Precursors for depositing silicon containing films and processes thereof

• US 7,122,222 B2
• Filed: 10/27/2003
• Issued: 10/17/2006
• Est. Priority Date: 01/23/2003
• Status: Expired due to Term

• Current Assignee: Versum Materials US, LLC (Merck & Co., Inc.)
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Hochberg, Arthur Kenneth, Xiao, Manchao, Cuthill, Kirk Scott
• Primary Examiner(s): CHEN, BRET P
• Application Number:
  US10/695,379
• Publication Number:
  US 20040146644A1
• Time in Patent Office: 1,086 Days
• Field of Search: 427/255.394, 427/255.28, 427/255.393, 427/255.29
• US Class Current: 427/255.29
• CPC Class Codes: C07F 7/10 containing nitrogen having a Si-N linkage
• CPC Class Codes: C23C 16/308 Oxynitrides
• CPC Class Codes: C23C 16/345 Silicon nitride
• CPC Class Codes: H01L 21/0214 the material being a silicon oxynitride, e.g. SiON or SiON:H
• CPC Class Codes: H01L 21/02164 the material being a silicon oxide, e.g. SiO2
• 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 21/02211 the compound being a silane, e.g. disilane, methylsilane or chlorosilane
• CPC Class Codes: H01L 21/02219 the compound comprising silicon and nitrogen
• CPC Class Codes: H01L 21/02222 the compound being a silazane
• CPC Class Codes: H01L 21/0226 formation by a deposition process per se C23C
• CPC Class Codes: H01L 21/02271 deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition H01L21/02266 takes precedence
• 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
• CPC Class Codes: H01L 21/3125 layers comprising silazane compounds
• CPC Class Codes: H01L 21/3185 of siliconnitrides

Abstract

Processes for precursors for silicon dielectric depositions of silicon nitride, silicon oxide and silicon oxynitride on a substrate using a hydrazinosilane of the formula:
[R¹₂N—NH]_nSi(R²)_4−n
where each R¹ is independently selected from alkyl groups of C₁ to C₆; each R² is independently selected from the group consisting of hydrogen, alkyl, vinyl, allyl, and phenyl; and n=1–4. Some of the hydrazinosilanes are novel precursors.

Claims

1. A process for the chemical vapor deposition of material selected from the group consisting of silicon nitride, silicon oxide, and silicon oxynitride on a substrate using a hydrazinosilane of the formula:

[R¹₂N—

NH]_nSi(R²)<sub>4−

n</sub>

where each R¹ is independently selected from alkyl groups of C₁ to C₆;

each R² is independently selected from the group consisting of hydrogen, alkyl, vinyl, allyl, and phenyl; and

n=1–

4.

2. The process of claim 1 wherein the hydrazinosilane is selected from the group consisting of:

Bis(1,1-dimethylhydrazino)methylsilane, Tris(1,1-dimethylhydrazino)silane, Tris(1,1-dimethylhydrazino)-t-butylsilane, Tris(1,1-dimethylhydrazino)s-butylsilane, Tris(1,1-dimethylhydrazino)ethylsilane, Bis(1,1-dimethylhydrazino)ethylsilane, Bis(1,1-dimethylhydrazino)Iso-propylsilane, Bis(1,1-dimethylhydrazino)allylsilane, Bis(1,1-dimethylhydrazino)silane, Tetrakis(1,1-dimethylhydrazino)silane, N,N′

,N″

-Tris(dimethylamino)cyclotrisilazane, N,N′

,N″

,N′

″

-Tetrakis(dimethylamino)cyclotrisilazane, Tris(1,1-dimethylhydrazino)Iso-propylsilane, Tris(1,1-dimethylhydrazino)allylsilane and mixtures thereof.

3. The process of claim 1 wherein the temperature of the substrate is in the range of approximately 100 to 800°

C.

4. The process of claim 1 wherein the pressure is in the range of approximately 10⁻

5 Torr to 760 Torr.

5. The process of claim 1 wherein the hydrazinosilane is reacted with a nitrogen source selected from the group consisting of nitrogen, ammonia, hydrazine, amines, and mixtures thereof.

6. The process of claim 5 wherein the molar ratio of ammonia to hydrazinosilane can be greater than or equal to zero.

7. The process of claim 1 wherein the substrate is silicon.

8. The process of claim 1 wherein the substrate is an electronic device.

9. The process of claim 1 wherein the substrate is a flat panel display.

10. The process of claim 1 wherein each R¹ is independently selected from the group consisting of methyl and ethyl and each R² is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, allyl and phenyl.

11. The process of claim 1 wherein the material is silicon nitride.

12. The process of claim 1 wherein the material is silicon oxynitride.

13. The process of claim 1 wherein the material is silicon nitride and the chemical vapor deposition is plasma enhanced chemical vapor deposition.

14. The process of claim 1 wherein the material is silicon oxide and the chemical vapor deposition is plasma enhanced chemical vapor deposition.

15. The process of claim 1 wherein the material is silicon oxynitride and the chemical vapor deposition is plasma enhanced chemical vapor deposition.

16. The process of claim 1 wherein the chemical vapor deposition is atomic layer deposition.

17. A low temperature chemical vapor deposition of silicon nitride in a reaction zone, comprising the steps of:

a) heating a substrate to a temperature in the range of approximately 100–

800°

C. in said zone;

b) maintaining the substrate in a vacuum at a pressure in the range of approximately 10<sup>−

5</sup> Torr–

760 Torr in said zone;

c) introducing into said zone a hydrazinosilane of the formula;

[R¹₂N—

NH]_nSi(R²)<sub>4−

n</sub>

 

where each R¹ is independently selected from alkyl groups of C₁ to C₆;

each R² is independently selected from the group consisting of hydrogen, alkyl, allyl, and phenyl; and

n=1–

4; and

d) maintaining the conditions of a) through c) sufficient to cause a film of silicon nitride to deposit on the substrate.

18. The process of claim 17 wherein the hydrazinosilane is selected from the group consisting of:

Bis(1,1-dimethylhydrazino)methylsilane, Tris(1,1-dimethylhydrazino)silane, Tris(1,1-dimethylhydrazino)-t-butylsilane, Tris(1,1-dimethylhydrazino)s-butylsilane, Tris(1,1-dimethylhydrazino)ethylsilane, Bis(1,1-dimethylhydrazino)ethylsilane, Bis(1,1-dimethylhydrazino)Iso-propylsilane, Bis(1,1-dimethylhydrazino)allylsilane, Bis(1,1-dimethylhydrazino)silane, Tetrakis(1,1-dimethylhydrazino)silane, N,N′

,N″

-Tris(dimethylamino)cyclotrisilazane, N,N′

,N″

,N′

″

-Tetrakis(dimethylamino)cyclotrisilazane, Tris(1,1-dimethylhydrazino)Iso-propylsilane, Tris(1,1-dimethylhydrazino)allylsilane and mixtures thereof.

19. The process of claim 17 wherein the hydrazinosilane is reacted with nitrogen source selected from the group consisting of nitrogen, ammonia hydrazine and mixtures thereof.