Atomic layer deposition of metal oxynitride layers as gate dielectrics and semiconductor device structures utilizing metal oxynitride layers

• US 20040144980A1
• Filed: 01/27/2003
• Published: 07/29/2004
• Est. Priority Date: 01/27/2003
• Status: Abandoned Application

• Current Assignee: Micron Technology, Inc.
• Original Assignee: Micron Technology, Inc.
• Inventors: Ahn, Kie Y., Forbes, Leonard
• Application Number:
  US10/352,507
• Publication Number:
  US 20040144980A1
• Time in Patent Office: Days
• US Class Current: 257/69
• CPC Class Codes: H01L 21/02175 characterised by the metal H01L21/02197 takes precedence
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/28194 by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition H01L21/28202 takes precedence
• CPC Class Codes: H01L 21/28202 in a nitrogen-containing ambient, e.g. nitride deposition, growth, oxynitridation, NH3 nitridation, N2O oxidation, thermal nitridation, RTN, plasma nitridation, RPN
• CPC Class Codes: H01L 21/3141 Deposition using atomic layer deposition techniques [ALD]
• CPC Class Codes: H01L 21/3143 composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers
• CPC Class Codes: H01L 29/513 the variation being perpendicular to the channel plane
• CPC Class Codes: H01L 29/518 the insulating material containing nitrogen, e.g. nitride, oxynitride, nitrogen-doped material

Abstract

A metal oxynitride layer formed by atomic layer deposition of a plurality of reacted monolayers, the monolayers comprising at least one each of a metal, an oxide and a nitride. The metal oxynitride layer is formed from zirconium oxynitride, hafnium oxynitride, tantalum oxynitride, or mixtures thereof. The metal oxynitride layer is used in gate dielectrics as a replacement material for silicon dioxide. A semiconductor device structure having a gate dielectric formed from a metal oxynitride layer is also disclosed.

Claims

1. A method of forming a metal oxynitride layer, comprising:

providing a semiconductor substrate; and

forming a metal oxynitride layer on a surface of the semiconductor substrate by atomic layer deposition.

2. The method of claim 1, wherein forming the metal oxynitride layer on a surface of the semiconductor substrate comprises separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate, the plurality of gaseous precursors comprising a metal gaseous precursor and at least two nonmetallic gaseous precursors.

3. The method of claim 2, wherein separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate comprises purging a first gaseous precursor of the plurality of gaseous precursors from the surface of the semiconductor substrate before a second gaseous precursor of the plurality of gaseous precursors is introduced to the surface of the semiconductor substrate.

4. The method of claim 2, wherein separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate comprises separately introducing the metal gaseous precursor selected from the group consisting of zirconium tetrachloride, zirconium tetraiodide, hafnium tetrachloride, hafnium tetraiodide, and a halogenated tantalum to the surface of the semiconductor substrate.

5. The method of claim 2, wherein separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate comprises separately introducing an oxygen-containing gaseous precursor and a nitrogen-containing gaseous precursor as the at least two nonmetallic gaseous precursors to the surface of the semiconductor substrate.

6. The method of claim 5, wherein separately introducing an oxygen-containing gaseous precursor and a nitrogen-containing gaseous precursor as the at least two nonmetallic gaseous precursors to the surface of the semiconductor substrate comprises separately introducing the oxygen-containing gaseous precursor selected from the group consisting of at least one of water and hydrogen peroxide and separately introducing the nitrogen-containing gaseous precursor selected from the group consisting of at least one of ammonia, tert-butylamine, allylamine, and 1,1-dimethylhydrazine.

7. The method of claim 1, wherein forming a metal oxynitride layer on a surface of the semiconductor substrate by atomic layer deposition comprises forming monolayers of metal, oxide, and nitride by atomic layer deposition and reacting the metal, oxide, and nitride monolayers to form the metal oxynitride layer.

8. The method of claim 1, wherein forming a metal oxynitride layer on a surface of the semiconductor substrate by atomic layer deposition comprises forming a zirconium oxynitride layer, a hafnium oxynitride layer, a tantalum oxynitride layer, or mixtures thereof on the surface of the semiconductor substrate.

9. The method of claim 1, wherein forming a metal oxynitride layer on a surface of the semiconductor substrate by atomic layer deposition comprises forming the metal oxynitride layer at a thickness of approximately 15 Å

to approximately 200 Å

.

10. The method of claim 1, wherein forming a metal oxynitride layer on a surface of the semiconductor substrate comprises depositing the metal oxynitride layer conformally.

11. A method of forming a metal oxynitride layer, comprising:

providing a semiconductor substrate; and

separately introducing a plurality of gaseous precursors to a surface of the semiconductor substrate, the plurality of gaseous precursors comprising a metal gaseous precursor and at least two nonmetallic gaseous precursors.

