Precursors for CVD Silicon Carbo-Nitride Films

• US 20110165346A1
• Filed: 03/18/2011
• Published: 07/07/2011
• Est. Priority Date: 05/16/2005
• Status: Active Grant

• Current Assignee: Versum Materials US Inc.
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Hochberg, Arthur Kenneth, Xiao, Manchao
• Granted Patent: US 8,383,849 B2
• Time in Patent Office: Days
• US Class Current: 427/577
• CPC Class Codes: C07F 7/025 without C-silicon linkages
• CPC Class Codes: C09D 5/00 Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced electrically insulating plastics, resins or waxes H01B3/30; Filling pastes
• CPC Class Codes: C23C 16/36 Carbonitrides
• 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 21/02211 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 21/02271 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

Abstract

Classes of liquid aminosilanes have been found which allow for the production of silicon carbo-nitride films of the general formula Si_xC_yN_z. These aminosilanes, in contrast, to some of the precursors employed heretofore, are liquid at room temperature and pressure allowing for convenient handling. In addition, the invention relates to a process for producing such films.

The classes of compounds are generally represented by the formulas:

• • and mixtures thereof, wherein R and R¹ in the formulas represent aliphatic groups typically having from 2 to about 10 carbon atoms, e.g., alkyl, cycloalkyl with R and R¹ in formula A also being combinable into a cyclic group, and R² representing a single bond, (CH₂)_n, a ring, or SiH₂.

Claims

1. A method of making an aminosilane represented by the following formulas A or B:

2. The method of claim 1 wherein the method further comprises:

separating the aminosilane having the formula A or B from the reaction mixture.

3. The method of claim 1 wherien the alkyl amine comprises one selected from the group consisting of ethyl, isopropyl, sec-butyl, t-butyl, or cyclohexyl.

4. The method of claim 3 wherein the alkyl amine comprises di-iso-propylamine.

5. The method of claim 3 wherein the alkyl amine comprises diethylamine.

6. The method of claim 1 wherein the reaction mixture further comprises a solvent.

7. The method of claim 1 wherein the reaction mixture further comprises triethylamine.

8. The method of claim 1 wherein the arylsilane comprises phenylsilane.

9. The method of claim 1 wherein the arylsilane comprises tolylsilane.

10. The method of claim 1 wherein the aminosilane comprises diethylaminosilane.

11. The method of claim 1 wherein the aminosilane comprises diisopropylaminosilane.

12. The method of claim 1 wherein the aminosilane comprises 2,4-di-tert-butyl-2,4-diaza-1,3,5-trisilapentane.

13. The method of claim 1 wherein the aminosilane comprises 2,4-dicyclohexyl-2,4-diaza-1,3,5-trisilapentane.

14. The method of claim 1 wherein the reaction mixture is cooled to a temperature of −

40°

C. prior to the adding step.

15. The method of claim 1 wherein the sulfonic acid comprises trifluoromethanesulfonic acid.

16. A method of making diisopropylaminosilane, the method comprising the steps of:

providing a reaction mixture comprising diisopropylamine;

adding to the reaction mixture an arylsilane and a sulfonic acid wherein the arylsilane and sulfonic acid react to form an intermediate and wherein the diisopropylamine reacts with the intermediate to provide diisopropylaminosilane.

17. The method of claim 16 wherein the arylsilane comprises phenylsilane.

18. The method of claim 16 wherein the reaction mixture further comprises triethylamine.

19. The method of claim 16 wherein the sulfonic acid comprises trifluoromethanesulfonic acid.

20. A method of making diethylaminosilane, the method comprising the steps of:

providing a reaction mixture comprising diethylamine; and

adding to the reaction mixture an arylsilane and a sulfonic acid wherein the arylsilane and sulfonic acid react to form an intermediate and wherein the diisopropylamine reacts with the intermediate to provide diethylaminosilane.

21. The method of claim 20 wherein the aryl silane comprises phenylsilane.

22. The method of claim 20 wherein the reaction mixture further comprises triethylamine.

23. The method of claim 20 wherein the sulfonic acid comprises trifluoromethanesulfonic acid.

24. A method of forming via a vapor deposition process a dielectric film having the formula Si_xC_yN_z, the method comprising:

providing a substrate within a vapor deposition chamber;

introducing into the vapor deposition chamber an aminosilane comprising the following formula A;

25. The method of claim 24 wherein the vapor deposition process is at least one selected from chemical vapor deposition, low pressure chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition.

26. The method of claim 25 wherein the vapor deposition process is chemical vapor deposition.

27. The method of claim 25 wherein the vapor deposition process is atomic layer deposition.

28. The method of claim 24 further comprising:

introducing an inert gas into the vapor deposition chamber.

29. The method of claim 24 further comprising:

introducing a precursor selected from the group consisting of bis-tert-butylaminosilane, tris-iso-propylaminosilane, bis-diethylaminosilane, tris-dimethylaminosilane, and bis-iso-propylaminosilane into the vapor deposition chamber.

30. The method of claim 24 wherein a mole ratio of nitrogen source to aminosilane precursor ranges from 0:

1 to 10;

1.

