Method of fabricating a highly reliable gate oxide

• US 6,514,828 B2
• Filed: 04/20/2001
• Issued: 02/04/2003
• Est. Priority Date: 04/20/2001
• Status: Expired due to Term

• Current Assignee: Micron Technology, Inc.
• Original Assignee: Micron Technology, Inc.
• Inventors: Ahn, Kie Y., Forbes, Leonard
• Primary Examiner(s): Nguyen, Tuan H.
• Assistant Examiner(s): NGUYEN, THANH T
• Application Number:
  US09/838,335
• Publication Number:
  US 20020155688A1
• Time in Patent Office: 655 Days
• Field of Search: 438/592, 438/3.197, 438/593-595, 438/585, 438/685, 438/656, 438/648, 438/287, 438/291
• US Class Current: 438/297
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02244 of a metallic layer
• CPC Class Codes: H01L 21/02252 formation by plasma treatment, e.g. plasma oxidation of the substrate after treatment of an insulating film by plasma H01L21/3105 and subgroups
• CPC Class Codes: H01L 21/28211 in a gaseous ambient using an oxygen or a water vapour, e.g. RTO, possibly through a layer H01L21/28194 and H01L21/28202 take precedence
• CPC Class Codes: H01L 21/31683 of metallic layers, e.g. Al deposited on the body, e.g. formation of multi-layer insulating structures
• CPC Class Codes: H01L 29/517 the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate H01L29/518 takes precedence

Abstract

An ultra-thin gate oxide layer of hafnium oxide (HfO₂) and a method of formation are disclosed. The ultra-thin gate oxide layer of hafnium oxide (HfO₂) is formed by a two-step process. A thin hafnium (Hf) film is first formed by thermal evaporation at a low substrate temperature, after which the thin hafnium film is radically oxidized using a krypton/oxygen (Kr/O₂) high-density plasma to form the ultra-thin gate oxide layer of hafnium oxide (HfO₂). The ultra-thin gate oxide layer of hafnium oxide (HfO₂) formed by the method of the present invention is thermally stable in contact with silicon and is resistive to impurity diffusion at the HfO₂/silicon interface. The formation of the ultra-thin gate oxide layer of hafnium oxide (HfO₂) eliminates the need for a diffusion barrier layer, allows thickness uniformity of the field oxide on the isolation regions and, more importantly, preserves the atomically smooth surface of the silicon substrate.

Claims

1. A method for forming a gate structure for a semiconductor device comprising the steps of:

forming a hafnium layer on a semiconductor substrate by thermal evaporation at a temperature of about 150°

C. to about 200°

C.;

converting said hafnium layer to a hafnium oxide layer by oxidizing said hafnium layer; and

forming a conductive layer over said hafnium oxide layer.

2. The method of claim 1, wherein said hafnium layer is formed to a thickness of about 10 Angstroms to about 100 Angstroms.

3. The method of claim 2, wherein said hafnium layer is formed to a thickness of about 10 Angstroms to about 50 Angstroms.

4. The method of claim 1, wherein said hafnium oxide layer is formed by oxidizing said hafnium layer with atomic oxygen.

5. The method of claim 4, wherein said hafnium oxide layer is formed by oxidizing said hafnium layer with a high-density krypton plasma.

6. The method of claim 5, wherein said hafnium oxide layer is formed by oxidizing said hafnium layer with a high-density krypton plasma at about 400°

C.

7. The method of claim 6, wherein said hafnium oxide layer is formed by oxidizing said hafnium layer with a high-density 3% oxygen/krypton plasma at about 400°

C.

8. The method of claim 7, wherein said hafnium oxide layer is formed by oxidizing said hafnium layer with a 3% high-density oxygen/krypton plasma at about 400°

C. and at about 1 Torr.

9. The method of claim 1, wherein said conductive layer is formed of a material selected from the group consisting of metals, metal silicides, polysilicon and metal oxides.

10. The method of claim 1, wherein said semiconductor substrate is a silicon substrate.

11. The method of claim 10, wherein said silicon substrate has a surface of <

100>

orientation, said surface being adjacent to said hafnium oxide layer.

12. The method of claim 10, wherein said silicon substrate has a surface of <

111>

orientation, said surface being adjacent to said hafnium oxide layer.

