ORGANOAMINOSILANE PRECURSORS AND METHODS FOR DEPOSITING FILMS COMPRISING SAME

• US 20150087139A1
• Filed: 09/11/2014
• Published: 03/26/2015
• Est. Priority Date: 09/20/2013
• Status: Active Grant

• Current Assignee: Versum Materials US Inc.
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: O'Neill, Mark Leonard, Xiao, Manchao, Lei, Xinjian, Ho, Richard, Chandra, Haripin, Wang, Meiliang, MacDonald, Matthew R.
• Granted Patent: US 10,453,675 B2
• Time in Patent Office: Days
• US Class Current: 438/482
• CPC Class Codes: C07F 7/10 containing nitrogen having a Si-N linkage
• CPC Class Codes: C09D 5/24 Electrically-conducting paints conductive materials H01B1/00
• CPC Class Codes: C23C 16/24 Deposition of silicon only
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: H01L 21/02126 the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
• 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 21/02167 the material being a silicon carbide not containing oxygen, e.g. SiC, SiC:H or silicon carbonitrides H01L21/02126 and H01L21/0214 take precedence
• 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 21/02271 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 21/02532 Silicon, silicon germanium, germanium
• CPC Class Codes: H01L 21/02592 amorphous
• CPC Class Codes: H01L 21/02598 monocrystalline
• CPC Class Codes: H01L 21/0262 Reduction or decomposition of gaseous compounds, e.g. CVD

Abstract

Described herein are precursors and methods for forming silicon-containing films. In one aspect, the precursor comprises a compound represented by one of following Formulae A through E below:

In one particular embodiment, the organoaminosilane precursors are effective for a low temperature (e.g., 350° C. or less), atomic layer deposition (ALD) or plasma enhanced atomic layer deposition (PEALD) of a silicon-containing film. In addition, described herein is a composition comprising an organoaminosilane described herein wherein the organoaminosilane is substantially free of at least one selected from the amines, halides (e.g., Cl, F, I, Br), higher molecular weight species, and trace metals.

Claims

1. An organoaminosilane comprising a compound represented by one of following Formulae A through E below:

2. The organoaminosilane of claim 1 wherein the R¹ and R² are linked together to form a ring.

3. The organoaminosilane of claim 1 comprising the compound having Formula A wherein R¹ and R² are the same and selected from the group consisting of methyl, ethyl, iso-propyl, n-propyl, and sec-butyl and wherein R³ is selected from the group consisting of methylene and ethylene;

n=1; and

m=0.

4. The organoaminosilane of claim 1 comprising the compound having Formula D wherein R¹ is not isopropyl (Prⁱ) when R³ is ethylene or propylene.

5. The organoaminosilane of claim 1 comprising the compound having Formula A wherein the compound is at least one selected from the group consisting of:

1-dimethylamino-1,3-disilapropane, di-isopropylamino-1,3-disilapropane, 1-di-secbutylamino-1,3-disilane propane, 1-di-isobutylamino-1,3-disilapropane, 1-di-tertpentylamino-1,3-disilapropane, 1-diethylamino-1,3-disilapropane, 1-dimethylamino-1,4-disilabutane, 1-diethylamino-1,4-disilabutane, 1-di-isopropylamino-1,4-disilabutane, 1,3-bis(dimethylamino)-1,3-disilapropane, 1,3-bis(di-isopropylamino)-1,3-disilapropane, 1,3-bis(di-sec-butylamino)-1,3-disilapropane, 1,3-bis(di-isobutylamino-1,3-disilapropane, 1,3-bis(di-tert-pentylamino)-1,3-disilapropane, 1,3-bis(diethylamino)-1,3-disilapropane, 1,4-bis(dimethylamino)-1,4-disilabutane, 1,4-bis(diethylamino)-1,4-disilabutane, 1,4-bis(di-isopropylamino)-1,3-disilabutane, 1,4-bis(di-sec-butylamino)-1,4-disilabutane, 1,4-bis(di-isobutylamino)-1,4-disilabutane, 1,4-bis(iso-propyl-n-propyl-amino)-1,4-disilabutane, 1,3-bis(ethylmethylamino)-1,3-disilabutane, and 1,4-bis(ethylmethylamino)-1,4-disilabutane.

