III-V nitride substrate boule and method of making and using the same

• US 6,596,079 B1
• Filed: 03/13/2000
• Issued: 07/22/2003
• Est. Priority Date: 03/13/2000
• Status: Expired due to Term

• Current Assignee: Wolfspeed, Inc.
• Original Assignee: Advanced Technology Materials, Inc. (Entegris Incorporated)
• Inventors: Flynn, Jeffrey S., Brandes, George R., Vaudo, Robert P., Redwing, Joan M., Tischler, Michael A.
• Primary Examiner(s): Jones, Deborah
• Assistant Examiner(s): STEIN, STEPHEN J
• Application Number:
  US09/524,062
• Time in Patent Office: 1,226 Days
• Field of Search: 117/87, 117/88, 117/89, 117/97, 117/101, 117/952, 117/84, 117/90, 117/95
• US Class Current: 117/97
• CPC Class Codes: C30B 23/00 Single-crystal growth by condensing evaporated or sublimed materials
• 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 21/02458 Nitrides
• CPC Class Codes: H01L 21/0254 Nitrides
• CPC Class Codes: H01L 21/02576 N-type
• CPC Class Codes: H01L 21/02579 P-type
• CPC Class Codes: H01L 21/02581 Transition metal or rare earth elements
• CPC Class Codes: H01L 21/0262 Reduction or decomposition of gaseous compounds, e.g. CVD
• CPC Class Codes: H01L 33/32 containing nitrogen

Abstract

A boule formed by high rate vapor phase growth of Group III-V nitride boules (ingots) on native nitride seeds, from which wafers may be derived for fabrication of microelectronic device structures. The boule is of microelectronic device quality, e.g., having a transverse dimension greater than 1 centimeter, a length greater than 1 millimeter, and a top surface defect density of less than 10⁷ defects cm⁻². The Group III-V nitride boule may be formed by growing a Group III-V nitride material on a corresponding native Group III-V nitride seed crystal by vapor phase epitaxy at a growth rate above 20 micrometers per hour.

Claims

1. A method of making a (Al,Ga,In)N boule, comprising:

providing a native (Al,Ga,In) N seed crystal for the boule; and

growing a (Al,Ga,In) N material on the seed crystal by vapor phase epitaxy, to yield said boule.

2. The method of claim 1, wherein said growing step is carried out at a growth rate in excess of 20 micrometers per hour.

3. The method of claim 1, wherein said growing step is carried out at a growth rate in excess of 50 micrometers per hour.

4. The method of claim 1, wherein said (Al,Ga,In)N material comprises GaN and growth is carried out at a temperature in the range of from about 900 to about 1000°

C.

5. The method of claim 1, wherein said (Al,Ga,In)N material comprises AlN and growth is carried out at a temperature in the range of from about 950 to about 1200°

C.

6. The method of claim 1, wherein said (Al,Ga,In)N material comprises InN and growth is carried out at a temperature in the range of from about 700 to about 900°

C.

7. The method of claim 1, wherein said vapor phase epitaxy comprises HVPE.

8. The method of claim 1, wherein growing a (Al,Ga,In)N material on the seed crystal comprises use of a nitrogen source reagent selected from the group consisting of ammonia, hydrazine, amines and polyamines.

9. The method of claim 1, wherein growing a (Al,Ga,In)N material on the seed crystal comprises a ratio of flow of a nitrogen-containing precursor to a Group III precursor wherein the flow rate of the nitrogen-containing precursor is substantially in excess of the flow rate of the Group III precursor.

10. The method of claim 1, wherein growing a (Al,Ga,In)N material on the seed crystal comprises a ratio of flow of a nitrogen-containing precursor to a Group III precursor in the range of from about 10 to about 1000.

11. The method of claim 1, wherein growing a (Al,Ga,In)N material on the seed crystal comprises delivering a liquid solution containing both Group III and Group V precursors to a growth reactor and conducting growth of the Group III-V nitride material in said growth reactor.

12. The method of claim 1, wherein the boule during growth is retracted from sources of respective precursors for the (Al,Ga,In)N material.

13. The method of claim 1, wherein the boule during growth is retracted from sources of respective precursors for the (Al,Ga,In)N material, to maintain a predetermined distance between the growth surface of the boule and said sources.

14. The method of claim 1, herein the boule is grown to a length of greater than 1 millimeter.

15. The method of claim 1, wherein the boule is grown to a length of greater than 4 millimeters.

16. The method of claim 1, wherein the boule is grown to a length of greater than 10 millimeters.

17. The method of claim 1, wherein the boule is grown at least until the growth surface defect density is less, than 10⁷ defects cm⁻

2.

