Organoaminosilane precursors and methods for depositing films comprising same

• US 8,912,353 B2
• Filed: 05/24/2011
• Issued: 12/16/2014
• Est. Priority Date: 06/02/2010
• Status: Active Grant

• Current Assignee: Versum Materials US, LLC (Merck & Co., Inc.)
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Xiao, Manchao, O'Neill, Mark Leonard, Bowen, Heather Regina, Cheng, Hansong, Lei, Xinjian
• Primary Examiner(s): Sajjadi, Fereydoun G
• Assistant Examiner(s): Adzamli, Kofi
• Application Number:
  US13/114,287
• Publication Number:
  US 20120128897A1
• Time in Patent Office: 1,302 Days
• Field of Search: 556/410
• US Class Current: 556/410
• CPC Class Codes: C07F 7/025 without C-silicon linkages
• CPC Class Codes: C23C 16/345 Silicon nitride
• CPC Class Codes: C23C 16/401 containing silicon

Abstract

Described herein are precursors and methods of forming dielectric films. In one aspect, there is provided a silicon precursor having the following formula I:

wherein R¹ is independently selected from hydrogen, a linear or branched C₁ to C₆ alkyl, a linear or branched C₂ to C₆ alkenyl, a linear or branched C₂ to C₆ alkynyl, a C₁ to C₆ alkoxy, a C₁ to C₆ dialkylamino and an electron withdrawing group and n is a number selected from 0, 1, 2, 3, 4, and 5; and R² is independently selected from hydrogen, a linear or branched C₁ to C₆ alkyl, a linear or branched C₂ to C₆ alkenyl, a linear or branched C₂ to C₆ alkynyl, a C₁ to C₆ alkoxy, a C₁ to C₆ dialkylamino, a C₆ to C₁₀ aryl, a linear or branched C₁ to C₆ fluorinated alkyl, and a C₄ to C₁₀ cyclic alkyl group.

Claims

1. An organoaminosilane precursor represented by the following formula I:

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

3. The organoaminosilane precursor of claim 1 wherein R¹ and R² are the same.

4. The organoaminosilane precursor of claim 1 wherein R¹ and R² are different.

5. The organoaminosilane precursor of claim 1 comprising at least one selected from the group consisting of phenylmethylaminosilane, phenylethylaminosilane, phenyl-iso-propylaminosilane, phenylallylaminosilane, m-tolylmethylaminosilane, N-silyl-tetrahydroquinoline, N-silyl-3-anilinopropionitrile, N-silyl-N-phenylglycinonitrile, N-silylcarbazole, phenylcyclohexylaminosilane, N-silyl-2-methylindoline, N-silylbenzomorpholine, N-silylindole, N-silyl-2-methylindole, N-silyl-3-methylindole, o-tolylethylaminosilane, p-tolylethylaminosilane, m-tolylethylaminosilane, p-tolylethylaminosilane, o-tolylethylaminosilane, and N-silyl-1,2,3,4-Tetrahydro-2-methylquinoline.

6. The organoaminosilane precursor of claim 5 comprising phenylmethylaminosilane.

7. The organoaminosilane precursor of claim 5 comprising phenylethylaminosilane.

8. The organoaminosilane precursor of claim 5 comprising m-tolylethylaminosilane.

9. An organoaminosilane precursor represented by the following formula I:

10. The organoaminosilane precursor of claim 9 comprising phenylmethylaminosilane.

11. The organoaminosilane precursor of claim 9 comprising phenylethylaminosilane.

12. The organoaminosilane precursor of claim 9 comprising m-tolylethylaminosilane.

13. A method for forming a dielectric film on at least one surface of a substrate by a deposition process chosen 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 having the following formula I in the reactor;

14. The method of claim 13 wherein the at least one organoaminosilane precursor is selected from the group consisting of phenylmethylaminosilane, phenylethylaminosilane, phenyl-iso-propylaminosilane, phenylallylaminosilane, m-tolylmethylaminosilane, N-silyl-tetrahydroquinoline, N-silyl-3-anilinopropionitrile, N-silyl-N-phenylglycinonitrile, N-silylcarbazole, phenylcyclohexylaminosilane, N-silyl-2-methylindoline, N-silylbenzomorpholine, N-silylindole, N-silyl-2-methylindole, N-silyl-3-methylindole, o-tolylethylaminosilane, p-tolylethylaminosilane, m-tolylethylaminosilane, p-tolylethylaminosilane, o-tolylethylaminosilane, and N-silyl-1,2,3,4-Tetrahydro-2-methylquinoline.

