Aluminum nitride bulk crystals having high transparency to ultraviolet light and methods of forming them

• US 9,034,103 B2
• Filed: 06/30/2010
• Issued: 05/19/2015
• Est. Priority Date: 03/30/2006
• Status: Active Grant

• Current Assignee: Crystal IS, Inc. (Asahi Kasei Corporation)
• Original Assignee: Crystal IS, Inc. (Asahi Kasei Corporation)
• Inventors: Schujman, Sandra B., Rao, Shailaja P., Bondokov, Robert T., Morgan, Kenneth E., Slack, Glen A., Schowalter, Leo J.
• Primary Examiner(s): SONG, MATTHEW J
• Application Number:
  US12/827,507
• Publication Number:
  US 20110008621A1
• Time in Patent Office: 1,784 Days
• Field of Search: 117/84, 117/88, 117/952
• US Class Current: 117/88
• CPC Class Codes: C30B 23/00 Single-crystal growth by condensing evaporated or sublimed materials
• CPC Class Codes: C30B 23/002 Controlling or regulating
• CPC Class Codes: C30B 23/02 Epitaxial-layer growth
• CPC Class Codes: C30B 23/066 Heating of the material to be evaporated
• CPC Class Codes: C30B 29/403 AIII-nitrides
• CPC Class Codes: C30B 33/02 Heat treatment C30B33/04, C30B33/06 take precedence
• CPC Class Codes: C30B 35/00 Apparatus not otherwise provided for, specially adapted for the growth, production or after-treatment of single crystals or of a homogeneous polycrystalline material with defined structure
• CPC Class Codes: H01L 21/02389 Nitrides
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]

Abstract

In various embodiments, methods of forming single-crystal AlN include providing a substantially undoped polycrystalline AlN ceramic having an oxygen concentration less than approximately 100 ppm, forming a single-crystal bulk AlN crystal by a sublimation-recondensation process at a temperature greater than approximately 2000° C., and cooling the bulk AlN crystal to a first temperature between approximately 1500° C. and approximately 1800° C. at a first rate less than approximately 250° C./hour.

Claims

1. A method of forming single-crystal AlN, the method comprising:

providing a substantially undoped polycrystalline AlN ceramic having an oxygen concentration less than approximately 100 ppm within a crystal growth enclosure, the crystal growth enclosure being disposed within a furnace;

utilizing the polycrystalline AlN ceramic, forming a single-crystal bulk AlN crystal by a sublimation-recondensation process at a growth temperature greater than approximately 2000°

C.; and

after the sublimation-recondensation process, (i) cooling the bulk AlN crystal from the growth temperature to a first temperature between approximately 1500°

C. and approximately 1800°

C. at a first rate ranging from 70°

C./hour to 150°

C./hour, the first rate being slowed via controlled application of heat from the furnace, and (ii) thereafter, cooling the bulk AlN crystal from the first temperature to a second temperature lower than the first temperature at a second rate greater than approximately 250°

C./hour.

2. The method of claim 1, wherein the second temperature is approximately room temperature.

3. The method of claim 1, wherein providing the polycrystalline AlN ceramic comprises:

cleaning a substantially undoped Al pellet; and

reacting the Al pellet with nitrogen gas to form the polycrystalline AlN ceramic,

wherein the polycrystalline AlN ceramic has the oxygen concentration of less than approximately 100 ppm after reaching approximately room temperature after the reaction.

4. The method of claim 3, wherein (i) the polycrystalline AlN ceramic has less than 1% excess Al after reaching approximately room temperature after the reaction, and (ii) the polycrystalline AlN ceramic does not undergo any sublimation-recondensation treatment prior to the sublimation-recondensation process to form the bulk AlN crystal.

5. The method of claim 3, further comprising cleaning and reacting a plurality of additional substantially undoped Al pellets.

6. The method of claim 3, wherein cleaning the undoped Al pellet comprises exposing the undoped Al pellet to hydrofluoric acid.

7. The method of claim 3, wherein cleaning the undoped Al pellet comprises:

exposing the undoped Al pellet to an organic solvent;

exposing the undoped Al pellet to hydrochloric acid; and

thereafter, exposing the undoped Al pellet to an acid mixture comprising nitric acid and hydrofluoric acid.

8. The method of claim 1, wherein an absorption coefficient of the bulk AlN crystal is less than approximately 20 cm⁻

1 in the entire wavelength range between about 4500 nm and approximately 215 nm.