6. The organoaminosilane of claim 1 selected from the group consisting of 1-di-isopropylamino-1,4-disilabutane, 1-ethylmethylamino-1,4-disilabutane, 1-di-sec-butylamino-1,4-disilabutane, 1-phenylmethylamino-1,4-disilabutane, 2,6-dimethylpiperidino-1,4-disilabutane, phenylethylamino-1,4-disilabutane, 1-di-isopropylamino-1,3-disilapropane, 1-ethylmethylamino-1,3-disilapropane, 1-di-sec-butylamino-1,3-disilapropane, 1-phenylmethylamino-1,3-disilapropane, 2,6-dimethylpiperidino-1,3-disilapropane, and phenylethylamino-1,3-disilapropane.

7. A composition comprising:

(a) at least one organoaminosilane comprising a compound represented by one of following Formulae A through E below;

8. The organoaminosilane precursor of claim 7 comprising at least one selected from the group consisting of 1-dimethylamino-1,4-disilabutane, 1-diethylamino-1,4-disilabutane, 1-ethylmethylamino-1,4-disilabutane, 1-di-isopropylamino-1,4-disilabutane, 1-di-sec-butylamino-1,4-disilabutane, 1-phenylmethylamino-1,4-disilabutane, 2,6-dimethylpiperidino-1,4-disilabutane, phenylethylamino-1,4-disilabutane, 1-dimethylamino-1,3-disilapropane, 1-diethylamino-1,3-disilapropane, 1-ethylmethylamino-1,3-disilapropane opylamino-1,3-disilapropane, 1-di-sec-butylamino-1,3-disilapropane, 1-phenylmethylamino-1,3-disilapropane, 2,6-dimethylpiperidino-1,3-disilapropane, and phenylethylamino-1,3-disilapropane.

9. The solvent of claim 7 comprising at least one selected from the group consisting of ether, tertiary amine, alkyl hydrocarbon, aromatic hydrocarbon, and tertiary aminoether.

10. A method for forming a silicon-containing film on at least one surface of a substrate by a deposition process selected from a chemical vapor deposition process and an atomic layer deposition process, the method comprising:

providing the at least one surface of the substrate in a reaction chamber;

introducing at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below;

11. The method of claim 10 wherein the at least one organoaminosilane precursor is selected from the group consisting of 1-dimethylamino-1,4-disilabutane, 1-diethylamino-1,4-disilabutane, 1-ethylmethylamino-1,4-disilabutane, 1-di-isopropylamino-1,4-disilabutane, 1-di-sec-butylamino-1,4-disilabutane, 1-phenylmethylamino-1,4-disilabutane, 2,6-dimethylpiperidino-1,4-disilabutane, phenylethylamino-1,4-disilabutane, 1-dimethylamino-1,3-disilapropane, 1-diethylamino-1,3-disilapropane, 1-ethylmethylamino-1,3-disilapropane, di-iso-propylamino-1,3-disilapropane, 1-di-sec-butylamino-1,3-disilapropane, 1-phenylmethylamino-1,3-disilapropane, 2,6-dimethylpiperidino-1,3-disilapropane, and phenylethylamino-1,3-disilapropane.

12. The method of claim 10 wherein the nitrogen-containing source is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/argon plasma, nitrogen/helium plasma, nitrogen/hydrogen plasma, organic amines, organic amine plasma, and mixtures thereof.

13. The method of claim 10 wherein the silicon-containing film is selected from the group consisting of silicon nitride and silicon carbonitride.

