Crystal growth method, crystal growth apparatus, group-III nitride crystal and group-III nitride semiconductor device

• US 6,949,140 B2
• Filed: 12/03/2002
• Issued: 09/27/2005
• Est. Priority Date: 12/05/2001
• Status: Active Grant

• Current Assignee: Ricoh Company Limited
• Original Assignee: Ricoh Company Limited
• Inventors: Sarayama, Seiji, Aoki, Masato, Iwata, Hirokazu, Yamane, Hisanori, Shimada, Masahiko
• Primary Examiner(s): KUNEMUND, ROBERT M
• Application Number:
  US10/308,149
• Publication Number:
  US 20030164138A1
• Time in Patent Office: 1,029 Days
• Field of Search: 117/223, 117/81, 117/82, 117/83, 117/904
• US Class Current: 117/81
• CPC Class Codes: C30B 11/00 Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method C30B13/00, C30B15/00, C30B17/00, C30B19/00 take precedence; under a protective fluid C30B27/00
• CPC Class Codes: C30B 29/403 AIII-nitrides
• CPC Class Codes: C30B 29/406 Gallium nitride
• CPC Class Codes: C30B 9/00 Single-crystal growth from melt solutions using molten solvents by normal or gradient freezing C30B11/00; by zone-melting C30B13/00; by crystal pulling C30B15/00; on immersed seed crystal C30B17/00; by liquid phase epitaxial growth C30B19/00; under a protective fluid C30B27/00
• CPC Class Codes: Y10T 117/1092 Shape defined by a solid member other than seed or product [e.g., Bridgman-Stockbarger]

Abstract

A group-III nitride crystal growth method, comprising the steps of: a) preparing a mixed molten liquid of an alkaline metal and a material at least comprising a group-III metal; b) growing a group-III nitride crystal of the group-III metal and nitrogen from the mixed molten liquid and a material at least comprising nitrogen; and c) setting a predetermined crystal growth condition according to a zone defined by a pressure and a temperature in said step b).

Claims

1. A group-III nitride crystal growth method, comprising the steps of:

a) preparing a mixed molten liquid of an alkaline metal and a material at least comprising a group-III metal;

b) growing a group-III nitride crystal of the group-III metal and nitrogen from the mixed molten liquid and a material at least comprising nitrogen; and

c) setting a predetermined crystal growth condition according to a zone defined by a pressure and a temperature in said step b).

2. The method as claimed in claim 1, wherein:

said step c) sets the predetermined crystal growth condition according to the zone from among a plurality of zones each defined by the pressure and temperature in said step b); and

different modes of crystal growth may occur according to respective ones of the plurality of zones.

3. The method as claimed in claim 2, wherein:

under the crystal growth condition according to a zone of the plurality of zones, the crystal grows from a seed crystal.

4. The method as claimed in claim 2, wherein:

the plurality of zones are defined by a curve expressed by the following expression;

log P=a/T+b

where;

P denotes the effective pressure (Pa) of nitrogen in a reaction vessel in which said step b) is performed;

T denotes the absolute temperature (K) of the mixed molten liquid; and

a and b denote coefficients.

5. The method as claimed in claim 4, wherein:

the curve expressed by the following formula;

log P=a/T+b

is controllable according to a ratio in amount between the alkaline metal and group-III metal to be used in said step b).

6. The method as claimed in claim 1, wherein:

in said step b), the crystal is made to grow from a seed crystal under the crystal growth condition such that crystal growth from a seed crystal may occur.

7. The method as claimed in claim 1, wherein:

in said step b), the crystal is made to grow in a pillar shape under the crystal growth condition such that crystal growth for a pillar-shape crystal may occur.

8. The method as claimed in claim 1, wherein:

in said step b), the crystal is made to grow in a plate shape under the crystal growth condition such that crystal growth for a plate-shape crystal may occur.

9. The method as claimed in claim 1, wherein:

the crystal growth is performed for a crystal of GaN where sodium (Na) is used as the alkaline metal;

gallium (Ga) is used as the material at least comprising a group-III metal; and

a nitrogen gas (N₂) is used as the material at least comprising nitrogen; and

the crystal growth condition is defined by the pressure of the nitrogen gas and the temperature of the mixed molten liquid of gallium and sodium.