9. The method of claim 1, wherein an absorption coefficient of the bulk AlN crystal is less than approximately 10 cm⁻

1 for the entire wavelength range between approximately 400 nm and approximately 250 nm.

10. The method of claim 1, wherein an oxygen concentration of the bulk AlN crystal is less than approximately 5 ppm.

11. The method of claim 1, wherein at least a portion of the polycrystalline AlN ceramic is in contact with a foil wrap during the sublimation-recondensation process, the foil wrap comprising a material inert to AlN.

12. The method of claim 11, wherein the foil wrap consists essentially of W.

13. The method of claim 11, wherein the foil wrap and the crystal growth enclosure comprise the same material.

14. The method of claim 1, wherein the second rate results from cooling without controlled application of heat from the furnace.

15. The method of claim 1, further comprising providing an AlN seed during the sublimation-recondensation process, wherein the bulk AlN crystal forms on the AlN seed.

16. A method of forming single-crystal AlN, the method comprising:

providing a polycrystalline AlN ceramic within a crystal growth enclosure, the crystal growth enclosure being disposed within a furnace;

utilizing the polycrystalline AlN ceramic, forming a single-crystal bulk AlN crystal by a sublimation-recondensation process at a growth temperature greater than approximately 2000°

C.; and

after the sublimation-recondensation process, (i) cooling the bulk AlN crystal from the growth temperature to a first temperature between approximately 1500°

C. and approximately 1800°

C. at a first rate ranging from 70°

C./hour to 150°

C./hour, the first rate being slowed via controlled application of heat from the furnace, and (ii) thereafter, cooling the bulk AlN crystal from the first temperature to a second temperature lower than the first temperature at a second rate greater than approximately 250°

C./hour.

17. The method of claim 16, wherein the polycrystalline AlN ceramic is substantially undoped.

18. The method of claim 16, wherein an oxygen concentration of the polycrystalline AlN ceramic is less than approximately 100 ppm.

19. The method of claim 16, wherein the second temperature is approximately room temperature.

20. The method of claim 16, wherein providing the polycrystalline AlN ceramic comprises:

cleaning an Al pellet; and

reacting the Al pellet with nitrogen gas to form the polycrystalline AlN ceramic,

wherein the polycrystalline AlN ceramic has an oxygen concentration of less than approximately 100 ppm after reaching approximately room temperature after the reaction.

21. The method of claim 20, wherein (i) the polycrystalline AlN ceramic has less than 1% excess Al after reaching approximately room temperature after the reaction, and (ii) the polycrystalline AlN ceramic does not undergo any sublimation-recondensation treatment prior to the sublimation-recondensation process to form the bulk AlN crystal.

22. The method of claim 20, further comprising cleaning and reacting a plurality of additional Al pellets.

23. The method of claim 20, wherein cleaning the Al pellet comprises exposing the Al pellet to hydrofluoric acid.

24. The method of claim 20, wherein cleaning the Al pellet comprises:

exposing the Al pellet to an organic solvent;

exposing the Al pellet to hydrochloric acid; and

thereafter, exposing the Al pellet to an acid mixture comprising nitric acid and hydrofluoric acid.

25. The method of claim 16, wherein an absorption coefficient of the bulk AlN crystal is less than approximately 20 cm⁻

1 in the entire wavelength range between about 4500 nm and approximately 215 nm.

26. The method of claim 16, wherein an absorption coefficient of the bulk AlN crystal is less than approximately 10 cm⁻

1 for the entire wavelength range between approximately 400 nm and approximately 250 nm.

27. The method of claim 16, wherein an oxygen concentration of the bulk AlN crystal is less than approximately 5 ppm.

28. The method of claim 16, wherein at least a portion of the polycrystalline AlN ceramic is in contact with a foil wrap during the sublimation-recondensation process, the foil wrap comprising a material inert to AlN.

29. The method of claim 28, wherein the foil wrap consists essentially of W.

30. The method of claim 28, wherein the foil wrap and the crystal growth enclosure comprise the same material.

31. The method of claim 16, wherein the second rate results from cooling without controlled application of heat from the furnace.

32. The method of claim 16, further comprising providing an AlN seed during the sublimation-recondensation process, wherein the bulk AlN crystal forms on the AlN seed.

33. The method of claim 16, wherein the polycrystalline AlN ceramic is doped with a non-oxygen dopant.

34. The method of claim 33, wherein the dopant comprises at least one of beryllium, magnesium, zinc, carbon, silicon, or lithium.

35. The method of claim 33, wherein the bulk AlN crystal comprises the dopant at a concentration greater than approximately 10¹⁶/cm³.