Polycrystalline group III metal nitride with getter and method of making

• US 8,987,156 B2
• Filed: 05/14/2013
• Issued: 03/24/2015
• Est. Priority Date: 12/12/2008
• Status: Expired

• Current Assignee: SL Technology Incorporated (Reliv' International, Inc.)
• Original Assignee: Soraa, Inc.
• Inventors: D'Evelyn, Mark P., Kamber, Derrick S.
• Primary Examiner(s): WIESE, NOAH S
• Application Number:
  US13/894,220
• Publication Number:
  US 20130251615A1
• Time in Patent Office: 679 Days
• Field of Search: 501/96.1, 501/96.4, 501/97.1, 501/97.2, 501/97.3, 501/98.4, 501/98.5
• US Class Current: 501/96.1
• CPC Class Codes: C01B 21/0632 with gallium, indium or thallium
• CPC Class Codes: C30B 28/06 by normal freezing or freezing under temperature gradient
• CPC Class Codes: C30B 29/403 AIII-nitrides
• CPC Class Codes: C30B 7/10 by application of pressure, e.g. hydrothermal processes
• 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

Abstract

A gettered polycrystalline group III metal nitride is formed by heating a group III metal with an added getter in a nitrogen-containing gas. Most of the residual oxygen in the gettered polycrystalline nitride is chemically bound by the getter. The gettered polycrystalline group III metal nitride is useful as a raw material for ammonothermal growth of bulk group III nitride crystals.

Claims

1. A method of preparing a polycrystalline group III metal nitride material, comprising:

providing a source material selected from a group III metal , a group III metal halide, or a combination thereof into a chamber, the source material comprising at least one metal selected from at least aluminum, gallium, and indium;

providing a getter at a level of at least 100 ppm with respect to the source material into the chamber such that the getter contacts the source material, wherein the getter is provided to the chamber via a vapor phase;

transferring a nitrogen-containing material into the chamber;

heating the chamber to a determined temperature;

pressurizing the chamber to a determined pressure;

processing the nitrogen-containing material with the source material in the chamber; and

forming a polycrystalline group III metal nitride material.

2. The method of claim 1, wherein the getter comprises at least one of an alkaline earth metal, boron, carbon, scandium, titanium, vanadium, chromium, yttrium, zirconium, niobium, a rare earth metal, hathium, tantalum, and tungsten, a nitride of any of the foregoing, an oxynitride of any of the foregoing, an oxyhalide of any of the foregoing, and a halide of any of the foregoing.

3. The method of claim 1, wherein the getter comprises at least one of boron, carbon, scandium, yttrium, and a rare earth metal.

4. The method of claim 1, wherein the getter is provided into a crucible within the chamber together with the source material.

5. The method of claim 4, wherein the getter is provided at a level greater than about 0.1% with respect to the source material.

6. The method of claim 1, wherein the getter is provided at a level greater than 300 parts per million with respect to the source material.

7. The method of claim 6, wherein the getter is provided at a level greater than about 1% with respect to the source material.

8. The method of claim 1, further comprising supplying a dopant or a dopant precursor to the chamber.

9. The method of claim 1, further comprising contacting the source material with one or more wetting agents, wherein the one or more wetting agents comprises bismuth, germanium, tin, lead, antimony, tellurium, polonium, and a combination of any of the foregoing.

10. The method of claim 1, further comprising:

cooling the chamber;

removing the polycrystalline group III nitride material from the chamber;

providing the polycrystalline group III nitride material to an autoclave or a capsule along with ammonia and a mineralizer; and

processing the polycrystalline group III nitride material in supercritical ammonia at a temperature greater than 400 degrees Celsius.

11. The method of claim 10, wherein the mineralizer comprises at least one of an alkali metal and an alkaline earth metal.

12. The method of claim 11, further comprising providing an additional getter comprising at least one of Be, Ca, Sr, Ba, Sc, Y, a rare earth metal, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W.

13. The method of claim 10, wherein the mineralizer comprises at least one of a chloride, a bromide, an iodide, and a fluoride.

14. The method of claim 13, further comprising providing an additional getter comprising at least one of Sc, Ti, V, Cr, Y, Zr, Nb, a rare earth metal, Hf, Ta, or W.

15. The method of claim 1, further comprising:

cooling the chamber;

removing the polycrystalline group III nitride material from the chamber;

providing the polycrystalline group III nitride material to a furnace along with a flux; and

processing the polycrystalline group III nitride material in a molten flux at a temperature greater than 400 degrees Celsius.

