Process for direct deposition of ALD RhO2

• US 6,881,260 B2
• Filed: 06/25/2002
• Issued: 04/19/2005
• Est. Priority Date: 06/25/2002
• Status: Active Grant

• Current Assignee: Micron Technology, Inc.
• Original Assignee: Micron Technology, Inc.
• Inventors: Uhlenbrock, Stefan, Marsh, Eugene P.
• Primary Examiner(s): KUNEMUND, ROBERT M
• Application Number:
  US10/179,946
• Publication Number:
  US 20030233976A1
• Time in Patent Office: 1,029 Days
• Field of Search: 117/89, 117/101, 117/104, 117/105
• US Class Current: 117/89
• CPC Class Codes: C30B 25/02 Epitaxial-layer growth
• CPC Class Codes: C30B 29/16 Oxides

Abstract

The present invention provides methods of performing atomic layer deposition to form conductive, oxidation-resistant rhodium oxide films and films comprising metals, such as platinum, alloyed with rhodium oxide. The present invention also provides memory devices and processors comprising films deposited by the above methods.

Claims

1. A method of conducting atomic layer deposition of a rhodium oxide layer on a substrate, comprising:

providing a deposition apparatus comprising a reactor chamber having a deposition region;

positioning said substrate on said deposition region;

introducing an organo rhodium group metal precursor into said reactor chamber under conditions permitting the formation of an organo rhodium monolayer on said substrate; and

introducing a reaction gas into said reactor chamber, such that said organo rhodium monolayer is oxidized to a conductive rhodium oxide layer on said substrate.

2. The method of claim 1, wherein said organo rhodium group metal precursor comprises an organic rhodium group metal precursor having the formula Ly[Rh]Yz, wherein L is independently selected from the group consisting of neutral and anionic ligands;

y is one of {1, 2, 3, 4};

Y is independently a pi-orbital bonding ligand selected from the group consisting of CO, NO, CN, CS, N₂, PX₃, PR₃, P(OR)₃, AsX₃, AsR₃, As(OR)₃, SbX₃, SbR₃, Sb(OR)₃, NH_xR_3-x, CNR, and RCN, wherein R is an organic group, X is a halide and x is one of {0, 1, 2, 3}; and

z is one of {0, 1, 2, 3, 4}.

3. The method of claim 1, wherein said reaction gas is ozone.

4. The method of claim 2, wherein said organo rhodium group metal precursor is dicarbonyl cyclopentadienyl rhodium.

5. The method of claim 1, wherein said atomic layer deposition is performed at a temperature of about 100°

C. to about 200°

C.

6. The method of claim 5, wherein said atomic layer deposition is performed at a temperature of about 100°

C. to about 150°

C.

7. The method of claim 1, wherein said organo rhodium group metal precursor is introduced into said reactor chamber at a rate of about 0.1 to about 500 sccm.

8. The method of claim 7, wherein said organo rhodium group metal precursor is introduced into said reactor chamber at a rate of about 0.1 to about 5 sccm.

9. The method of claim 1, wherein said reaction gas is introduced into said reactor chamber at a rate of about 1 to about 500 sccm.

10. The method of claim 9, wherein said reaction gas is introduced into said reactor chamber at a rate of about 10 to about 200 sccm.

11. The method of claim 1, further comprising introducing a first purge gas into said reactor chamber after said introducing a rhodium group metal precursor and before said introducing a reaction gas.

12. The method of claim 11, wherein said first purge gas is selected from the group consisting of helium, argon and nitrogen.

13. The method of claim 11 further comprising introducing a second purge gas into said reactor chamber after said introducing a reaction gas.

14. The method of claim 13, wherein said second purge gas is selected from the group consisting of helium, argon and nitrogen.

15. The method of claim 1, wherein said rhodium oxide layer has a resistivity of less than about 100 μ

Ω

cm.

16. A method of conducting atomic layer deposition of a rhodium oxide on an integrated circuit material layer, comprising:

providing a deposition apparatus comprising a reactor chamber having a deposition region;

positioning said material layer in said deposition region;

introducing an organo rhodium group metal precursor into said reactor chamber under conditions permitting the formation of an organo rhodium monolayer on said material layer; and

introducing a reaction gas into said reactor chamber, such that said organo rhodium monolayer is oxidized to a conductive rhodium oxide layer.

17. The method of claim 16, wherein said rhodium group metal precursor comprises an organic rhodium group metal precursor having the formula Ly[Rh]Yz, wherein L is independently selected from the group consisting of neutral and anionic ligands;

y is one of {1, 2, 3, 4};

Y is independently a pi-orbital bonding ligand selected from the group consisting of CO, NO, CN, CS, N₂, PX₃, PR₃, P(OR)₃, AsX₃, AsR₃, As(OR)₃, SbX₃, SbR₃, Sb(OR)₃, NH_xR_3-x, CNR, and RCN, wherein R is an organic group, X is a halide and x is one of {0, 1, 2, 3}; and

z is one of {0, 1, 2, 3, 4}.

