METHOD FOR ACHIEVING IMPROVED EPITAXY QUALITY (SURFACE TEXTURE AND DEFECT DENSITY) ON FREE-STANDING (ALUMINUM, INDIUM, GALLIUM) NITRIDE ((AL,IN,GA)N) SUBSTRATES FOR OPTO-ELECTRONIC AND ELECTRONIC DEVICES

• US 6,447,604 B1
• Filed: 06/28/2000
• Issued: 09/10/2002
• Est. Priority Date: 03/13/2000
• Status: Expired due to Term

• Current Assignee: Wolfspeed, Inc.
• Original Assignee: Advanced Technology Materials, Inc. (Entegris Incorporated)
• Inventors: Keogh, David M., Brandes, George R., Xu, Xueping, Vaudo, Robert P., Flynn, Jeffrey S., Landini, Barbara E.
• Primary Examiner(s): KUNEMUND, ROBERT M
• Application Number:
  US09/605,195
• Time in Patent Office: 804 Days
• Field of Search: 117/89, 117/93, 117/94, 117/95, 117/952
• US Class Current: 117/89
• CPC Class Codes: C30B 23/002 Controlling or regulating
• CPC Class Codes: C30B 23/02 Epitaxial-layer growth
• CPC Class Codes: C30B 25/00 Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
• CPC Class Codes: C30B 25/02 Epitaxial-layer growth
• CPC Class Codes: C30B 25/183 being provided with a buffer layer, e.g. a lattice matching layer
• CPC Class Codes: C30B 29/403 AIII-nitrides
• CPC Class Codes: C30B 29/406 Gallium nitride
• CPC Class Codes: H01L 21/02389 Nitrides
• CPC Class Codes: H01L 21/0243 Surface structure
• CPC Class Codes: H01L 21/02433 Crystal orientation
• 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 21/02634 Homoepitaxy
• CPC Class Codes: H01L 21/02636 Selective deposition, e.g. simultaneous growth of mono- and non-monocrystalline semiconductor materials
• CPC Class Codes: H01L 21/02658 Pretreatments cleaning in general H01L21/02041
• CPC Class Codes: H01L 33/32 containing nitrogen
• CPC Class Codes: H01S 5/1228 DFB lasers with a complex coupled grating, e.g. gain or loss coupling
• CPC Class Codes: H01S 5/1231 Grating growth or overgrowth details
• CPC Class Codes: H01S 5/2095 using melting or mass transport
• CPC Class Codes: H01S 5/32341 blue laser based on GaN or GaP

Abstract

A III-V nitride homoepitaxial microelectronic device structure comprising a III-V nitride homoepitaxial epi layer on a III-V nitride material substrate, e.g., of freestanding character. Various processing techniques are described, including a method of forming a III-V nitride homoepitaxial layer on a corresponding III-V nitride material substrate, by depositing the III-V nitride homoepitaxial layer by a VPE process using Group III source material and nitrogen source material under process conditions including V/III ratio in a range of from about 1 to about 10⁵, nitrogen source material partial pressure in a range of from about 1 to about 10³ torr, growth temperature in a range of from about 500 to about 1250 degrees Celsius, and growth rate in a range of from about 0.1 to about 500 microns per hour. The III-V nitride homoepitaxial microelectronic device structures are usefully employed in device applications such as UV LEDs, high electron mobility transistors, and the like.

Claims

1. A method of forming a III-V nitride homoepitaxial layer on a corresponding III-V nitride material substrate, comprising depositing the III-V nitride homoepitaxial layer by a VPE process using Group III source material and nitrogen source material under deposition conditions including V/III ratio in a range of from about 1 to about 10⁵, nitrogen source material partial pressure in a range of from about 1 to about 10³ torr, growth temperature in a range of from about 500 to about 1250 degrees Celsius, and growth rate in a range of from about 0.1 micron per hour to about 500 microns per hour.

2. The method of claim 1, wherein the III-V nitride homoepitaxial layer comprises a nitride compound selected from the group consisting of AlN, AlInN, AlGaN, AlInGaN, InN, InGaN, and GaN.