31. The method of claim 30 wherein the mole ratio of nitrogen source to aminosilane precursor ranges from 0:

1 to 4;

1.

32. A method of forming via a vapor deposition process a dielectric film having the formula Si_xC_yN_z, the method comprising:

providing a substrate within a vapor deposition chamber;

introducing into the vapor deposition chamber an aminosilane comprising the following formula B;

33. The method of claim 32 wherein the vapor deposition process is at least one selected from chemical vapor deposition, low pressure chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition.

34. The method of claim 33 wherein the vapor deposition process is chemical vapor deposition.

35. The method of claim 33 wherein the vapor deposition process is atomic layer deposition.

36. The method of claim 32 further comprising:

introducing an inert gas into the vapor deposition chamber.

37. The method of claim 32 further comprising:

introducing a precursor selected from the group consisting of bis-tert-butylaminosilane, tris-iso-propylaminosilane, bis-diethylaminosilane, tris-dimethylaminosilane, and bis-iso-propylaminosilane into the vapor deposition chamber.

38. The method of claim 32 wherein a mole ratio of nitrogen source to aminosilane precursor ranges from 0:

1 to 10;

1.

39. The method of claim 38 wherein the mole ratio of nitrogen source to aminosilane precursor ranges from 0:

1 to 4;

1.

40. A method of forming via a vapor deposition process a dielectric film having the formula Si_xC_yN_z, the method comprising:

providing a substrate within a vapor deposition chamber;

introducing into the vapor deposition chamber an aminosilane comprising the following formula C;

41. The method of claim 40 wherein the vapor deposition process is at least one selected from chemical vapor deposition, low pressure chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition.

42. The method of claim 41 wherein the vapor deposition process is chemical vapor deposition.

43. The method of claim 41 wherein the vapor deposition process is atomic layer deposition.

44. The method of claim 40 further comprising:

introducing an inert gas into the vapor deposition chamber.

45. The method of claim 40 further comprising:

introducing a precursor selected from the group consisting of bis-tert-butylaminosilane, tris-iso-propylaminosilane, bis-diethylaminosilane, tris-dimethylaminosilane, and bis-iso-propylaminosilane into the vapor deposition chamber.

46. The method of claim 40 wherein a mole ratio of nitrogen source to aminosilane precursor ranges from 0:

1 to 10;

1.

47. The method of claim 46 wherein the mole ratio of nitrogen source to aminosilane precursor ranges from 0:

1 to 4;

1.

48. A composition for depositing a dielectric film comprising:

an aminosilane comprising the following formula A;

49. The composition of claim 48 wherein R and R¹ are combined into a cyclic group.

50. The composition of claim 48 wherein R and R¹ are isopropyl groups.

51. The composition of claim 48 wherein R and R¹ are sec-butyl groups.

52. The composition of claim 48 wherein the precursor comprises bis-tert-butylaminosilane.

53. The composition of claim 48 wherein the precursor comprises tris-iso-propylaminosilane.

54. The composition of claim 48 wherein the precursor comprises bis-diethylaminosilane.

55. The composition of claim 48 wherein the precursor comprises tris-dimethylaminosilane.

56. The composition of claim 48 wherein the precursor comprises bis-iso-propylaminosilane.

57. A composition for depositing a dielectric film comprising:

an aminosilane comprising the following formula B;

58. The composition of claim 57 wherein R is t-pentyl.

59. The composition of claim 57 wherein R is cyclohexyl.

60. The composition of claim 57 wherein the precursor comprises bis-tert-butylaminosilane.

61. The composition of claim 57 wherein the precursor comprises tris-iso-propylaminosilane.

62. The composition of claim 57 wherein the precursor comprises bis-diethylaminosilane.

63. The composition of claim 57 wherein the precursor comprises tris-dimethylaminosilane.

64. The composition of claim 57 wherein the precursor comprises bis-iso-propylaminosilane.

65. A composition for depositing a dielectric film comprising:

an aminosilane comprising the following formula C;

66. The composition of claim 65 wherein the precursor comprises bis-tert-butylaminosilane.

67. The composition of claim 65 wherein the precursor comprises tris-iso-propylaminosilane.

68. The composition of claim 65 wherein the precursor comprises bis-diethylaminosilane.

69. The composition of claim 65 wherein the precursor comprises tris-dimethylaminosilane.

70. The composition of claim 65 wherein the precursor comprises bis-iso-propylaminosilane.

71. An aminosilane compound selected from the group having the following formulas:

72. The aminosilane of claim 71 comprising:

73. The aminosilane of claim 71 comprising:

74. The aminosilane of claim 71 comprising:

75. The aminosilane of claim 71 comprising:

76. The aminosilane of claim 71 comprising:

77. An aminosilane compound selected from the group consisting of:

78. The aminosilane of claim 77 comprising:

79. The aminosilane of claim 77 comprising:

80. The aminosilane of claim 77 comprising:

81. The aminosilane of claim 77 comprising:

82. An aminosilane selected from the group consisting of:

83. The aminosilane of claim 82 comprising:

84. The aminosilane of claim 82 comprising:

85. The aminosilane of claim 82 comprising: