Method of forming an epitaxially grown nitride-based compound semiconductor crystal substrate structure and the same substrate structure

• US 6,812,051 B2
• Filed: 05/21/2002
• Issued: 11/02/2004
• Est. Priority Date: 05/21/2001
• Status: Expired due to Term

• Current Assignee: Sumitomo Chemical Company Limited
• Original Assignee: NEC Corporation, Hitachi Cable Limited (Proterial Ltd.)
• Inventors: Oshima, Yuichi, Shibata, Masatomo, Usui, Akira
• Primary Examiner(s): Mulpuri, Savitri
• Application Number:
  US10/150,960
• Publication Number:
  US 20030017685A1
• Time in Patent Office: 896 Days
• Field of Search: 438/21-47, 438/479-509, 438/795-797
• US Class Current: 438/22
• CPC Class Codes: C30B 25/02 Epitaxial-layer growth
• CPC Class Codes: C30B 25/18 characterised by the substrate
• CPC Class Codes: C30B 29/403 AIII-nitrides
• CPC Class Codes: C30B 29/406 Gallium nitride
• CPC Class Codes: H01L 21/0242 Crystalline insulating materials
• CPC Class Codes: H01L 21/02458 Nitrides
• CPC Class Codes: H01L 21/02491 Conductive materials
• CPC Class Codes: H01L 21/02502 consisting of two layers
• CPC Class Codes: H01L 21/02513 Microstructure
• CPC Class Codes: H01L 21/0254 Nitrides
• CPC Class Codes: H01L 21/0262 Reduction or decomposition of gaseous compounds, e.g. CVD
• CPC Class Codes: H01L 21/02639 Preparation of substrate for selective deposition
• CPC Class Codes: H01L 21/02647 Lateral overgrowth
• CPC Class Codes: H01L 33/0075 comprising nitride compounds

Abstract

A metal layer is formed directly on a nitride-based compound semiconductor base layer over a substrate body. The metal layer includes at least one metal exhibiting an atomic interaction, with assistance of a heat treatment, to atoms constituting the base layer to promote removal of constitutional atoms from the base layer, whereby pores penetrating the metal layer are formed, while many voids are formed in the nitride-based compound semiconductor base layer. An epitaxial growth of a nitride-based compound semiconductor crystal is made with an initial transient epitaxial growth, which fills the voids, and a subsequent main epitaxial growth over the porous metal layer.

Claims

1. A method of forming an epitaxially grown nitride-based compound semiconductor crystal substrate structure, said method comprising:

forming, directly on a nitride-based compound semiconductor base layer, a metal layer including at least one selected from the group consisting of metals which promote, with assistance of a thermal energy, removal of constitutional atoms of said nitride-based compound semiconductor base layer;

forming pores penetrating said metal layer and voids in said nitride-based compound semiconductor base layer with supply of a thermal energy; and

epitaxially growing a nitride-based compound semiconductor crystal with filling said voids in an initial process and subsequently over said metal layer in a main process to form an epitaxially grown nitride-based compound semiconductor crystal layer over said metal layer.

2. The method as claimed in claim 1, wherein a nitride of said at least one selected metal for said metal layer has a lower free energy than a free energy of said nitride-based compound semiconductor base layer.

3. The method as claimed in claim 2, wherein said at least one selected metal includes Ti, Ti-containing alloys, Fe, Ni, Zr, Hf, W, and Pt.

4. The method as claimed in claim 1, wherein said voids have an averaged depth of not less than 10 nanometers.

5. The method as claimed in claim 1, wherein said voids are formed at a porosity rate in the range of 10% to 90%.

6. The method as claimed in claim 1, wherein said metal layer has a thickness of not more than 500 nanometers.

7. The method as claimed in claim 1, wherein said thermal energy is supplied by a heat treatment at a temperature of not less than 700°

C.

8. The method as claimed in claim 7, wherein said heat treatment is carried out in the presence of hydrogen.

9. The method as claimed in claim 8, wherein said heat treatment is carried out in the presence of a mixture gas containing hydrogen and nitrogen.

10. The method as claimed in claim 7, wherein said heat treatment and said epitaxial growth process for said nitride-based semiconductor crystal are carried out in a same reaction chamber sequentially without exposure to an open atmosphere.

