. to no more than 750° C.

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

8. The method of claim 7 , wherein a WER of the silicon oxide film as deposited, normalized with thermal SiO 2 , is from 2 to 4.

9. The method of claim 1 , wherein the ALD process is a thermal ALD.

10. A method for forming a Si-containing film on a substrate, the method comprising the steps of:
heating a substrate in a reactor to a temperature of higher than 550° C.; and
forming a chemisorbed and/or physisorbed film, on the surface of the substrate, of a Si-containing precursor selected from SiH(NH—Si(CH 3 ) 3 ) 3 , SiHCl(NH—Si(CH 3 ) 3 ) 2 , SiCl 2 (NH—Si(CH 3 ) 3 ) 2 , or Si(NH—Si(CH 3 ) 3 ) 4 .

11. The method of claim 10 , further comprising the step of chemically reacting the chemisorbed and/or physisorbed film comprising the Si-containing precursor with a co-reactant.

12. The method of claim 11 , wherein the co-reactant reacting with the Si-containing precursor in the chemisorbed and/or physisorbed film produces a reaction product that forms a second film on the surface of the substrate.

13. The method of claim 12 , wherein the co-reactant is selected from O 3 , O 2 , H 2 O, NO, N 2 O, NO 2 , H 2 O 2 , O radicals and combinations thereof.

14. The method of claim 12 , wherein the co-reactant is selected from NH 3 , NO, N 2 O, hydrazines, N 2 plasma, N 2 /H 2 plasma, NH 3 plasma, amines and combinations thereof.

Assignees

• Air Liquide

Inventors

• Noda Naoto
• Nakagawa Naohisa
• Girard Jean-Marc
• Wan Zhiwen
• Kizu Takio

Classifications

• H10P14/69433

  the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz · CPC title

• H10P14/6339

  deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD · CPC title

• H10P14/6689 Primary

  the compound being a silazane · CPC title

• H10P14/6336

  in the presence of a plasma [PECVD] · CPC title

• H10P14/69215

  the material being a silicon oxide, e.g. SiO2 · CPC title