18. The method of claim 16, wherein said reaction gas is ozone.

19. The method of claim 17, wherein said rhodium group metal precursor is dicarbonyl cyclopentadienyl rhodium.

20. The method of claim 16, wherein said atomic layer deposition is performed at a temperature of about 100°

C. to about 200°

C.

21. The method of claim 20, wherein said atomic layer deposition is performed at a temperature of about 100°

C. to about 150°

C.

22. The method of claim 16, wherein said rhodium group metal precursor is introduced into said reactor chamber at a rate of about 0.1 to about 500 sccm.

23. The method of claim 22, wherein said rhodium group metal precursor is introduced into said reactor chamber at a rate of about 0.1 to about 5 sccm.

24. The method of claim 16, wherein said reaction gas is introduced into said reactor chamber at a rate of about 1 to about 500 sccm.

25. The method of claim 24, wherein said reaction gas is introduced into said reactor chamber at a rate of about 10 to about 200 sccm.

26. The method of claim 16, further comprising introducing a first purge gas into said reactor chamber after said introducing a rhodium group metal precursor and before said introducing a reaction gas.

27. The method of claim 26, wherein said first purge gas is selected from the group consisting of helium, argon and nitrogen.

28. The method of claim 26 further comprising introducing a second purge gas into said reactor chamber after said introducing a reaction gas.

29. The method of claim 28, wherein said second purge gas is selected from the group consisting of helium, argon and nitrogen.

30. The method of claim 16, wherein said rhodium oxide layer has a resistivity of less than about 100 μ

Ω

cm.

31. A method of conducting atomic layer deposition of an alloy layer of rhodium oxide and a metal selected from the group consisting of Pt, Os, Pd, and Ir on a substrate, said method comprising:

providing a deposition apparatus comprising a reactor chamber having a deposition region;

positioning said substrate on said deposition region;

introducing a rhodium group metal precursor into said reactor chamber under conditions permitting the formation of a rhodium monolayer on said substrate;

introducing a first reaction gas into said reactor chamber, such that said rhodium monolayer is oxidized to a conductive rhodium oxide layer;

introducing a precursor compound comprising a metal selected from the group consisting of Pt, Os, Pd, and Ir;

introducing a second reaction gas into said reactor chamber, wherein said introduction causes removal of organic components from the precursor compound, yielding a conductive alloy layer of rhodium oxide and a metal selected from the group consisting of Pt, Os, Pd, and Ir on said substrate.

32. The method of claim 31, wherein said rhodium group metal precursor comprises an organic rhodium group metal precursor having the formula Ly[Rh]Yz, wherein L is independently selected from the group consisting of neutral and anionic ligands;

y is one of {1, 2, 3, 4};

Y is independently a pi-orbital bonding ligand selected from the group consisting of CO, NO, CN, CS, N₂, PX₃, PR₃, P(OR)₃, AsX₃, AsR₃, As(OR)₃, SbX₃, SbR₃, Sb(OR)₃, NH_xR_3-x, CNR, and RCN, wherein R is an organic group, X is a halide and x is one of {0, 1, 2, 3}; and

z is one of {0, 1, 2, 3, 4}.

33. The method of claim 31, wherein said first reaction gas is ozone.

34. The method of claim 31, wherein said second reaction gas is selected from the group consisting of ozone and oxygen.

35. The method of claim 32, wherein said rhodium group metal precursor is dicarbonyl cyclopentadienyl rhodium.

36. The method of claim 31, wherein said atomic layer deposition is performed at a temperature of about 100°

C. to about 200°

C.

37. The method of claim 36, wherein said atomic layer deposition is performed at a temperature of about 100°

C. to about 150°

C.

38. The method of claim 31, wherein said rhodium group metal precursor is introduced into said reactor chamber at a rate of about 0.1 to about 500 sccm.

39. The method of claim 38, wherein said rhodium group metal precursor is introduced into said reactor chamber at a rate of about 0.1 to about 5 sccm.

40. The method of claim 31, wherein said reaction gas is introduced into said reactor chamber at a rate of about 1 to about 500 sccm.

41. The method of claim 40, wherein said reaction gas is introduced into said reactor chamber at a rate of about 10 to about 200 sccm.

42. The method of claim 31, further comprising introducing a first purge gas into said reactor chamber after said introducing a rhodium group metal precursor and before said introducing a first reaction gas.

43. The method of claim 42, wherein said first purge gas is selected from the group consisting of helium, argon and nitrogen.

44. The method of claim 42 further comprising introducing a second purge gas into said reactor chamber after said introducing a first reaction gas.

45. The method of claim 44, wherein said second purge gas is selected from the group consisting of helium, argon and nitrogen.

46. The method of claim 44, further comprising introducing a third purge gas into said reactor chamber after said introducing a precursor compound comprising a metal selected from the group consisting of Pt, Os, Pd, and Ir.

47. The method of claim 46, wherein said third purge gas is selected from the group consisting of helium, argon and nitrogen.

48. The method of claim 46, further comprising introducing a fourth purge gas into said reactor chamber after said introducing a second reaction gas.

49. The method of claim 48, wherein said fourth purge gas is selected from the group consisting of helium, argon and nitrogen.

50. A method of conducting atomic layer deposition of an alloy layer of rhodium oxide and a metal selected from the group consisting of Pt, Os, Pd, and Ir on an integrated circuit material layer, said method comprising:

providing a deposition apparatus comprising a reactor chamber having a deposition region;

positioning said integrated circuit material layer on said deposition region;

introducing a rhodium group metal precursor into said reactor chamber under conditions permitting the formation of a rhodium monolayer on said material layer;

introducing a first reaction gas into said reactor chamber, such that said rhodium monolayer is oxidized to a rhodium oxide layer;

introducing a precursor compound comprising a metal selected from the group consisting of Pt, Os, Pd, and Ir;

introducing a second reaction gas into said reactor chamber, wherein said introduction causes removal of organic components from the precursor compound, yielding a conductive alloy layer of rhodium oxide and a metal selected from the group consisting of Pt, Os, Pd, and Ir on said material layer.

51. The method of claim 50, wherein said rhodium group metal precursor comprises an organic rhodium group metal precursor having the formula Ly[Rh]Yz, wherein L is independently selected from the group consisting of neutral and anionic ligands;

y is one of {1, 2, 3, 4};

Y is independently a pi-orbital bonding ligand selected from the group consisting of CO, NO, CN, CS, N₂, PX₃, PR₃, P(OR)₃, AsX₃, AsR₃, As(OR)₃, SbX₃, SbR₃, Sb(OR)₃, NH_xR_3-x, CNR, and RCN, wherein R is an organic group, X is a halide and x is one of {0, 1, 2, 3}; and

z is one of {0, 1, 2, 3, 4}.

52. The method of claim 50, wherein said first reaction gas is ozone.

53. The method of claim 50, wherein said second reaction gas is selected from the group consisting of ozone and oxygen.

54. The method of claim 51, wherein said rhodium group metal precursor is dicarbonyl cyclopentadienyl rhodium.

55. The method of claim 50, wherein said atomic layer deposition is performed at a temperature of about 100°

C. to about 200°

C.

56. The method of claim 55, wherein said atomic layer deposition is performed at a temperature of about 100°

C. to about 150°

C.

57. The method of claim 50, wherein said rhodium group metal precursor is introduced into said reactor chamber at a rate of about 0.1 to about 500 sccm.

58. The method of claim 57, wherein said rhodium group metal precursor is introduced into said reactor chamber at a rate of about 0.1 to about 5 sccm.

59. The method of claim 50, wherein said reaction gas is introduced into said reactor chamber at a rate of about 1 to about 500 sccm.

60. The method of claim 59, wherein said reaction gas is introduced into said reactor chamber at a rate of about 10 to about 200 sccm.

61. The method of claim 50, further comprising introducing a first purge gas into said reactor chamber after said introducing a rhodium group metal precursor and before said introducing a first reaction gas.

62. The method of claim 61, wherein said first purge gas is selected from the group consisting of helium, argon and nitrogen.

63. The method of claim 61 further comprising introducing a second purge gas into said reactor chamber after said introducing a first reaction gas.

64. The method of claim 63, wherein said second purge gas is selected from the group consisting of helium, argon and nitrogen.

65. The method of claim 63, further comprising introducing a third purge gas into said reactor chamber after said introducing a precursor compound comprising a metal selected from the group consisting of Pt, Os, Pd, and Ir.

66. The method of claim 65, wherein said third purge gas is selected from the group consisting of helium, argon and nitrogen.

67. The method of claim 65, further comprising introducing a fourth purge gas into said reactor chamber after said introducing a second reaction gas.

68. The method of claim 67, wherein said fourth purge gas is selected from the group consisting of helium, argon and nitrogen.

69. A method of forming a capacitor, said method comprising:

forming a first and second electrode; and

forming a dielectric layer between said first and second electrode, wherein at least one of said first and second electrode is formed by performing atomic layer deposition of a conductive rhodium oxide layer.

70. A method of forming a capacitor, said method comprising:

forming a first and second electrode; and

forming a dielectric layer between said first and second electrode, wherein at least one of said first and second electrode is formed by performing atomic layer deposition of a conductive alloy layer of rhodium oxide and a metal selected from the group consisting of Pt, Os, Pd, and Ir.

71. A capacitor comprising:

a first electrode;

a second electrode; and

a dielectric positioned between said first electrode and said second electrode, wherein at least one of said first and second electrode comprises a continuous ALD deposited conductive rhodium oxide film layer.

72. A capacitor comprising:

a first electrode;

a second electrode; and

a dielectric positioned between said first electrode and said second electrode;

wherein at least one of said first and second electrode comprises a continuous ALD deposited conductive film comprising an alloy of rhodium oxide and a metal selected from the group consisting of Pt, Os, Pd, and Ir.

73. A processor system comprising:

a processor; and

a memory device coupled to exchange data with said processor, said memory device comprising;

at least one continuous ALD deposited conductive rhodium oxide film layer.

74. A processor system comprising:

a processor; and

a memory device coupled to exchange data with said processor, said memory device comprising;

at least one continuous ALD deposited conductive film layer comprising an alloy of rhodium oxide and a metal selected from the group consisting of Pt, Os, Pd, and Ir.

75. A method of conducting atomic layer deposition of a rhodium oxide layer on a substrate, comprising:

providing a deposition apparatus comprising a reactor chamber having a deposition region;

positioning said substrate on said deposition region;

introducing an organo rhodium group metal precursor into said reactor chamber under conditions permitting the formation of an organo rhodium monolayer on said substrate; and

introducing a reaction gas into said reactor chamber, such that said organo rhodium monolayer is fully oxidized to a conductive rhodium oxide layer on said substrate.

76. A method of conducting atomic layer deposition of a rhodium oxide on an integrated circuit material layer, comprising:

providing a deposition apparatus comprising a reactor chamber having a deposition region;

positioning said material layer in said deposition region;

introducing an organo rhodium group metal precursor into said reactor chamber under conditions permitting the formation of an organo rhodium monolayer on said material layer; and

introducing a reaction gas into said reactor chamber, such that said organo rhodium monolayer is fully oxidized to a conductive rhodium oxide layer.

77. A method of conducting atomic layer deposition of an alloy layer of rhodium oxide and a metal selected from the group consisting of Pt, Os, Pd, and Ir on a substrate, said method comprising:

providing a deposition apparatus comprising a reactor chamber having a deposition region;

positioning said substrate on said deposition region;

introducing a rhodium group metal precursor into said reactor chamber under conditions permitting the formation of a rhodium monolayer on said substrate;

introducing a first reaction gas into said reactor chamber, such that said rhodium monolayer is fully oxidized to a conductive rhodium oxide layer;

introducing a precursor compound comprising a metal selected from the group consisting of Pt, Os, Pd, and Ir; and

introducing a second reaction gas into said reactor chamber, wherein said introduction causes removal of organic components from the precursor compound, yielding a conductive alloy layer of fully oxidized rhodium oxide and a metal selected from the group consisting of Pt, Os, Pd, and Ir on said substrate.

78. A method of conducting atomic layer deposition of an alloy layer of rhodium oxide and a metal selected from the group consisting of Pt, Os, Pd, and Ir on an integrated circuit material layer, said method comprising:

providing a deposition apparatus comprising a reactor chamber having a deposition region;

positioning said integrated circuit material layer on said deposition region;

introducing a rhodium group metal precursor into said reactor chamber under conditions permitting the formation of a rhodium monolayer on said material layer;

introducing a first reaction gas into said reactor chamber, such that said rhodium monolayer is fully oxidized to a rhodium oxide layer;

introducing a precursor compound comprising a metal selected from the group consisting of Pt, Os, Pd, and Ir; and

introducing a second reaction gas into said reactor chamber, wherein said introduction causes removal of organic components from the precursor compound, yielding a conductive alloy layer of fully oxidized rhodium oxide and a metal selected from the group consisting of Pt, Os, Pd, and Ir on said material layer.

79. A method of forming a capacitor, said method comprising:

forming a first and second electrode; and

forming a dielectric layer between said first and second electrode, wherein at least one of said first and second electrode is formed by performing atomic layer deposition of a fully oxidized, conductive rhodium oxide layer.

80. A method of forming a capacitor, said method comprising:

forming a first and second electrode; and

forming a dielectric layer between said first and second electrode, wherein at least one of said first and second electrode is formed by performing atomic layer deposition of a conductive alloy layer of fully oxidized rhodium oxide and a metal selected from the group consisting of Pt, Os, Pd, and Ir.