WO2010017232A1

WO2010017232A1 - Process for large-scale ammonothermal manufacturing of gallium nitride boules

Info

Publication number: WO2010017232A1
Application number: PCT/US2009/052750
Authority: WO
Inventors: Mark P. D'evelyn
Original assignee: Soraa Inc
Current assignee: Soraa Inc
Priority date: 2008-08-07
Filing date: 2009-08-04
Publication date: 2010-02-11
Anticipated expiration: 2011-02-07
Also published as: CN102144052A; JP2011530471A; PL394857A1

Abstract

A method for large-scale manufacturing of gallium nitride boules. Large-area single crystal seed plates are suspended in a rack, placed in a large diameter autoclave or internally-heated high pressure apparatus along with ammonia and a mineralizer, and grown ammonothermally. The seed orientation and mounting geometry are chosen to provide efficient utilization of the seed plates and of the volume inside the autoclave or high pressure apparatus. The method is scalable up to very large volumes and is cost effective.

Description

PROCESS FOR LARGE-SCALE AMMONOTHERMAL MANUFACTURING OF GALLIUM NITRIDE BOULES

CROSS-REFERENCES TO RELATED APPLICATIONS [0001] The present application claims priority to U.S. Provisional Serial Numbers

61/087,122, filed August 07, 2008, 61/087,135, filed August 07, 2008, 61/086,801, filed August 07, 2008, 61/086,800, filed August 07, 2008, 61/086,799, filed August 07, 2008, commonly assigned, and hereby incorporated by reference herein.

STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT

[0002] NOT APPLICABLE

REFERENCE TO A "SEQUENCE LISTING," A TABLE, OR A COMPUTER

PROGRAM LISTING APPENDIX SUBMITTED ON A COMPACT DISK. [0003] NOT APPLICABLE

BACKGROUND OF THE INVENTION

[0004] The present invention generally relates to processing of materials for growth of crystals. More particularly, the present invention provides a method for obtaining a gallium- containing nitride crystal by an ammonobasic or ammonoacidic technique, but there can be others. In other embodiments, the present invention provides an apparatus for large scale processing of nitride crystals, but it would be recognized that other crystals and materials can also be processed. Such crystals and materials include, but are not limited to, GaN, AlN, InN, InGaN, AlGaN, and AlInGaN, and others for manufacture of bulk or patterned substrates. Such bulk or patterned substrates can be used for a variety of applications including optoelectronic devices, lasers, light emitting diodes, solar cells, photoelectrochemical water splitting and hydrogen generation, photodetectors, integrated circuits, and transistors, among other devices.

[0005] Gallium nitride containing crystalline materials serve as a starting point for manufacture of conventional optoelectronic devices, such as blue light emitting diodes and lasers. Such optoelectronic devices have been commonly manufactured on sapphire or silicon carbide substrates that differ in composition from the deposited nitride layers. In the conventional Metal-Organic Chemical Vapor Deposition (MOCVD) method, deposition of GaN is performed from ammonia and organometallic compounds in the gas phase. Although successful, conventional growth rates achieved make it difficult to provide a bulk layer of GaN material. Additionally, dislocation densities are also high and lead to poorer optoelectronic device performance.

[0006] Other techniques have been proposed for obtaining bulk monocrystalline gallium nitride. Such techniques include use of epitaxial deposition employing halides and hydrides in a vapor phase and is called Hydride Vapor Phase Epitaxy (HVPE) ["Growth and characterization of freestanding GaN substrates" K. Motoku et al, Journal of Crystal Growth 237-239, 912

(2002)]. Unfortunately, drawbacks exist with HVPE techniques. In some cases, the quality of the bulk monocrystalline gallium nitride is not generally sufficient for high quality laser diodes because of issues with dislocation density, stress, and the like.

[0007] Techniques using supercritical ammonia have been proposed. Peters has described the ammonothermal synthesis of aluminum nitride [J. Cryst. Growth 104, 411 418 (1990)]. R.