15. The method of claim 14 wherein the at least one organoaminosilane precursor comprises phenylmethylaminosilane.

16. The method of claim 14 wherein the at least one organoaminosilane precursor comprises phenylethylaminosilane.

17. The method of claim 14 wherein the at least one organoaminosilane precursor comprises m-tolylethylaminosilane.

18. The method of claim 13 wherein the nitrogen-containing source is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, and mixtures thereof.

19. The method of claim 13 wherein the dielectric film is selected from the group consisting of silicon nitride and silicon carbonitride.

20. A method of forming a dielectric 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 an at least one organoaminosilane precursor having the following formula I;

21. The method of claim 20 wherein the at least one organoaminosilane precursor is selected from the group consisting of phenylmethylaminosilane, phenylethylaminosilane, phenyl-iso-propylaminosilane, phenylallylaminosilane, m-tolylmethylaminosilane, N-silyl-tetrahydroquinoline, N-silyl-3-anilinopropionitrile, N-silyl-N-phenylglycinonitrile, N-silylcarbazole, phenylcyclohexylaminosilane, N-silyl-2-methylindoline, N-silylbenzomorpholine, N-silylindole, N-silyl-2-methylindole, N-silyl-3-methylindole, o-tolylethylaminosilane, p-tolylethylaminosilane, m-tolylethylaminosilane, p-tolylethylaminosilane, o-tolylethylaminosilane, and N-silyl-1,2,3,4-Tetrahydro-2-methylquinoline.

22. The method of claim 21 wherein the at least one organoaminosilane precursor comprises phenylmethylaminosilane.

23. The method of claim 21 wherein the at least one organoaminosilane precursor comprises phenylethylaminosilane.

24. The method of claim 21 wherein the at least one organoaminosilane precursor comprises m-tolylethylaminosilane.

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

26. The method of claim 20 wherein the dielectric film is selected from the group consisting of silicon nitride and silicon carbonitride.

27. A method of forming a dielectric film onto at least a surface of a substrate using a plasma enhanced atomic layer deposition (PEALD) process, the method comprising:

a. providing a substrate in an ALD reactor;

b. providing in the ALD reactor an at least one organoaminosilane precursor having the following formula I;

28. The method of claim 27 wherein the at least one organoaminosilane precursor is selected from the group consisting of phenylmethylaminosilane, phenylethylaminosilane, phenyl-iso-propylaminosilane, phenylallylaminosilane, m-tolylmethylaminosilane, N-silyl-tetrahydroquinoline, N-silyl-3-anilinopropionitrile, N-silyl-N-phenylglycinonitrile, N-silylcarbazole, phenylcyclohexylaminosilane, N-silyl-2-methylindoline, N-silylbenzomorpholine, N-silylindole, N-silyl-2-methylindole, N-silyl-3-methylindole, o-tolylethylaminosilane, p-tolylethylaminosilane, m-tolylethylaminosilane, p-tolylethylaminosilane, o-tolylethylaminosilane, and N-silyl-1,2,3,4-Tetrahydro-2-methylquinoline.

29. The method of claim 28 wherein the at least one organoaminosilane precursor comprises phenylmethylaminosilane.

30. The method of claim 28 wherein the at least one organoaminosilane precursor comprises phenylethylaminosilane.

31. The method of claim 28 wherein the at least one organoaminosilane precursor comprises m-tolylethylaminosilane.

32. The method of claim 27 wherein the nitrogen-containing source is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, and mixtures thereof.

33. The method of claim 27 wherein the dielectric film is selected from the group consisting of silicon nitride and silicon carbonitride.

34. A method for forming a silicon oxide film on a substrate comprising:

reacting an oxidizing agent with a precursor comprising an organoaminosilane represented by the following formula I;

35. The method of claim 34 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.

36. The method of claim 34 wherein the at least one organoaminosilane precursor is selected from the group consisting of phenylmethylaminosilane, phenylethylaminosilane, phenyl-iso-propylaminosilane, phenylallylaminosilane, m-tolylmethylaminosilane, N-silyl-tetrahydroquinoline, N-silyl-3-anilinopropionitrile, N-silyl-N-phenylglycinonitrile, N-silylcarbazole, phenylcyclohexylaminosilane, N-silyl-2-methylindoline, N-silylbenzomorpholine, N-silylindole, N-silyl-2-methylindole, N-silyl-3-methylindole, o-tolylethylaminosilane, p-tolylethylaminosilane, m-tolylethylaminosilane, p-tolylethylaminosilane, o-tolylethylaminosilane, and N-silyl-1,2,3,4-tetrahydro-2-methylquinoline.