14. A method of forming a silicon-containing film via an atomic layer deposition (ALD) process, the method comprising the steps of:

a. providing a substrate in an ALD reactor;

b. providing in the ALD reactor at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below;

15. The method of claim 14 wherein the at least one organoaminosilane precursor is selected from the group consisting of 1-dimethylamino-1,4-disilabutane, 1-diethylamino-1,4-disilabutane, 1-ethylmethylamino-1,4-disilabutane, 1-di-isopropylamino-1,4-disilabutane, 1-di-sec-butylamino-1,4-disilabutane, 1-phenylmethylamino-1,4-disilabutane, 2,6-dimethylpiperidino-1,4-disilabutane, phenylethylamino-1,4-disilabutane, 1-dimethylamino-1,3-disilapropane, 1-diethylamino-1,3-disilapropane, 1-ethylmethylamino-1,3-disilapropane, di-iso-propylamino-1,3-disilapropane, 1-di-sec-butylamino-1,3-disilapropane, 1-phenylmethylamino-1,3-disilapropane, 2,6-dimethylpiperidino-1,3-disilapropane, and phenylethylamino-1,3-disilapropane.

16. The method of claim 14 wherein the nitrogen-containing source is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/argon plasma, nitrogen/helium plasma, nitrogen/hydrogen plasma, organic amines, organic amine plasma, and mixtures thereof.

17. The method of claim 14 wherein the silicon-containing film is selected from the group consisting of silicon nitride and silicon carbonitride.

18. A method of forming a silicon-containing film onto at least a surface of a substrate using a deposition process selected from a plasma enhanced atomic layer (PEALD) process and a PECCVD process, the method comprising:

a. providing a substrate in an ALD reactor;

b. providing in the ALD reactor at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below;

19. The method of claim 18 wherein the at least one organoaminosilane precursor is selected from the group consisting of 1-dimethylamino-1,4-disilabutane, 1-diethylamino-1,4-disilabutane, 1-ethylmethylamino-1,4-disilabutane, 1-di-isopropylamino-1,4-disilabutane, 1-di-sec-butylamino-1,4-disilabutane, 1-phenylmethylamino-1,4-disilabutane, 2,6-dimethylpiperidino-1,4-disilabutane, phenylethylamino-1,4-disilabutane, 1-dimethylamino-1,3-disilapropane, 1-diethylamino-1,3-disilapropane, 1-ethylmethylamino-1,3-disilapropane, di-iso-propylamino-1,3-disilapropane, 1-di-sec-butylamino-1,3-disilapropane, 1-phenylmethylamino-1,3-disilapropane, 2,6-dimethylpiperidino-1,3-disilapropane, and phenylethylamino-1,3-disilapropane.

20. The method of claim 18 wherein the nitrogen-containing source is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/argon plasma, nitrogen/helium plasma, nitrogen/hydrogen plasma, organic amines, organic amine plasma, and mixtures thereof.

21. The method of claim 18 wherein the silicon-containing film is selected from the group consisting of silicon nitride and silicon carbonitride.

22. A method for forming a silicon oxide or a carbon doped silicon oxide film on a substrate comprising:

reacting an oxygen-containing source with a precursor comprising at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below;

23. The method of claim 22 wherein the vapor deposition is at least one selected from the group consisting of at least one selected from chemical vapor deposition, low pressure vapor deposition, plasma enhanced chemical vapor deposition, cyclic chemical vapor deposition, plasma enhanced cyclic chemical vapor deposition, atomic layer deposition, and plasma enhanced atomic layer deposition.

