Precursors for depositing silicon containing films and processes thereof

• US 20040146644A1
• Filed: 10/27/2003
• Published: 07/29/2004
• Est. Priority Date: 01/23/2003
• Status: Active Grant

• Current Assignee: Versum Materials US Inc.
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Hochberg, Arthur Kenneth, Xiao, Manchao, Cuthill, Kirk Scott
• Granted Patent: US 7,122,222 B2
• Time in Patent Office: Days
• US Class Current: 427/255.28
• 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 21/02219 the compound comprising silicon and nitrogen
• 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 silicon nitride 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.

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 for the deposition of silicon nitride by chemical vapor deposition.

12. The process of claim 1 for the deposition of silicon oxynitride by chemical vapor deposition.

13. The process of claim 1 for the deposition of silicon nitride by plasma enhanced chemical vapor deposition.

14. The process of claim 1 for the deposition of silicon oxide by plasma enhanced chemical vapor deposition.

15. The process of claim 1 for the deposition of silicon oxynitride by plasma enhanced chemical vapor deposition.

16. The process of claim 1 for the deposition of materials selected from the group consisting of silicon oxide, silicon oxynitride, and silicon nitride by 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)_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, 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-dimethyihydrazino)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.

20. A composition selected from the group consisting of 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)-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, and Tris(1,1-dimethylhydrazino)allylsilane.

21. A composition comprising Tris(1,1-dimethylhydrazino)silane.

22. A composition comprising Tris(1,1-dimethylhydrazino)-t-butylsilane

23. A composition comprising Tris(1,1-dimethylhydrazino)-s-butylsilane.

24. A composition comprising Bis(1,1-dimethylhydrazino)-iso-propylsilane.

25. A composition comprising Bis(1,1-dimethylhydrazino)allylsilane.

26. A composition comprising Bis(1,1-dimethylhydrazino)silane.

27. A composition comprising Tetrakis(1,1-dimethylhydrazino)silane.

28. A composition comprising N,N′

,N″

-Tris(dimethylamino)cyclotrisilazane.

29. A composition comprising Tris(1,1-dimethylhydrazino)-iso-propylsilane.

30. A composition comprising Tris(1,1-dimethylhydrazino)allylsilane.