10. The method as claimed in claim 9, wherein:

the crystal growth is performed from a seed crystal under the crystal growth condition defined by the following expression;

a1/T+b1≦

log P≦

a2/T+b2

where;

P denotes the effective pressure (Pa) of the nitrogen gas;

T denotes the absolute temperature (K) of the mixed molten liquid;

a1=−

5.40×

10<sup>−

3</sup>;

b1=4.83;

a2=−

5.59×

10<sup>−

3</sup>;

b2=5.47.

11. The method as claimed in claim 9, wherein:

the crystal growth is performed into a pillar-shaped crystal under the crystal growth condition defined by the following expression;

a2/T+b2≦

log P≦

a3/T+b3

where;

P denotes the effective pressure (Pa) of the nitrogen gas;

T denotes the absolute temperature (K) of the mixed molten liquid;

a2=−

5.59×

10<sup>−

3</sup>;

b2=5.47;

a3=−

5.67×

10<sup>−

3</sup>;

b3=5.83.

12. The method as claimed in claim 9, wherein:

the crystal growth is performed into a plate-shaped crystal under the crystal growth condition defined by the following expression;

a3/T+b3≦

log P

where;

P denotes the effective pressure (Pa) of the nitrogen gas;

T denotes the absolute temperature (K) of the mixed molten liquid;

a3=−

5.67×

10<sup>−

3</sup>;

b3=5.83.

13. The method as claimed in claim 1, wherein:

said step b) is performed in a reaction vessel; and

the atmosphere in said reaction vessel in said step b) comprises a mixed gas of the material at least comprising nitrogen and an inactive gas.

14. The method as claimed in claim 13, further comprising the step of:

d) controlling in said step b) the pressure of the material at least comprising nitrogen and the pressure of the inactive gas of the mixed gas in said reaction vessel independently from one another.

15. The method as claimed in claim 14, wherein:

said step d) comprises a step of supplying the mixed gas into said reaction vessel after preparing the mixed gas by mixing the material at least comprising nitrogen and the inactive gas at a beforehand controlled pressure ratio therebetween.

16. The method as claimed in claim 13, further comprising the step of d) continuously supplying the material at least comprising nitrogen during said step b).

17. The method as claimed in claim 13, wherein:

the material at least comprising nitrogen comprises a nitrogen gas.

18. The method as claimed in claim 13, wherein:

the inactive gas comprises an argon gas.

19. The method as claimed in claim 1, further comprising the step of:

d) maintaining the group-III nitride crystal on growth during said step b) around a gas-to-liquid interface between a gas of the material at least comprising nitrogen and the mixed molten liquid, or a gas-to-liquid interface between a nitrogen gas produced from decomposition of the material at least comprising nitrogen and the mixed molten liquid.

20. The method as claimed in claim 19, wherein:

said step d) comprises steps of d-1) holding a seed crystal of the group-III nitride in a manner such that a predetermined crystal plane thereof is made parallel to the gas-to-liquid interface so as to grow a plate-shaped group-III nitride crystal having the main surface parallel to the gas-to-liquid interface.

21. The method as claimed in claim 20, wherein:

the predetermined crystal plane of the seed crystal to be made parallel to the gas-to-liquid interface comprises (1-100) in-plane, or (11-20) a-plane, and, therefrom, the plate-shaped group-III nitride crystal having the m-plane or a-plane parallel to the gas-to-liquid interface is made to grow.

58. A group-III nitride crystal yielded according to the method claimed in claim 1.

59. A group-III nitride crystal yielded according to the method claimed in claim 13.

60. A group-III nitride crystal yielded according to the method claimed in claim 19.

61. A semiconductor device employing the group-III nitride crystal claimed in claim 58.

62. A semiconductor device employing the group-III nitride crystal claimed in claim 59.

63. A semiconductor device employing the group-III nitride crystal claimed in claim 60.

64. The semiconductor device claimed in claim 61, forming an optical device.

65. The semiconductor device claimed in claim 62, forming an optical device.

66. The semiconductor device claimed in claim 63, forming an optical device.

67. The semiconductor device claimed in claim 61, forming an electronic device.

68. The semiconductor device claimed in claim 62, forming an electronic device.

69. The semiconductor device claimed in claim 63, forming an electronic device.

22. A group-III nitride crystal growth apparatus comprising:

a reaction vessel in which a mixed molten liquid of an alkaline metal and a material at least comprising a group-III metal is prepared; and

a crystal growth condition setting unit for setting a crystal growth condition for growing a group-III nitride crystal of the group-III metal and nitrogen from the mixed molten liquid and a material at least comprising nitrogen,

wherein said crystal growth condition setting unit sets the predetermined crystal growth condition according to a zone defined by a pressure and a temperature in the crystal growth process.