11. The method as claimed in claim 1, wherein said pores are uniformly distributed over said metal layer, and said voids are also uniformly distributed over said nitride-based compound semiconductor base layer.

12. The method as claimed in claim 11, wherein said pores are formed in said metal layer at an averaged pore diameter in the order of 0.1 micrometer and at an averaged distance between adjacent twos of said pores in the order of 0.1 micrometer.

13. The method as claimed in claim 1, wherein said nitride-based compound semiconductor crystal within said voids is lower in dislocation density than said nitride-based compound semiconductor base layer over said metal layer.

14. The method as claimed in claim 1, wherein said epitaxially grown nitride-based compound semiconductor crystal includes a surface region which has a dislocation density of 1E8 cm⁻

2.

15. The method as claimed in claim 14, wherein said surface region of said epitaxially grown nitride-based compound semiconductor crystal has a surface planarity within ±

0.2 micrometers in a length order of 500 micrometers.

16. The method as claimed in claim 14, wherein, of said surface region of said epitaxially grown nitride-based compound semiconductor crystal, a full width at half maximum of a (0002)-diffraction rocking curve and another full width at half maximum of a (10—

10)-diffraction rocking curve are both at most 0.1 degree respectively.

17. The method as claimed in claim 1, wherein said surface region of said epitaxially grown nitride-based compound semiconductor crystal has a C-plane.

18. The method as claimed in claim 17, wherein said nitride-based compound semiconductor base layer has a surface generally oriented to [0001], and said metal layer has a hexagonal crystal structure generally oriented to [0001].

19. The method as claimed in claim 17, wherein said nitride-based compound semiconductor base layer has a surface generally oriented to [0001], and said metal layer has a cubic crystal structure generally oriented to [111].

20. The method as claimed in claim 1, further comprising:

forming said nitride-based compound semiconductor base layer over a crystal supporting substrate.

21. The method as claimed in claim 20, further comprising:

removing said crystal supporting substrate, said nitride-based compound semiconductor base layer and said metal layer to form a single layered substrate structure of said epitaxially grown nitride-based compound semiconductor crystal.

22. The method as claimed in claim 1, further comprising:

forming a dielectric mask pattern over a crystal supporting substrate; and

epitaxially growing said nitride-based compound semiconductor base layer over said dielectric mask pattern.

23. The method as claimed in claim 22, further comprising:

removing said crystal supporting substrate, said dielectric mask pattern, said nitride-based compound semiconductor base layer and said metal layer to form a single layered substrate structure of said epitaxially grown nitride-based compound semiconductor crystal.

24. The method as claimed in claim 1, further comprising;

forming a dielectric mask pattern over said epitaxially grown nitride-based compound semiconductor crystal over said metal layer; and

further epitaxially growing a nitride-based compound semiconductor crystal top layer over said dielectric mask pattern.

25. The method as claimed in claim 24, further comprising:

removing said crystal supporting substrate, said nitride-based compound semiconductor base layer, said metal layer, said dielectric mask pattern, and said epitaxially grown nitride-based compound semiconductor crystal to form a single layered substrate structure of said nitride-based compound semiconductor crystal top layer.

26. A method of forming an epitaxially grown nitride-based compound semiconductor crystal substrate structure, said method comprising:

forming voids in a nitride-based compound semiconductor base layer and pores penetrating a metal layer directly on said nitride-based compound semiconductor base layer with supplying a thermal energy, wherein said metal layer includes at least one selected from the group consisting of metals which promote, with assistance of said thermal energy, removal of constitutional elements of said nitride-based compound semiconductor base layer; and

epitaxially growing a nitride-based compound semiconductor crystal with filling said voids in an initial process and subsequently over said metal layer in a main process to form an epitaxially grown nitride-based compound semiconductor crystal layer over said metal layer.

27. The method as claimed in claim 26, wherein a nitride of said at least one selected metal for said metal layer has a lower free energy than a free energy of said nitride-based compound semiconductor base layer.

28. The method as claimed in claim 26, wherein said voids have an averaged depth of not less than 10 nanometers.

29. The method as claimed in claim 26, wherein said voids are formed at a porosity rate in the range of 10% to 90%.

30. The method as claimed in claim 26, wherein said metal layer has a thickness of not more than 500 nanometers.

31. The method as claimed in claim 26, wherein said thermal energy is supplied by a heat treatment at a temperature of not less than 700°

C.