13. The method of claim 1 further comprising forming a silicide layer overlying said conductive layer.

14. The method of claim 13 further comprising forming a cap layer overlying said silicide layer.

15. A method of forming a memory cell comprising the steps of:

forming at least one gate stack over a substrate, said gate stack comprising a hafnium oxide layer of about 10 Angstroms to about 100 Angstroms thick and a conductive layer over and in contact with said hafnium oxide layer, wherein said hafnium oxide layer is formed by oxidizing a hafnium layer with a high-density krypton plasma;

forming source and drain regions in said substrate on opposite sides of each of said plurality of gate stacks; and

forming a storage device connected to one of said source and drain regions.

16. The method of claim 15, wherein said hafnium layer is formed by thermal evaporation.

17. The method of claim 16, wherein said hafnium layer is formed by electron beam evaporation.

18. The method of claim 17, wherein said hafnium layer is formed at a temperature of about 150°

C. to about 200°

C.

19. The method of claim 18, wherein said hafnium layer is formed to a thickness of about 10 Angstroms to about 100 Angstroms.

20. The method of claim 19, wherein said hafnium layer is formed to a thickness of about 10 Angstroms to about 50 Angstroms.

21. The method of claim 15, wherein said hafnium oxide layer is formed by oxidizing said hafnium layer with a high-density krypton plasma at about 400°

C.

22. The method of claim 21, wherein said hafnium oxide layer is formed by oxidizing said hafnium layer with a high-density 3% oxygen/krypton plasma at about 400°

C.

23. The method of claim 22, wherein said hafnium oxide layer is formed by oxidizing said hafnium layer with a 3% high-density oxygen/krypton plasma at about 400°

C. and at about 1 Torr.

24. The method of claim 15, wherein said conductive layer is formed of a material selected from the group consisting of metals, metal silicides, polysilicon and metal oxides.

25. The method of claim 15, wherein said substrate is a semiconductor substrate.

26. The method of claim 25, wherein said semiconductor substrate is a silicon substrate.

27. The method of claim 26, wherein said silicon substrate has a surface of <

100>

orientation, said surface being adjacent to said hafnium oxide layer.

28. The method of claim 26, wherein said silicon substrate has a surface of <

111>

orientation, said surface being adjacent to said hafnium oxide layer.

29. A method of providing an oxide layer over of a surface of a silicon substrate comprising the steps of:

thermally evaporating a hafnium layer over said surface at a temperature of about 150°

C. to about 200°

C.; and

oxidizing said hafnium layer with a high-density krypton plasma to form a hafnium oxide layer.

30. The method of claim 29, wherein said hafnium layer is formed by electron beam evaporation.

31. The method of claim 29, wherein said hafnium layer is formed to a thickness of about 10 Angstroms to about 100 Angstroms.

32. The method of claim 31, wherein said hafnium layer is formed to a thickness of about 10 Angstroms to about 50 Angstroms.

33. The method of claim 29, wherein said hafnium oxide layer is formed by oxidizing said hafnium layer with a high-density krypton plasma at about 400°

C.

34. The method of claim 33, wherein said hafnium oxide layer is formed by oxidizing said hafnium layer with a high-density 3% oxygen/krypton plasma at about 400°

C.

35. The method of claim 34, wherein said hafnium oxide layer is formed by oxidizing said hafnium layer with a 3% high-density oxygen/krypton plasma at about 400°

C. and at about 1 Torr.

36. The method of claim 29, wherein said surface has <

100>

orientation.

37. The method of claim 29, wherein said surface has <

111>

orientation.

38. A method of forming a gate structure for a semiconductor device comprising the steps of:

thermally evaporating a hafnium layer over a surface of a silicon substrate at a temperature of about 150°

C. to about 200°

C.;

oxidizing said hafnium layer with a high-density 3% oxygen/krypton plasma at about 400°

C. and at about 1 Torr to form a hafnium oxide layer; and

forming a conductive layer over said hafnium oxide layer.

39. A method of providing a hafnium oxide layer having a thickness of about 10 Angstroms over of a surface of a silicon substrate comprising the steps of:

thermally evaporating a hafnium layer over said surface at a temperature of about 150°

C. to about 200°

C.; and

oxidizing said hafnium layer with a high-density 3% oxygen/krypton plasma at about 400°

C. and at about 1 Torr to form said hafnium oxide layer.