23. The apparatus as claimed in claim 22, wherein:

said crystal growth condition setting unit sets the predetermined crystal growth condition according to the zone from among a plurality of zones each defined by the pressure and temperature in the crystal growth process; and

different modes of crystal growth may occur according to respective ones of the plurality of zones.

24. The apparatus as claimed in claim 23, wherein:

under the crystal growth condition according to a zone of the plurality of zones, the crystal grows from a seed crystal.

25. The method as claimed in claim 23, wherein:

the plurality of zones are defined by a curve expressed by the following expression;

log P=a/T+b

where;

P denotes the effective pressure (Pa) of nitrogen in a reaction vessel in which the crystal growth occurs;

T denotes the absolute temperature (K) of the mixed molten liquid; and

a and b denote coefficients.

26. The apparatus as claimed in claim 25, wherein:

the curve expressed by the following formula;

log P=a/T+b

is controllable according to a ratio in amount between the alkaline metal and group-III metal to be used in the crystal growth process.

27. The apparatus as claimed in claim 22, wherein:

in the crystal growth process, a crystal is made to grow from a seed crystal under the crystal growth condition such that crystal growth may occur from a seed crystal.

28. The apparatus as claimed in claim 22, wherein:

in the crystal growth, a crystal is made to grow in a pillar shape under the crystal growth condition such that crystal growth for a pillar-shape crystal may occur.

29. The apparatus as claimed in claim 22, wherein:

in the crystal growth, the crystal is made to grow in a plate shape under the crystal growth condition such that crystal growth for a plate-shape crystal may occur.

30. The apparatus as claimed in claim 22, wherein:

the crystal growth is performed for the crystal of GaN where sodium (Na) is used as the alkaline metal;

gallium (Ga) is used as the material at least comprising a group-III metal; and

a nitrogen gas (N₂) is used as the material at least comprising nitrogen; and

the crystal growth condition is defined by the pressure of the nitrogen gas and the temperature of the mixed molten liquid of gallium and sodium.

31. The apparatus as claimed in claim 30, wherein:

the crystal growth is performed from a seed crystal under the crystal growth condition defined by the following expression;

a1/T+b1≦

log P≦

a2/T+b2

where;

P denotes the effective pressure (Pa) of the nitrogen gas;

T denotes the absolute temperature (K) of the mixed molten liquid;

a1=−

5.40×

10<sup>−

3</sup>;

b1=4.83;

a2=−

5.59×

10<sup>−

3</sup>;

b2=5.47.

32. The apparatus as claimed in claim 30, wherein:

the crystal growth is performed into a pillar-shaped crystal under the crystal growth condition defined by the following expression;

a2/T+b2≦

log P≦

a3/T+b3

where;

P denotes the effective pressure (Pa) of the nitrogen gas;

T denotes the absolute temperature (K) of the mixed molten liquid;

a2=−

5.59×

10<sup>−

3</sup>;

b2=5.47;

a3=−

5.67×

10<sup>−

3</sup>;

b3=5.83.

33. The apparatus as claimed in claim 30, wherein:

the crystal growth is performed into a plate-shaped crystal under the crystal growth condition defined by the following expression;

a3/T+b3≦

log P

where;

P denotes the effective pressure (Pa) of the nitrogen gas;

T denotes the absolute temperature (K) of the mixed molten liquid;

a3=−

5.67×

10<sup>−

3</sup>;

b3=5.83.

34. The apparatus as claimed in claim 22, further comprising:

an atmosphere setting unit setting the atmosphere in said reaction vessel so as to make it comprise a mixed gas of the material at least comprising nitrogen and an inactive gas.

35. The apparatus as claimed in claim 34, further comprising:

a unit controlling the pressure of the material at least comprising nitrogen and the pressure of the inactive gas of the mixed gas in said reaction vessel independently from one another.