3. The method of claim 1, wherein the III-V nitride homoepitaxial layer comprises GaN.

4. The method of claim 1, wherein the III-V nitride material substrate is a free-standing substrate.

5. The method of claim 1, wherein the III-V nitride material substrate is a free-standing finished substrate.

6. The method of claim 1, wherein the III-V nitride material substrate is a free-standing unfinished substrate.

7. The method of claim 1, wherein the III-V nitride material substrate is a free-standing chemical mechanical polished substrate.

8. The method of claim 1, wherein prior to the depositing step, the substrate is subjected to heat-up in an ambient to a temperature in said growth temperature range, wherein said ambient includes one or more species selected from the group consisting of hydrogen, nitrogen, argon, helium, neon, hydrogen chloride, and mixtures of two or more of the foregoing.

9. The method of claim 1, wherein the growth temperature is in a range of from about 1000 to about 1250 degrees Celsius.

10. The method of claim 1, wherein the growth temperature is >

1050 degrees Celsius.

11. The method of claim 1, wherein the growth temperature is substantially about 1050 degrees Celsius.

12. The method of claim 1, where the homoepitaxial layer is at least 0.5 microns in thickness.

13. The method of claim 1, where the homoepitaxial layer is at least 3.0 microns in thickness.

14. The method of claim 13, wherein the III-V nitride material substrate is a free-standing unfinished substrate.

15. The method of claim 1, wherein said process conditions include V/III ratio of from about 10¹ to about 10⁵.

16. The method of claim 1, wherein said process conditions include V/III ratio of greater than about 10⁴.

17. The method of claim 1, wherein said process conditions include V/III ratio of from about 10³ to about 5×

10⁴, nitrogen source material partial pressure of from about 20 to about 400 torr, growth temperature of from about 1000 to about 1150 degrees Celsius, and growth rate of from about 0.5 to about 10 microns per hour.

18. The method of claim 1, wherein said VPE process comprises an MOVPE process.

19. The method of claim 1, wherein the substrate has a crystallographic orientation selected from the group consisting of (0001), (000{overscore (1)}), and offcuts thereof.

20. The method of claim 1, wherein the substrate has a crystallographic orientation selected from the group consisting of {0001}, {11{overscore (2)}0}, {1{overscore (1)}00}, and offcuts therefrom.

21. The method of claim 1, wherein the substrate is GaN and the epitaxial layer is deposited on the Ga face of the substrate.

22. The method of claim 1, wherein the substrate is GaN and the epitaxial layer is deposited on the N face of the substrate.

23. The method of claim 1, wherein said VPE process comprises an HVPE process.

24. The method of claim 1, wherein the III-V nitride material substrate is heated up to growth temperature in a heat-up effecting one or more of the steps of:

(a) smoothing a deposition surface of the substrate;

(b) removing damage on a deposition surface of the substrate;

(c) removing contaminants on a deposition surface of the substrate;

(d) reducing defect propagation at an interface of the III-V nitride homoepitaxial layer and the substrate in said depositing step;

(e) eliminating new defect formation at an interface of the III-V nitride homoepitaxial layer and the substrate in said depositing step;

(f) reducing electrically active defects in said III-V nitride homoepitaxial layer or substrate;

(g) reducing substrate impurity outgassing in said depositing step; and

(h) compensating charge at a homoepitaxial layer/substrate interface.

25. The method of claim 24, wherein said heat-up comprises process conditions including nitrogen source material partial pressure in a range of from about 1 to about 1000 torr, ramp time in a range of from about 1 to about 1000 minutes, ramp rates in a range of from about 10 to about 1000 degrees Celsius per minute, and an ambient including one or more species selected from the group consisting of hydrogen, nitrogen, argon, helium, neon, hydrogen chloride, and mixtures of two or more of the foregoing.

26. The method of claim 24, wherein said heat-up comprises process conditions including nitrogen source material partial pressure in a range of from about 10 to about 400 torr, ramp time in a range of from about 1 to about 100 minutes, ramp rates in a range of from about 100 to about 400 degrees Celsius per minute, and an ambient including one or more species selected from the group consisting of hydrogen, nitrogen, argon, helium, neon, hydrogen chloride, and mixtures of two or more of the foregoing.