18. The method of claim 1, wherein the boule is grown with a transverse dimension greater than 1 centimeter.

19. The method of claim 1, wherein the boule is grown with a transverse cross-sectional area of at least 5 centimeters².

20. The method of claim 1, wherein the seed crystal has an orientation selected from the group consisting of c-axis, a-axis, m-axis, r-axis, and offcut less than 0.5 degrees from a primary crystal axis.

21. The method of claim 1, wherein the seed crystal has an orientation offcut from 0.5 to 10 degrees from a primary crystal axis.

22. The method of claim 1, wherein the boule growth was carried out on the N-face or (Al,Ga,In)-face of a c-axis-oreinted seed crystal.

23. The method of claim 1, wherein the boule is grown on a seed crystal derived from a GaN boule.

24. The method of claim 1, wherein the seed crystal has been produced by an HVPE/optical liftoff technique.

25. The method of claim 1, wherein the (Al,Ga,In) N material grown on a seed crystal is produced by growth of (Al,Ga,In) N on a sacrificial template and removal of the template by a removal technique selected from the group consisting of physical, thermal, etching, H-fracture and embrittlement removal techniques.

26. The method of claim 1, wherein the (Al,Ga,In)N material is grown with at least one interlayer between the seed crystal and the nitride material.

27. The method of claim 1, wherein the at least one interlayer is deposited by a process selected from the group consisting of VPE, CVD, PVD, MBE, MOVPE, and HVPE or otherwise formed in or with the seed crystal.

28. The method of claim 1, comprising incorporating an impurity to regulate the crystalline quality or polytype of the (Al,Ga,In)N material during growth thereof.

29. The method of claim 1, further comprising doping the (Ga,Al,In)N material with a dopant species selected from the group consisting of vanadium, chromium, iron, arsenic, manganese, cobalt, nickel and copper.

30. The method of claim 1, wherein the growth of (Al,Ga,In)N material is carried out with in situ source replenishment of source components for the (Al,Ga,In)N material, maintenance of source to boule distance during growth, growth rate of the (Al,Ga,In)N material exceeding 20 micrometers per hour.

31. The method of claim 30, conducted for sufficient time to grow the (Al,Ga,In)N material to a thickness greater than 4 millimeters.

32. The method of claim 1, comprising in situ parting of the boule from a non-native seed.

33. The method of claim 1, further comprising deriving a wafer from the boule.

34. The method of claim 33, wherein the wafer is derived by slicing the boule with a wire saw.

35. The method of claim 33, further comprising subjecting the wafer to a forming operation selected from the group consisting of core drilling, abrasive particle jet exposure, wire sawing, laser exposure, chemical mechanical polishing, photoelectrochemical etching, and reactive ion etching.

36. The method of claim 35, further comprising processing the wafer to impart a RMS roughness of less than 10 Angstroms on a 10×

10 micrometers² area of the wafer.

37. The method of claim 35, further comprising processing the wafer to remove subsurface damage thereof.

38. The method of claim 33, further comprising fabricating a microelectronic device structure on the wafer.

39. The method of claim 38, wherein the device structure comprises at least part of a device selected from the group consisting of light emitting diodes, laser diodes, ultraviolet photodetectors, bipolar transistors, heterostructure bipolar transistors, high electron mobility transistors, high power rectifiers, and wavelength division multiplexing components.

40. The method of claim 33, wherein the boule is sized before deriving the wafer therefrom.

41. The method of claim 33, wherein the (Al,Ga,In)N material comprises GaN.

42. The method of claim 33, further comprising polishing the wafer.

43. The method of claim 33, further comprising lapping the wafer with coarse and medium abrasive media, followed by polishing with a fine abrasive medium.

44. The method of claim 43, wherein the abrasive media comprise at least one abrasive material selected from the group consisting of diamond, boron carbide, silicon carbide and alumina.

45. The method of claim 33, further comprising chemical mechanical polishing the wafer with a slurry composition selected from the group consisting of acidic CMP slurry compositions and basic CMP slurry compositions.

46. The method of claim 33, further comprising reactive ion etching at least one face of the wafer to yield a surface suitable for epitaxial growth.

47. The method of claim 1, wherein the boule comprises a lateral extremity that is larger than the seed crystal.

48. A method of making a doped (Al,Ga,In)N boule, comprising:

providing a native (Al,Ga,In) N seed crystal for the boule;

growing a (Al,Ga,In) N material on the seed crystal by vapor phase epitaxy, to yield said boule; and

doping said boule by nuclear transmutation doping.

49. A method of making a (Al,Ga,In)N boule, comprising:

providing a native (Al ,Ga,In) N seed crystal for the boule; and

growing a (Al,Ga,In) N material on the seed crystal by vapor phase epitaxy, with growth of a parting layer therein, to yield said boule, so that said boule contains said parting layer, wherein said parting layer is more highly absorptive of a selected radiation than said (Al,Ga,In)N material.