12. The method of claim 11, wherein separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate comprises purging a first gaseous precursor of the plurality of gaseous precursors from the surface of the semiconductor substrate before a second gaseous precursor of the plurality of gaseous precursors is introduced to the surface of the semiconductor substrate.

13. The method of claim 11, wherein separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate comprises separately introducing the metal gaseous precursor selected from the group consisting of zirconium tetrachloride, zirconium tetraiodide, hafnium tetrachloride, hafnium tetraiodide, and a halogenated tantalum to the surface of the semiconductor substrate.

14. The method of claim 11, wherein separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate comprises separately introducing an oxygen-containing gaseous precursor and a nitrogen-containing gaseous precursor to the surface of the semiconductor substrate.

15. The method of claim 14, wherein separately introducing an oxygen-containing gaseous precursor and a nitrogen-containing gaseous precursor to the surface of the semiconductor substrate comprises separately introducing at least one of water or hydrogen peroxide as the oxygen-containing gaseous precursor and separately introducing at least one of ammonia, tert-butylamine, allylamine, and 1,1-dimethylhydrazine as the nitrogen-containing gaseous precursor.

16. The method of claim 11, further comprising forming monolayers of metal, oxide, and nitride and reacting the metal, oxide, and nitride monolayers to form the metal oxynitride layer.

17. The method of claim 16, wherein forming monolayers of metal, oxide, and nitride and reacting the metal, oxide, and nitride monolayers to form the metal oxynitride layer comprises forming a zirconium oxynitride layer, a hafnium oxynitride layer, a tantalum oxynitride layer, or mixtures thereof on the surface of the semiconductor substrate.

18. The method of claim 16, wherein forming monolayers of metal, oxide, and nitride and reacting the metal, oxide, and nitride monolayers to form the metal oxynitride layer comprises forming the metal oxynitride layer at a thickness of approximately 15 Å

to approximately 200 Å

.

19. A method of forming a semiconductor device structure, comprising:

providing a semiconductor substrate;

forming a metal oxynitride gate dielectric layer by atomic layer deposition on a surface of the semiconductor substrate; and

forming a gate over the metal oxynitride gate dielectric layer.

20. The method of claim 19, wherein forming a metal oxynitride gate dielectric layer by atomic layer deposition on a surface of the semiconductor substrate comprises separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate, the plurality of gaseous precursors comprising a metal gaseous precursor and at least two nonmetallic gaseous precursors.

21. The method of claim 20, wherein separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate comprises purging a first gaseous precursor of the plurality of gaseous precursors from the surface of the semiconductor substrate before a second gaseous precursor of the plurality of gaseous precursors is introduced to the surface of the semiconductor substrate.

22. The method of claim 21, wherein separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate comprises separately introducing the metal gaseous precursor selected from the group consisting of zirconium tetrachloride, zirconium tetraiodide, hafnium tetrachloride, hafnium tetraiodide, and a halogenated tantalum to the surface of the semiconductor substrate.

23. The method of claim 21, wherein separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate comprises separately introducing an oxygen-containing gaseous precursor and a nitrogen-containing gaseous precursor to the surface of the semiconductor substrate.

24. The method of claim 23, wherein separately introducing an oxygen-containing gaseous precursor and a nitrogen-containing gaseous precursor to the surface of the semiconductor substrate comprises separately introducing at least one of water or hydrogen peroxide as the oxygen-containing gaseous precursor and separately introducing at least one of ammonia, tert-butylamine, allylamine, and 1,1-dimethylhydrazine as the nitrogen-containing gaseous precursor.

25. The method of claim 19, wherein forming a metal oxynitride gate dielectric layer by atomic layer deposition on a surface of the semiconductor substrate comprises forming monolayers of metal, oxide, and nitride by atomic layer deposition and reacting the metal, oxide, and nitride monolayers to form the metal oxynitride layer.

26. The method of claim 19, wherein forming a metal oxynitride gate dielectric layer by atomic layer deposition on a surface of the semiconductor substrate comprises forming a zirconium oxynitride layer, a hafnium oxynitride layer, a tantalum oxynitride layer, or mixtures thereof on the surface of the semiconductor substrate.

27. The method of claim 19, wherein forming a metal oxynitride gate dielectric layer by atomic layer deposition on a surface of the semiconductor substrate comprises forming the metal oxynitride gate dielectric layer at a thickness of approximately 15 Å

to approximately 200 Å

.

28. The method of claim 19, wherein forming a metal oxynitride gate dielectric layer by atomic layer deposition on a surface of the semiconductor substrate comprises depositing the metal oxynitride layer conformally.

29. A semiconductor device structure, comprising:

a semiconductor substrate;

a metal oxynitride gate dielectric layer comprising a plurality of reacted monolayers on a surface of the semiconductor substrate; and

a gate over the metal oxynitride gate dielectric layer.

30. The semiconductor device structure of claim 29, wherein the metal oxynitride gate dielectric layer comprises a conformally deposited metal oxynitride layer.

31. The semiconductor device structure of claim 29, wherein the metal oxynitride gate dielectric layer comprises zirconium oxynitride, hafnium oxynitride, tantalum oxynitride, or mixtures thereof.

32. The semiconductor device structure of claim 29, wherein the metal oxynitride gate dielectric layer has a thickness of approximately 15 Å

to approximately 200 Å

.

33. An atomic deposition layer, comprising:

a metal oxynitride layer comprising a plurality of reacted monolayers.

34. The atomic deposition layer of claim 33, wherein the plurality of reacted monolayers of the metal oxynitride layer comprises at least one metal monolayer, at least one nitride monolayer, and at least one oxide monolayer.

35. The atomic deposition layer of claim 33, wherein the metal oxynitride layer comprises zirconium oxynitride, hafnium oxynitride, tantalum oxynitride, or mixtures thereof.

36. The atomic deposition layer of claim 33, wherein the metal oxynitride layer is approximately 15 Å

to approximately 200 Å

thick.

37. A semiconductor device structure comprising a metal oxynitride layer formed by the process comprising:

providing a semiconductor substrate; and

forming the metal oxynitride layer on a surface of the semiconductor substrate by separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate.

38. The semiconductor device structure of claim 37, wherein forming the metal oxynitride layer on a surface of the semiconductor substrate by separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate comprises separately introducing a metal gaseous precursor and at least two nonmetallic gaseous precursors to the surface of the semiconductor substrate.

39. The semiconductor device structure of claim 38, wherein separately introducing a metal gaseous precursor and at least two nonmetallic gaseous precursors to the surface of the semiconductor substrate comprises separately introducing the metal gaseous precursor selected from the group consisting of zirconium tetrachloride, zirconium tetraiodide, hafnium tetrachloride, hafnium tetraiodide, and a halogenated tantalum.

40. The semiconductor device structure of claim 38, wherein separately introducing a metal gaseous precursor and at least two nonmetallic gaseous precursors to the surface of the semiconductor substrate comprises separately introducing an oxygen-containing gaseous precursor and a nitrogen-containing gaseous precursor to the surface of the semiconductor substrate.

41. The semiconductor device structure of claim 40, wherein separately introducing an oxygen-containing gaseous precursor and a nitrogen-containing gaseous precursor to the surface of the semiconductor substrate comprises separately introducing at least one of water or hydrogen peroxide as the oxygen-containing gaseous precursor and separately introducing at least one of ammonia, tert-butylamine, allylamine, and 1,1-dimethylhydrazine as the nitrogen-containing gaseous precursor.

42. The semiconductor device structure of claim 37, wherein forming the metal oxynitride layer on a surface of the semiconductor substrate by separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate comprises purging a first gaseous precursor of the plurality of gaseous precursors from the surface of the semiconductor substrate before a second gaseous precursor of the plurality of gaseous precursors is introduced to the surface of the semiconductor substrate.

43. The semiconductor device structure of claim 37, wherein forming the metal oxynitride layer on a surface of the semiconductor substrate by separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate comprises forming monolayers of metal, oxide, and nitride by atomic layer deposition and reacting the metal, oxide, and nitride monolayers to form the metal oxynitride layer.

44. The semiconductor device structure of claim 37, wherein forming the metal oxynitride layer on a surface of the semiconductor substrate by separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate comprises forming a zirconium oxynitride layer, a hafnium oxynitride layer, a tantalum oxynitride layer, or mixtures thereof on the surface of the semiconductor substrate.

45. The semiconductor device structure of claim 37, wherein forming the metal oxynitride layer on a surface of the semiconductor substrate by separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate comprises forming the metal oxynitride layer at a thickness of approximately 15 Å

to approximately 200 Å

.

46. The semiconductor device structure of claim 37, wherein forming the metal oxynitride layer on a surface of the semiconductor substrate by separately introducing a plurality of gaseous precursors to the surface of the semiconductor substrate comprises depositing the metal oxynitride layer conformally.

47. A method of forming a metal oxynitride layer, comprising:

providing a semiconductor substrate;

interacting a plurality of gaseous precursors with a surface of the semiconductor substrate to form a plurality of metal, oxide, and nitride monolayers thereon; and

reacting the plurality of metal, oxide, and nitride monolayers to form the metal oxynitride layer.