27. The method of claim 1, wherein said III-V nitride homoepitaxial layer is deposited in said depositing step on a deposition surface of the substrate having a crystallographic orientation that is offcut from (0001).

28. The method of claim 27, wherein the offcut defines an offcut angle in the range of from 0.1 to 10 degrees from (0001).

29. The method of claim 1, wherein said III-V nitride homoepitaxial layer is deposited in said depositing step on a deposition surface of the substrate having an offcut direction towards the <

11{overscore (2)}0>

direction.

30. The method of claim 1, wherein said III-V nitride homoepitaxial layer is deposited in said depositing step on a deposition surface of the substrate having an offcut direction towards the <

10{overscore (1)}0>

direction.

31. The method of claim 1, wherein said III-V nitride homoepitaxial layer is deposited in said depositing step on a deposition surface of the substrate having an offcut direction between <

11{overscore (2)}0>

and <

10{overscore (1)}0>

.

32. The method of claim 1, wherein the III-V nitride material substrate is cleaned with an aqueous acid cleaning composition before said depositing step.

33. The method of claim 1, wherein the III-V nitride material substrate is cleaned with an aqueous basic cleaning composition before said depositing step.

34. The method of claim 1, wherein the III-V nitride material substrate is cleaned to remove NH₄Cl from the substrate before said depositing step.

38. The method of claim 1, wherein the III-V nitride material substrate is cleaned by RIE before said depositing step.

39. The method of claim 1, wherein said III-V nitride homoepitaxial layer is deposited in said depositing step on a deposition surface exposed by RIE or wet etch before said depositing step.

40. The method of claim 1, further comprising impurity addition in said depositing step.

41. The method of claim 1, further comprising a multi-step smoothing process.

53. The method of claim 1, wherein the III-V nitride material substrate before said depositing step is subjected to a treatment selected from the group consisting of polishing and etching.

54. The method of claim 1, wherein the III-V nitride material substrate before said depositing step is subjected to a masking treatment for masking of defects in the substrate, and said depositing step effects defect overgrowth and elimination.

56. The method of claim 1, further comprising forming a mesa in the III-V nitride material substrate before said depositing step and depositing said III-V nitride homoepitaxial layer on or laterally from said mesa.

57. The method of claim 56, wherein said mesa is of sufficient area to enable crystallographic propagation termination and dislocation termination in said depositing step.

58. The method of claim 56, further comprising masking an area around said mesa to prevent growth thereon during said depositing step.

59. The method of claim 56, further comprising etching an area around said mesa to contain growth in said area during said depositing step.

60. The method of claim 1, wherein the III-V nitride homoepitaxial layer and corresponding III-V nitride material substrate, each comprise GaN.

61. The method of claim 1, wherein the III-V nitride homoepitaxial layer and corresponding III-V nitride material substrate, each comprise AlGaN.

62. The method of claim 1, wherein the III-V nitride homoepitaxial layer and corresponding III-V nitride material substrate, each comprise AlInGaN.

63. The method of claim 1, wherein the substrate comprises free-standing GaN and the epitaxial layer is deposited by HVPE.

64. The method of claim 1, wherein the epitaxial layer is doped n-type, p-type or semi-insulating.

65. The method of claim 1, wherein the substrate is free-standing GaN, having a finished or unfinished character, and wherein the homoepitaxial layer is selected from the group consisting of AlGaN, InGaN and AlInGaN, InN, GaN, AlN.

66. The method of claim 1, wherein the layer and substrate have a sheet resistance greater than 1E5 ohms per square centimeter.

67. The method of claim 1, where the layer and substrate have a sheet resistance greater than 1E4 ohms per square centimeter.