24. The method of claim 22 wherein the at least one organoaminosilane precursor is selected from the group consisting of 1-dimethylamino-1,4-disilabutane, 1-diethylamino-1,4-disilabutane, 1-ethylmethylamino-1,4-disilabutane, 1-di-isopropylamino-1,4-disilabutane, 1-di-sec-butylamino-1,4-disilabutane, 1-phenylmethylamino-1,4-disilabutane, 2,6-dimethylpiperidino-1,4-disilabutane, phenylethylamino-1,4-disilabutane, 1-dimethylamino-1,3-disilapropane, 1-diethylamino-1,3-disilapropane, 1-ethylmethylamino-1,3-disilapropane, di-iso-propylamino-1,3-disilapropane, 1-di-sec-butylamino-1,3-disilapropane, 1-phenylmethylamino-1,3-disilapropane, 2,6-dimethylpiperidino-1,3-disilapropane, and phenylethylamino-1,3-disilapropane.

25. The method of claim 22 wherein the reacting step is conducted at a temperature of 200°

C. or less.

26. The method of claim 22 wherein the reacting step is conducted at a temperature of 100°

C. or less.

27. The method of claim 22 wherein the reacting step is conducted at 50°

C. or less.

28. A method for forming a silicon oxide or carbon doped silicon oxide film on a substrate comprising:

forming via vapor deposition the film on the substrate from a composition comprising at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below;

29. The method of claim 28 wherein the at least one organoaminosilane precursor is selected from the group consisting of 1-dimethylamino-1,4-disilabutane, 1-diethylamino-1,4-disilabutane, 1-ethylmethylamino-1,4-disilabutane, 1-di-isopropylamino-1,4-disilabutane, 1-di-sec-butylamino-1,4-disilabutane, 1-phenylmethylamino-1,4-disilabutane, 2,6-dimethylpiperidino-1,4-disilabutane, phenylethylamino-1,4-disilabutane, 1-dimethylamino-1,3-disilapropane, 1-diethylamino-1,3-disilapropane, 1-ethylmethylamino-1,3-disilapropane, di-iso-propylamino-1,3-disilapropane, 1-di-sec-butylamino-1,3-disilapropane, 1-phenylmethylamino-1,3-disilapropane, 2,6-dimethylpiperidino-1,3-disilapropane, and phenylethylamino-1,3-disilapropane.

30. The method of claim 28 wherein the forming step is conducted at a temperature of 200°

C. or less.

31. The method of claim 28 wherein the forming step is conducted at a temperature of 100°

C. or less.

32. The method of claim 28 wherein the forming step is conducted at 50°

C. or less.

33. A method for forming a silicon oxide or carbon doped silicon oxide film on a substrate comprising:

introducing at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below;

34. A method for forming a silicon oxide or carbon doped silicon oxide film on a substrate wherein the film comprises a thickness, the method comprising:

a. introducing at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below;

35. The method of claim 34 wherein steps a. through d. and optional step e. are repeated until the thickness of film is established.

36. The method of claim 34 wherein the at least one organoaminosilane precursor is selected from the group consisting of 1-dimethylamino-1,4-disilabutane, 1-diethylamino-1,4-disilabutane, 1-ethylmethylamino-1,4-disilabutane, 1-di-isopropylamino-1,4-disilabutane, 1-di-sec-butylamino-1,4-disilabutane, 1-phenylmethylamino-1,4-disilabutane, 2,6-dimethylpiperidino-1,4-disilabutane, phenylethylamino-1,4-disilabutane, 1-dimethylamino-1,3-disilapropane, 1-diethylamino-1,3-disilapropane, 1-ethylmethylamino-1,3-disilapropane, di-iso-propylamino-1,3-disilapropane, 1-di-sec-butylamino-1,3-disilapropane, 1-phenylmethylamino-1,3-disilapropane, 2,6-dimethylpiperidino-1,3-disilapropane, and phenylethylamino-1,3-disilapropane.