36. The apparatus as claimed in claim 35, wherein:

said atmosphere setting unit comprises a unit supplying the mixed gas into said reaction vessel after preparing the mixed gas by mixing the material at least comprising nitrogen and the inactive gas at a beforehand controlled pressure ratio therebetween.

37. The apparatus as claimed in claim 34, further comprising a unit continuously supplying the material at least comprising nitrogen during the crystal growth process.

38. The apparatus as claimed in claim 34, wherein:

the material at least comprising nitrogen comprises a nitrogen gas.

39. The apparatus as claimed in claim 34, wherein:

the inactive gas comprises an argon gas.

40. The apparatus as claimed in claim 22, further comprising a crystal maintaining unit maintaining the group-III nitride crystal on growth around a gas-to-liquid interface between a gas of the material at least comprising nitrogen and the mixed molten liquid, or a gas-to-liquid interface between a nitrogen gas produced from decomposition of the material at least comprising nitrogen and the mixed molten liquid.

41. The apparatus as claimed in claim 40, wherein:

said crystal maintain unit comprises a mechanism maintaining the gas-to-liquid interface at a predetermined height during progress of the crystal growth.

42. The apparatus as claimed in claim 40, wherein:

said crystal maintaining unit comprises a mechanism maintaining the group-III nitride crystal on growth at the same height as that of the gas-to-liquid interface during progress of the crystal growth.

43. The apparatus as claimed in claim 42, wherein:

said mechanism comprises a mechanism for moving a jig holding the group-III nitride crystal on growth upward or downward.

44. The apparatus as claimed in claim 42, wherein:

said mechanism comprises a mechanism for causing a jig holding the crystal on growth to float on the mixed molten liquid.

45. The apparatus as claimed in claim 42, wherein:

said mechanism comprises a device setting a seed crystal of the group-III nitride.

46. The apparatus as claimed in claim 22, further comprising a heating unit inside of said reaction vessel for controlling the temperature therein so as to set it at a temperature such that the group-III nitride crystal may grow there.

47. The apparatus as claimed in claim 46, wherein:

said heating unit comprises a temperature control unit by which the temperature in said reaction vessel is controlled so that the group-III nitride crystal may grow there.

48. The apparatus as claimed in claim 46, wherein:

said heating unit comprises a plurality of heating devices each independently controllable in its heating function.

49. The apparatus as claimed in claim 48, wherein:

said plurality of heating devices comprises a first heating device controlling the temperature of the inside or the surface of the mixed molten liquid and a second heating device controlling the temperature above the surface of the mixed molten liquid.

50. The apparatus as claimed in claim 46, further comprising a heating element in said mixed molten liquid container holding the mixed molten liquid.

51. The apparatus as claimed in claim 22, further comprising an external vessel containing said reaction vessel,

wherein:

the mixed molten liquid of the alkaline metal and the material at least comprising a group-III metal is prepared, and the group-III nitride crystal of the group-III metal and nitrogen is made to grow from said mixed molten liquid and the material at least comprising nitrogen in said reaction vessel; and

a heating unit heating said reaction vessel such that the group-ill nitride crystal may grow in said reaction vessel is provided outside of said reaction vessel and inside of said external vessel.

52. The apparatus as claimed in claim 51, wherein:

a configuration is provided such that the atmosphere inside of said reaction vessel and the atmosphere outside of said reaction vessels and inside of said external vessel are controllable independently from one another.

53. The apparatus as claimed in claim 51, wherein:

a configuration is provided such that the alkaline metal steam occurring from the mixed molten liquid is prevented from escaping from said reaction vessel.

54. The apparatus as claimed in claim 51, wherein:

a configuration is provided such that a pressure difference between the pressure inside of the reaction vessel and the pressure outside of the same and inside of external vessel may be reduced.

55. The apparatus as claimed in claim 51, wherein:

said heating unit comprises a temperature control unit by which the temperature in said reaction vessel is controlled such that the group-III nitride crystal may grow therein.

56. The apparatus as claimed in claim 51, wherein:

said heating device comprises a plurality of heating devices each independently controllable in its heating function.

57. The apparatus as claimed in claim 56, wherein:

said plurality of heating devices comprises a first heating device controlling the temperature of the inside or the surface of the mixed molten liquid and a second heating device controlling the temperature above the surface of the mixed molten liquid.