35. A method of forming a III-V nitride homoepitaxial layer on a corresponding III-V nitride material substrate, comprising depositing the III-V nitride homoepitaxial layer by a VPE process using Group III source material and nitrogen source material under deposition conditions including V/III ratio in a range of from about 1 to about 10⁵, nitrogen source material partial pressure in a range of from about 1 to about 10³ torr, growth temperature in a range of from about 500 to about 1250 degrees Celsius, and growth rate in a range of from about 0.1 micron per hour to about 500 microns per hour, wherein the III-V nitride material substrate is transformed into a dissimilar compound on a deposition surface thereof and dissimilar compound is stripped, before said depositing step.

36. The method of claim 35, wherein the III-V nitride material substrate is oxidized on a deposition surface thereof and resulting oxide is selectively stripped, before said depositing step.

37. The method of claim 35, wherein the III-V nitride material substrate is oxidized for smoothing of the substrate before said depositing step.

42. A method of forming a III-V nitride homoepitaxial layer on a corresponding III-V nitride material substrate, comprising depositing the III-V nitride homoepitaxial layer by a VPE process using Group III source material and nitrogen source material under deposition conditions including V/III ratio in a range of from about 1 to about 10⁵, nitrogen source material partial pressure in a range of from about 1 to about 10³ torr, growth temperature in a range of from about 500 to about 1250 degrees Celsius, and growth rate in a range of from about 0.1 micron per hour to about 500 microns per hour, wherein said method further comprises a backside evaporative protection process.

43. The process of claim 42, wherein the backside evaporative protection process comprises applying to the substrate a material protecting a backside surface of the substrate from evaporation.

44. The process of claim 42, wherein the backside evaporative protection process comprises polishing a backside surface of the substrate.

45. The process of claim 42, wherein the backside evaporative protection process comprises chemical etching.

46. The process of claim 45, wherein the chemical etching comprises exposing a backside surface of the substrate to a hot acid or a hot base.

47. A method of forming a III-V nitride homoepitaxial layer on a corresponding III-V nitride material substrate, comprising depositing the III-V nitride homoepitaxial layer by a VPE process using Group III source material and nitrogen source material under deposition conditions including V/III ratio in a range of from about 1 to about 10⁵, nitrogen source material partial pressure in a range of from about 1 to about 10³ torr, growth temperature in a range of from about 500 to about 1250 degrees Celsius, and growth rate in a range of from about 0.1 micron per hour to about 500 microns per hour, wherein said method further comprises applying an epi interlayer to a deposition surface of the substrate before depositing the III-V nitride homoepitaxial layer.

48. The method of claim 47, wherein the epi interlayer comprises different lattice-matched or lattice-mismatched (Al,In,Ga)N compounds.

49. The method of claim 47, whereby morphology of the homoepitaxial layer formed by said method is improved, dislocation defects are reduced, in relation to a corresponding process lacking applying of said epi interlayer to the deposition surface.

50. A method of forming a III-V nitride homoepitaxial layer on a corresponding III-V nitride material substrate, comprising depositing the III-V nitride homoepitaxial layer by a VPE process using Group III source material and nitrogen source material under deposition conditions including V/III ratio in a range of from about 1 to about 10⁵, nitrogen source material partial pressure in a range of from about 1 to about 10³ torr, growth temperature in a range of from about 500 to about 1250 degrees Celsius, and growth rate in a range of from about 0.1 micron per hour to about 500 microns per hour, wherein said method further comprises annealing the substrate before depositing the III-V nitride homoepitaxial layer.

51. A method of forming a III-V nitride homoepitaxial layer on a corresponding III-V nitride material substrate, comprising depositing the III-V nitride homoepitaxial layer by a VPE process using Group III source material and nitrogen source material under deposition conditions including V/III ratio in a range of from about 1 to about 10⁵, nitrogen source material partial pressure in a range of from about 1 to about 10³ torr, growth temperature in a range of from about 500 to about 1250 degrees Celsius, and growth rate in a range of from about 0.1 micron per hour to about 500 microns per hour, wherein said method further comprises applying a surfactant to a deposition surface of the substrate for nucleation of the III-V nitride homoepitaxial layer thereon.