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

C. or less.

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

C. or less.

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

C. or less.

40. A method for forming a silicon oxide film on a substrate comprising:

forming via vapor deposition of the silicon oxide film on the substrate from a composition comprising at least one organoaminosilane precursor having the following Formula I;

41. The method of claim 40 wherein the at least one organoaminosilane precursor is selected from the group consisting of phenylmethylaminosilane, phenylethylaminosilane, phenyl-iso-propylaminosilane, phenylallylaminosilane, m-tolylmethylaminosilane, N-silyl-tetrahydroquinoline, N-silyl-3-anilinopropionitrile, N-silyl-N-phenylglycinonitrile, N-silylcarbazole, phenylcyclohexylaminosilane, N-silyl-2-methylindoline, N-silylbenzomorpholine, N-silylindole, N-silyl-2-methylindole, N-silyl-3-methylindole, o-tolylethylaminosilane, p-tolylethylaminosilane, m-tolylethylaminosilane, p-tolylethylaminosilane, o-tolylethylaminosilane, and N-silyl-1,2,3,4-Tetrahydro-2-methylquinoline.

42. The method of claim 40 wherein the reacting step is conducted at a temperature of 200°

C. or less.

43. The method of claim 40 wherein the reacting step is conducted at a temperature of 100°

C. or less.

44. The method of claim 40 wherein the reacting step is conducted at 50°

C. or less.

45. A method for forming a silicon oxide film on a substrate comprising:

introducing an organoaminosilane represented by the following formula I;

50. The method of claim 45 wherein the reacting step is conducted at a temperature of 100°

C. or less.

46. A method for forming a silicon oxide film on a substrate wherein the film comprises a thickness, the method comprising:

a. introducing an at least one organoaminosilane represented by the formula I into a deposition chamber;

47. The method of claim 46 wherein steps a. through d. and optional step e. are repeated until the thickness of film is established.

48. The method of claim 46 wherein the at least one organoaminosilane precursor is selected from the group consisting of phenylmethylaminosilane, phenylethylaminosilane, phenyl-iso-propylaminosilane, phenylallylaminosilane, m-tolylmethylaminosilane, N-silyl-tetrahydroquinoline, N-silyl-3-anilinopropionitrile, N-silyl-N-phenylglycinonitrile, N-silylcarbazole, phenylcyclohexylaminosilane, N-silyl-2-methylindoline, N-silylbenzomorpholine, N-silylindole, N-silyl-2-methylindole, N-silyl-3-methylindole, o-tolylethylaminosilane, p-tolylethylaminosilane, m-tolylethylaminosilane, p-tolylethylaminosilane, o-tolylethylaminosilane, and N-silyl-1,2,3,4-Tetrahydro-2-methylquinoline.

49. The method of claim 46 wherein the reacting step is conducted at a temperature of 200°

C. or less.

51. The method of claim 49 wherein the reacting step is conducted at 50°

C. or less.

52. The method of claim 46 is an atomic layer deposition process.

53. The method of claim 46 is a plasma enhanced cyclic chemical vapor deposition process.

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

the precursor represented by the following formula I;

55. The vessel of claim 54 wherein the vessel is comprised of stainless steel.

56. An organoaminosilane precursor for depositing a dielectric film comprising at least one compound selected from the group consisting of:

phenylmethylaminosilane, phenylethylaminosilane, phenyl-iso-propylaminosilane, phenylallylaminosilane, m-tolylmethylaminosilane, N-silyl-tetrahydroquinoline, N-silyl-3-anilinopropionitrile, N-silyl-N-phenylglycinonitrile, N-silylcarbazole, phenylcyclohexylaminosilane, N-silyl-2-methylindoline, N-silylbenzomorpholine, N-silylindole, N-silyl-2-methylindole, N-silyl-3-methylindole, o-tolylethylaminosilane, p-tolylethylaminosilane, m-tolylethylaminosilane, p-tolylethylaminosilane, o-tolylethylaminosilane, and N-silyl-1,2,3,4-Tetrahydro-2-methylquinoline.

57. The organoaminosilane precursor of claim 56 comprising at least one selected from the group consisting of phenylmethylaminosilane, phenylethylaminosilane, and m-tolylethylaminosilane.