16. The method of claim 1, wherein the getter comprises one or more of a hydrocarbon (C_wH_y,where w, y >

0), a halocarbon C_wX_z, where w, z >

0 and X is selected from F, Cl, Br, and I), a halohydrocarbon (C_wH_yX_z, where w, y, z >

0 and X is selected from F, Cl, Br, and I), phosgene (COC1₂), thionyl chloride (SOC1₂), boron trichloride (BC1₃), diborane (B₂H₆), hydrogen sulfide (H₂S), a halide of an alkaline earth metal, boron, carbon, scandium, titanium, vanadium, chromium, yttrium, zirconium, niobium, the rare earth metals, hathium, tantalum, or tungsten, a hydride of an alkaline earth metal, boron, carbon, scandium, titanium, vanadium, chromium, yttrium, zirconium, niobium, the rare earth metals, hafnium, tantalum, or tungsten.

17. The method of claim 1, wherein the polycrystalline group III metal nitride material is formed downstream from a crucible containing the source material.

18. The method of claim 1, wherein one or more of a crucible for containment of group III metal, a reactor housing wall, a liner for the chamber, a gas inlet to the chamber, a baffle for gas mixing, and a substrate on which the polycrystalline group III metal nitride material is deposited comprises a material selected from tantalum carbide (TaC), silicon carbide (SiC), and pyrolytic boron nitride.

19. The method of claim 1, wherein one or more components of the chamber are loaded from a glove box before synthesis and the polycrystalline group III metal nitride material is removed from the chamber to the glove box after synthesis without substantial exposure to ambient air.

20. The method of claim 1, wherein:

the polycrystalline group III metal nitride material is a polycrystalline gallium-containing group III metal nitride material;

the group III metal is a gallium-containing group III metal; and

the group III metal halide is a gallium-containing group III metal halide.

21. The method of claim 1, wherein:

the determined temperature is from 800°

C. to 1,300 °

C.; and

the determined pressure is greater than 0.02 GPa.

22. A method of forming a polycrystalline gallium-containing group III metal nitride material, comprising:

providing a gallium-containing group III metal or a group III metal halide source material to a chamber, the gallium-containing group III metal or metal halide source material comprising at least one metal selected from aluminum, gallium, and indium;

providing a getter at a level of at least 100 ppm with respect to the source material into the chamber such that the getter contacts the source material;

transferring a nitrogen-containing material into the chamber;

heating the chamber to a determined temperature;

pressurizing the chamber to a determined pressure;

processing the nitrogen-containing material with the source material in the chamber to form a polycrystalline gallium-containing group III metal nitride material comprising a plurality of grains of a crystalline gallium-containing group III metal nitride;

the plurality of grains having an average grain size in a range from about 10nanometers to about 10 millimeters and defining a plurality of grain boundaries; and

the polycrystalline gallium-containing group III metal nitride material having;

an atomic fraction of a gallium-containing group III metal in a range from about 0.49 to about 0.55, the gallium-containing group III metal being selected from at least one of aluminum, indium, and gallium; and

an oxygen content in the form of a gallium-containing group III metal oxide or a substitutional impurity within the polycrystalline gallium-containing group III metal nitride material less than about 10 parts per million (ppm); and

a plurality of inclusions within at least one of the plurality of grain boundaries and the plurality of grains, the plurality of inclusions comprising a getter, the getter constituting a distinct phase from the crystalline gallium-containing group III metal nitride and located within individual grains of the crystalline gallium-containing group III metal nitride and/or at the grain boundaries of the crystalline gallium-containing group III metal nitride and being incorporated into the polycrystalline gallium-containing group III metal nitride at a level greater than about 200 parts per million, and;

forming a crystalline gallium-containing group III metal nitride crystal from the polycrystalline gallium-containing group III metal nitride material characterized by a wurtzite structure substantially free from any cubic entities and an optical absorption coefficient less than or equal to about 2 cm^-1 at wavelengths between about 405 nanometers and about 750nanometers.

23. The method of claim 22, wherein the polycrystalline gallium-containing group III metal nitride material comprises a plurality of grains of a crystalline gallium-containing group III metal nitride;

wherein

the plurality of grains is characterized by an average grain size in a range of from about 10 nanometers to about 10 millimeters and defines a plurality of grain boundaries; and

the polycrystalline gallium-containing group III metal nitride material is characterized by;

an atomic fraction of a gallium-containing group III metal in a range of from about 0.49 to about 0.55, the gallium-containing group III metal being selected from at least one of aluminum, indium, and gallium; and

an oxygen content in the form of a gallium-containing group III metal oxide or a substitutional impurity within the crystalline gallium-containing group III metal nitride less than about 10 parts per million (ppm); and

a plurality of inclusions within at least one of the plurality of grain boundaries and the plurality of grains, the plurality of inclusions comprising a getter, the getter constituting a distinct phase from the crystalline gallium-containing group III metal nitride and located within individual grains of the crystalline gallium-containing group III metal nitride and/or at grain boundaries of the crystalline gallium-containing group III metal nitride and being incorporated into the polycrystalline gallium-containing group III metal nitride material at a level greater than about 200 parts per million.