52. A method of forming a III-V nitride homoepitaxial layer on a corresponding III-V nitride material substrate, comprising depositing the III-V nitride homoepitaxial layer by a VPE process using Group III source material and nitrogen source material under deposition conditions including V/III ratio in a range of from about 1 to about 10⁵, nitrogen source material partial pressure in a range of from about 1 to about 10³ torr, growth temperature in a range of from about 500 to about 1250 degrees Celsius, and growth rate in a range of from about 0.1 micron per hour to about 500 microns per hour, wherein said method further comprises conducting a mass transport process to produce a smoothed morphology of the III-V nitride homoepitaxial layer.

55. A method of forming a III-V nitride homoepitaxial layer on a corresponding III-V nitride material substrate, comprising depositing the III-V nitride homoepitaxial layer by a VPE process using Group III source material and nitrogen source material under deposition conditions including V/III ratio in a range of from about 1 to about 10⁵, nitrogen source material partial pressure in a range of from about 1 to about 10³ torr, growth temperature in a range of from about 500 to about 1250 degrees Celsius, and growth rate in a range of from about 0.1 micron per hour to about 500 microns per hour, wherein said depositing step is carried out in a growth environment, and a surfactant is added to the growth environment during said depositing step.

68. A method of forming a III-V nitride homoepitaxial layer on a corresponding III-V nitride material substrate, comprising depositing the III-V nitride homoepitaxial layer by a VPE process using Group III source material and nitrogen source material, wherein the substrate is reposed on a susceptor surface during said depositing step, said method further comprising coating said susceptor surface with a corresponding III-V nitride material prior to reposing the substrate thereon for said depositing step.

69. A method of forming a III-V nitride homoepitaxial layer on a corresponding III-V nitride material substrate, comprising depositing the III-V nitride homoepitaxial layer by a VPE process using Group III source material and nitrogen source material, and including an anneal step in an ambient prior to said depositing step at a temperature >

600 degrees Celsius to relieve the strain in the layer, with the ambient of the anneal being different from that of said depositing step to protect the substrate surface and promote substrate strain relaxation.

70. A method of forming a III-V nitride homoepitaxial layer on a corresponding unfinished III-V nitride material substrate, comprising depositing the III-V nitride homoepitaxial layer by a VPE process using Group III source material and nitrogen source material, wherein the substrate is subjected to a mass transport smoothing of a growth surface of said substrate, wherein said mass transport smoothing comprises at least one step selected from the group consisting of:

a. annealing the substrate in an ambient comprising ammonia and H₂;

b. growing a thin epitaxial layer having a thickness of not more than 1000 Angstroms to dilute impurities from the substrate material;

c. adding a surfactant to smooth out the surface of the substrate; and

d. adding charge compensating impurities to negate impurities-related charges.

71. A method of forming a III-V nitride homoepitaxial layer on a corresponding unfinished III-V nitride material substrate, comprising depositing the III-V nitride homoepitaxial layer in a growth ambient, by an HVPE process using Group III source material and nitrogen source material, with addition of surfactant into the growth ambient of the reactor during said depositing, to facilitate and enhance the smoothing of the substrate.

72. A method of forming a III-V nitride homoepitaxial layer on a corresponding unfinished III-V nitride material substrate, comprising depositing the III-V nitride homoepitaxial layer by a VPE process using Group III source material and nitrogen source material, wherein the substrate comprises FS (Al,In,Ga)N and said substrate is conditioned for said depositing, by oxidizing the FS (Al,In,Ga)N substrate in O₂, air, an air/inert gas mixture, or a wet mixture to create a thin oxide layer, and stripping the oxide layer in an alkali solution or etch removing same, to remove potential impurities from the substrate.

73. A method of forming a III-V nitride homoepitaxial layer on a corresponding unfinished III-V nitride material substrate, comprising depositing the III-V nitride homoepitaxial layer by a VPE process using Group III source material and nitrogen source material, wherein the homoepitaxial layer is doped, but wherein said doping is paused during a portion of said depositing, to form a film thickness of undoped material in said homoepitaxial layer of a sufficient thickness to eliminate interrupted morphology in growth of said homoepitaxial layer.