37. The method of claim 34 wherein the chemisorbing step is conducted at a temperature of 200°

C. or less.

38. The method of claim 34 wherein the chemisorbing step is conducted at a temperature of 100°

C. or less.

39. The method of claim 34 wherein the chemisorbing step is conducted at 50°

C. or less.

40. The method of claim 34 is an atomic layer deposition process.

41. The method of claim 34 is a plasma enhanced cyclic chemical vapor deposition process.

42. A method for forming a silicon containing film using a deposition method selected from ALD or cyclic CVD that comprises the steps of:

a. placing a substrates into a reactor which is heated to one or more temperatures ranging from about ambient temperature to about 700°

C.;

b. introducing at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below;

43. The method of claim 42 wherein the reducing agent is at least one selected from the group consisting of hydrogen, hydrogen plasma, or hydrogen chloride.

44. A method of depositing an amorphous or a crystalline silicon film via a deposition process selected from an atomic layer deposition, a cyclic chemical vapor deposition process and a chemical vapor deposition, the method comprising the steps of:

a. providing a substrate in a reactor;

b. introducing into the reactor at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below;

45. The method of claim 44 wherein the at least one organoaminosilane precursor is selected from the group consisting of 1-dimethylamino-1,4-disilabutane, 1-diethylamino-1,4-disilabutane, 1-ethylmethylamino-1,4-disilabutane, 1-di-isopropylamino-1,4-disilabutane, 1-di-sec-butylamino-1,4-disilabutane, 1-phenylmethylamino-1,4-disilabutane, 2,6-dimethylpiperidino-1,4-disilabutane, phenylethylamino-1,4-disilabutane, 1-dimethylamino-1,3-disilapropane, 1-diethylamino-1,3-disilapropane, 1-ethylmethylamino-1,3-disilapropane, di-iso-propylamino-1,3-disilapropane, 1-di-sec-butylamino-1,3-disilapropane, 1-phenylmethylamino-1,3-disilapropane, 2,6-dimethylpiperidino-1,3-disilapropane, and phenylethylamino-1,3-disilapropane.

46. A method of forming a silicon-containing film onto at least a surface of a substrate using a deposition process selected from a plasma enhanced atomic layer (PEALD) process and a plasma enhanced cyclic chemical vapor deposition (PECCVD) process, the method comprising:

a. providing a substrate in an ALD reactor;

b. providing in the ALD reactor at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below;

47. The method of claim 46 wherein the at least one organoaminosilane precursor is selected from the group consisting of 1-dimethylamino-1,4-disilabutane, 1-diethylamino-1,4-disilabutane, 1-ethylmethylamino-1,4-disilabutane, 1-di-isopropylamino-1,4-disilabutane, 1-di-sec-butylamino-1,4-disilabutane, 1-phenylmethylamino-1,4-disilabutane, 2,6-dimethylpiperidino-1,4-disilabutane, phenylethylamino-1,4-disilabutane, 1-dimethylamino-1,3-disilapropane, 1-diethylamino-1,3-disilapropane, 1-ethylmethylamino-1,3-disilapropane, di-iso-propylamino-1,3-disilapropane, 1-di-sec-butylamino-1,3-disilapropane, 1-phenylmethylamino-1,3-disilapropane, 2,6-dimethylpiperidino-1,3-disilapropane, and phenylethylamino-1,3-disilapropane.

48. The method of claim 46 wherein the plasma source is selected from the group consisting of hydrogen plasma, hydrogen/argon plasma, argon plasma, helium plasma, hydrogen/helium plasma, neon plasma, hydrogen/neon plasma, xenon plasma, hydrogen/xenon plasma, and mixtures thereof.

49. The method of claim 46 wherein the silicon-containing film is selected from the group consisting of silicon carbonitride, silicon carbide, silicon nitride, silicon carbonitride, and silicon carboxynitride.

50. A vessel which is used to deliver a precursor for the deposition of a silicon-containing film, the vessel comprising:

at least one organoaminosilane precursor comprising a compound represented by one of following Formulae A through E below;

51. The vessel of claim 50 wherein the vessel is comprised of stainless steel.

52. A method for preparing an organoaminosilane comprising a compound represented by one of following Formulae A through E below: