Cyclical deposition of tungsten nitride for metal oxide gate electrode

• US 6,833,161 B2
• Filed: 02/26/2002
• Issued: 12/21/2004
• Est. Priority Date: 02/26/2002
• Status: Expired due to Term

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Li, Ming, Wang, Shulin, Luo, Lee, Chen, Aihua, Kroemer, Ulrich
• Primary Examiner(s): CHEN, BRET P
• Application Number:
  US10/084,767
• Publication Number:
  US 20030161952A1
• Time in Patent Office: 1,029 Days
• Field of Search: 427/250, 427/253, 427/255.392, 427/255.394, 427/255.7
• US Class Current: 427/250
• CPC Class Codes: C23C 16/02 Pretreatment of the material to be coated C23C16/04 takes precedence
• CPC Class Codes: C23C 16/34 Nitrides C23C16/303 takes precedence
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: C23C 16/45527 characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
• CPC Class Codes: H01L 21/28061 the conductor comprising a metal or metal silicide formed by deposition, e.g. sputter deposition, i.e. without a silicidation reaction H01L21/28052 takes precedence
• CPC Class Codes: H01L 21/28562 Selective deposition
• CPC Class Codes: H01L 21/28568 the conductive layers comprising transition metals H01L21/28518 takes precedence
• CPC Class Codes: H01L 21/76841 Barrier, adhesion or liner layers
• CPC Class Codes: H01L 28/60 Electrodes
• CPC Class Codes: H01L 29/4941 with a barrier layer between the silicon and the metal or metal silicide upper layer, e.g. Silicide/TiN/Polysilicon
• CPC Class Codes: H01L 29/66181 Conductor-insulator-semiconductor capacitors, e.g. trench capacitors
• CPC Class Codes: H10B 12/038 the capacitor being in a trench in the substrate

Abstract

A method for depositing a tungsten nitride layer is provided. The method includes a cyclical process of alternately adsorbing a tungsten-containing compound and a nitrogen-containing compound on a substrate. The barrier layer has a reduced resistivity, lower concentration of fluorine, and can be deposited at any desired thickness, such as less than 100 angstroms, to minimize the amount of barrier layer material.

Claims

1. A method for forming a tungsten layer, comprising:

depositing a tungsten nitride barrier layer by alternately pulsing a first tungsten-containing compound and a nitrogen-containing compound; and

depositing a tungsten layer by alternately pulsing a second tungsten-containing compound and a reducing compound.

2. The method of claim 1, wherein the first tungsten-containing compound and the second tungsten-containing compound are each selected from the group consisting of tungsten hexafluoride, tungsten hexacarbonyl, and a combination thereof.

3. The method of claim 1, wherein the first tungsten-containing compound and the second tungsten-containing compound both comprise tungsten hexafluoride.

4. The method of claim 1, wherein the nitrogen-containing compound is selected from the group consisting of nitrogen gas, ammonia, hydrazine, monomethyl hydrazine, dimethyl hydrazine, t-butyl hydrazine, phenyl hydrazine, 2,2′

-azoisobutane, ethylazide, and combinations thereof.

5. The method of claim 1, wherein the nitrogen-containing compound comprises ammonia.

6. The method of claim 1, wherein the reducing compound is selected from the group consisting of silane, disilane, dichlorosilane, borane, diborane, triborane, tetraborane, pentaborane, hexaborane, heptaborane, octaborane, nonaborane and decaborane, and combinations thereof.

7. The method of claim 1, wherein the reducing compound comprises silane.

8. The method of claim 1, further comprising continuously flowing argon.

9. The method of claim 1, wherein the pulsing occurs at a pressure of about 1.5 Torr and a temperature of about 550°

C. or more.

10. The method of claim 1, wherein each pulse of the first and second tungsten-containing compounds has a duration between about 0.2 seconds and about 1 second.

11. The method of claim 1, wherein each pulse of the nitrogen-containing compound has a duration between about 0.2 seconds and about 1 second.

12. The method of claim 1, wherein each pulse of the reducing compound has a duration between about 0.2 seconds and about 1 second.

13. The method of claim 1, wherein each pulse of the first and second tungsten-containing compounds has a flowrate between about 1 sccm and about 400 sccm.

14. The method of claim 1, wherein each pulse of the nitrogen-containing compound has a flowrate between about 5 sccm and about 150 sccm.

15. The method of claim 1, wherein each pulse of the reducing compound has a flowrate between about 5 sccm and about 150 sccm.

16. The method of claim 1, wherein the tungsten nitride barrier layer has a thickness of about 20 angstroms.

17. The method of claim 1, wherein the tungsten layer has a thickness greater than 300 angstroms.

18. The method of claim 1, further comprising pulsing argon between the alternate pulses of the first tungsten-containing compound and the nitrogen-containing compound.

19. The method of claim 1, further comprising pulsing argon between the alternate pulses of the second tungsten-containing compound and the reducing compound.

20. A method for forming a tungsten layer, comprising:

depositing a tungsten nitride barrier layer by alternately pulsing a first tungsten-containing compound and a nitrogen-containing compound; and

depositing a tungsten layer on the barrier layer.

21. The method of claim 20, wherein the tungsten layer is deposited by chemical vapor deposition or physical vapor deposition techniques.

22. The method of claim 20, wherein the tungsten layer is deposited by alternately pulsing a second tungsten-containing compound and a reducing compound.

23. The method of claim 22, wherein the tungsten layer is deposited by alternately pulsing the second tungsten-containing compound and the reducing compound to form a pre-layer having a thickness of about 50 angstroms or less followed by bulk tungsten deposition using chemical vapor deposition or physical vapor deposition.

24. The method claim 20, wherein the first tungsten-containing compound is selected from the group consisting of tungsten hexafluoride, tungsten hexacarbonyl, and a combination thereof.

25. The method of claim 22, wherein the second tungsten-containing compound is selected from the group consisting of tungsten hexafluoride, tungsten hexacarbonyl, and a combination thereof.

26. The method of claim 22, wherein the first tungsten-containing compound and the second tungsten-containing compound both comprise tungsten hexafluoride.

27. The method of claim 20, wherein the nitrogen-containing compound is selected from the group consisting of nitrogen gas, ammonia, hydrazine, monomethyl hydrazine, dimethyl hydrazine, t-butyl hydrazine, phenyl hydrazine, 2,2′

-azoisobutane, ethylazide, and combinations thereof.

28. The method of claim 22, wherein the reducing compound is selected from the group consisting of silane, disilane, dichlorosilane, borane, diborane, triborane, tetraborane, pentaborane, hexaborane, heptaborane, octaborane, nonaborane and decaborane, and combinations thereof.

29. The method of claim 22, wherein the reducing compound comprises silane.

30. The method of claim 20, further comprising continuously flowing argon.

31. The method of claim 20, wherein the pulsing occurs at a pressure of about 1.5 Torr and a temperature of about 550°

C. or more.

32. The method of claim 20, wherein the tungsten nitride barrier layer has a thickness less than 20 angstroms and the tungsten layer has a thickness greater than 300 angstroms.

33. A method for forming a metal gate electrode, comprising:

heating a wafer having a polysilicon layer disposed thereon to a temperature of about 550°

C. or more;

forming a chlorine terminated surface by exposing the polysilicon layer to a chlorine-containing compound;

depositing a tungsten nitride barrier layer over the polysilicon layer, wherein the tungsten nitride barrier layer is formed by alternately pulsing a first tungsten-containing compound and a nitrogen-containing compound until a tungsten nitride layer having a thickness less than about 50 angstroms is deposited; and

depositing a tungsten layer on the tungsten nitride barrier layer.

34. The method of claim 33, wherein the chlorine-containing compound comprises dichlorosilane.

35. The method of claim 33, wherein the nitrogen-containing compound is pulsed first and the first tungsten-containing compound is pulsed second.

36. The method of claim 33, wherein the tungsten layer is deposited by alternately pulsing a second tungsten-containing compound and a reducing compound.

37. The method of claim 33, wherein the tungsten layer is deposited by chemical vapor deposition or physical vapor deposition.

38. The method of claim 36, wherein the tungsten layer is deposited by alternately pulsing the second tungsten-containing compound and the reducing compound to form a pre-layer having a thickness of about 50 angstroms or less followed by chemical vapor deposition or physical vapor deposition to complete the tungsten layer.

39. The method of claim 33, wherein the tungsten layer has a thickness greater than 300 angstroms.

40. The method of claim 33, wherein the first tungsten-containing compound is selected from the group consisting of tungsten hexafluoride, tungsten hexacarbonyl, and a combination thereof.

41. The method of claim 36, wherein the second tungsten-containing compound is selected from the group consisting of tungsten hexafluoride, tungsten hexacarbonyl, and a combination thereof.

42. The method of claim 33, wherein the nitrogen-containing compound is selected from the group consisting of nitrogen gas, ammonia, hydrazine, monomethyl hydrazine, dimethyl hydrazine, t-butyl hydrazine, phenyl hydrazine, 2,2′

-azoisobutane ethylazide, and combinations thereof.

43. The method of claim 36, wherein the reducing compound is selected from the group consisting of silane, disilane, dichlorosilane, borane, diborane, triborane, tetraborane, pentaborane, hexaborane, heptaborane, octaborane, nonaborane and decaborane, and combinations thereof.

44. The method of claim 36, wherein the reducing compound comprises silane.

45. The method of claim 33, further comprising continuously flowing argon.

46. The method of claim 33, wherein the pulsing occurs at a pressure of about 1.5 Torr.

47. A method for forming a metal gate electrode on a wafer, comprising:

heating a wafer having a polysilicon layer disposed thereon to a temperature of about 550°

C. or more;

forming a chlorine terminated surface by exposing the polysilicon layer to a chlorine-containing compound;

reducing the chlorine terminated surface by exposing the polysilicon layer to a nitrogen-containing compound; and

depositing a tungsten layer over the polysilicon layer, wherein the tungsten layer is formed by alternately pulsing a tungsten-containing compound and a reducing compound.

48. The method of claim 47, further comprising depositing a tungsten nitride barrier layer over the polysilicon layer prior to depositing the tungsten layer, wherein the tungsten nitride barrier layer is formed by alternately pulsing tungsten hexafluoride and ammonia until a tungsten nitride layer having a thickness less than 50 angstroms is deposited.

49. The method of claim 47, wherein the chlorine-containing compound comprises dichlorosilane.

50. The method of claim 47, wherein the reducing compound is selected from the group consisting of silane, disilane, dichlorosilane, borane, diborane, triborane, tetraborane, pentaborane, hexaborane, heptaborane, octaborane, nonaborane and decaborane, and combinations thereof.

51. The method of claim 47, wherein the tungsten-containing compound is selected from the group consisting of tungsten hexafluoride, tungsten hexacarbonyl, and a combination thereof.

52. The method of claim 47, wherein the nitrogen-containing compound is selected from the group consisting of nitrogen gas, ammonia, hydrazine, monomethyl hydrazine, dimethyl hydrazine, t-butyl hydrazine, phenyl hydrazine, 2,2′

-azoisobutane, ethylazide, and combinations thereof.

53. The method of claim 47, wherein the tungsten layer has a thickness greater than 300 angstroms.