32. The method as claimed in claim 26, wherein said nitride-based compound semiconductor crystal within said voids is lower in dislocation density than said nitride-based compound semiconductor base layer over said metal layer.

33. The method as claimed in claim 26, wherein said epitaxially grown nitride-based compound semiconductor crystal includes a surface region which has a dislocation density of 1E8 cm⁻

2.

34. The method as claimed in claim 33, wherein said surface region of said epitaxially grown nitride-based compound semiconductor crystal has a surface planarity within ±

0.2 micrometers in a length order of 500 micrometers.

35. The method as claimed in claim 33, wherein, of said surface region of said epitaxially grown nitride-based compound semiconductor crystal, a full width at half maximum of a (0002)-diffraction rocking curve and another full width at half maximum of a (10—

10)-diffraction rocking curve are both at most 0.1 degree respectively.

36. The method as claimed in claim 26, further comprising:

forming said nitride-based compound semiconductor base layer over a crystal supporting substrate.

37. The method as claimed in claim 36, further comprising:

removing said crystal supporting substrate, said nitride-based compound semiconductor base layer and said metal layer to form a single layered substrate structure of said epitaxially grown nitride-based compound semiconductor crystal.

38. The method as claimed in claim 26, further comprising:

forming a dielectric mask pattern over a crystal supporting substrate; and

epitaxially growing said nitride-based compound semiconductor base layer over said dielectric mask pattern.

39. The method as claimed in claim 38, further comprising:

removing said crystal supporting substrate, said dielectric mask pattern, said nitride-based compound semiconductor base layer and said metal layer to form a single layered substrate structure of said epitaxially grown nitride-based compound semiconductor crystal.

40. The method as claimed in claim 26, further comprising:

forming a dielectric mask pattern over said epitaxially grown nitride-based compound semiconductor crystal over said metal layer; and

further epitaxially growing a nitride-based compound semiconductor crystal top layer over said dielectric mask pattern.

41. The method as claimed in claim 40, further comprising:

removing said crystal supporting substrate, said nitride-based compound semiconductor base layer, said metal layer, said dielectric mask pattern, and said epitaxially grown nitride-based compound semiconductor crystal to form a single layered substrate structure of said nitride-based compound semiconductor crystal top layer.

42. A method of epitaxially growing a nitride-based compound semiconductor crystal, said method comprising:

forming voids in a nitride-based compound semiconductor base layer and pores penetrating a metal layer with supplying an energy in the presence of a direct contact between said nitride-based compound semiconductor base layer and said metal layer, wherein said metal layer includes at least one selected from the group consisting of metals which promote, with assistance of said energy, removal of constitutional atoms of said nitride-based compound semiconductor base layer; and

carrying out an epitaxial growth of a nitride-based compound semiconductor crystal with filling said voids in an initial process and subsequently over said metal layer in a main process.

43. The method as claimed in claim 42, wherein a nitride of said at least one selected metal for said metal layer has a lower free energy than a free energy of said nitride-based compound semiconductor base layer.

44. The method as claimed in claim 42, wherein said voids have an averaged depth of not less than 10 nanometers.

45. The method as claimed in claim 42, wherein said voids are formed at a porosity rate in the range of 10% to 90%.

46. The method as claimed in claim 42, wherein said metal layer has a thickness of not more than 500 nanometers.

47. The method as claimed in claim 42, wherein said thermal energy is supplied by a heat treatment at a temperature of not less than 700°

C.

48. The method as claimed in claim 42, wherein said nitride-based compound semiconductor crystal within said voids is lower in dislocation density than said nitride-based compound semiconductor base layer over said metal layer.

49. The method as claimed in claim 42, wherein said epitaxially grown nitride-based compound semiconductor crystal includes a surface region which has a dislocation density of 1E8 cm⁻

2.

50. The method as claimed in claim 49, wherein said surface region of said epitaxially grown nitride-based compound semiconductor crystal has a surface planarity within ±

0.2 micrometers in a length order of 500 micrometers.

51. The method as claimed in claim 49, wherein, of said surface region of said epitaxially grown nitride-based compound semiconductor crystal, a full width at half maximum of a (0002)-diffraction rocking curve and another full width at half maximum of a (10—

10)-diffraction rocking curve are both at most 0.1 degree respectively.