Dwiliήski et al. have shown, in particular, that it is possible to obtain a fine-crystalline gallium nitride by a synthesis from gallium and ammonia, provided that the latter contains alkali metal amides (KNH₂ or LiNH₂). These and other techniques have been described in "AMMONO method of BN, AlN, and GaN synthesis and crystal growth", Proc. EGW-3, Warsaw, Jun. 22 24, 1998, MRS Internet Journal of Nitride Semiconductor Research, http://nsr.mij.mrs.Org/3/25, "Crystal growth of gallium nitride in supercritical ammonia" J. W. Kolis et al., J. Cryst. Growth 222, 431 434 (2001), and Mat. Res. Soc. Symp. Proc. Vol. 495, 367 372 (1998) by J. W. Kolis et al. However, using these supercritical ammonia processes, no wide scale production of bulk monocrystalline was achieved. [0008] Dwiliήski, in U.S. Patent Nos. 6,656,615 and 7,335,262, and D'Evelyn, in U.S. Patent Nos. 7,078,731 and 7,101,433, discuss apparatus and methods for conventional ammonothermal crystal growth of GaN. These methods are useful for growth of relatively small GaN crystals. Unfortunately, such methods have limitations for large scale manufacturing. The conventional apparatus with an inner diameter of 40 mm is useful for growing smaller diameter GaN crystals but is not suitable for large scale growth GaN boules. Additionally, conventional suspension of seed crystals using wires passing through single laser-drilled holes may be adequate for small crystals but is likely to be tedious and ineffective for large scale manufacturing. Other limitations may also exist.

[0009] From the above, it is seen that techniques for large scale crystal growth are highly desired. BRIEF SUMMARY OF THE INVENTION

[0010] According to the present invention, techniques related to processing of materials for growth of crystal are provided. More particularly, the present invention provides a method for obtaining a gallium-containing nitride crystal by an ammonobasic technique, but there can be others. In other embodiments, the present invention provides an apparatus for large scale processing of nitride crystals, but it would be recognized that other crystals and materials can also be processed. Such crystals and materials include, but are not limited to, GaN, AlN, InN, InGaN, AlGaN, and AlInGaN, and others for manufacture of bulk or patterned substrates. Such bulk or patterned substrates can be used for a variety of applications including optoelectronic devices, lasers, light emitting diodes, solar cells, photoelectrochemical water splitting and hydrogen generation, photodetectors, integrated circuits, and transistors, among other devices.

[0011] In a specific embodiment, the present invention provides a method for growth of a gallium-containing nitride crystal, e.g., GaN. The method includes providing gallium- containing source material and providing a mineralizer. In a specific embodiment, the method includes providing at least two seed plates, including a first seed plate and a second seed plate. The method includes supporting the first seed plate and the second seed plate in a first site and a second site of a seed rack. In a preferred embodiment, the first seed plate and the second seed plate have substantially an equivalent crystallo graphic orientation to within five degrees. Each of the first seed plate and the second seed plate have a length, e.g., at least 1 centimeter, according to a specific embodiment. The method includes placing the source material, mineralizer, and seed plates in a sealable container (e.g., autoclave, capsule) and introducing a nitrogen containing solvent into the sealable container. In a specific embodiment, the method includes processing the source material, mineralizer, and seed plates contained in the sealable container in a supercritical fluid at a temperature higher than about, for example, 400 degrees Celsius and a pressure higher than about, for example, 2 kbar. Of course, there can be other variations, modifications, and alternatives.

[0012] In an alternative specific embodiment, the present invention provides a method for growth a gallium-containing nitride crystal. The method includes providing gallium-containing source material and providing a mineralizer. The method also includes providing at least a first seed plate and a second seed plate. In a specific embodiment, the first seed plate has a first side having a first crystallographic orientation and a second side has a second crystallographic orientation. In a specific embodiment, the second seed plate has a first side having a first crystallographic orientation and a second side has a second crystallographic orientation. In a specific embodiment, the method also includes supporting the first seed plate and the second seed plate such that the first side of the first seed crystal faces the first side of the second seed crystal and spaced by a predetermined gap between the first side of the first seed crystal and the first side of the second seed crystal. The method includes placing the source material, mineralizer, and the seed plates in a sealable container. The method introduces a nitrogen- containing solvent in the sealable container and processes the source material, mineralizer, and seed plates contained in the sealable container in a supercritical fluid at a temperature higher than about, for example, 400 degrees Celsius and a pressure higher than about, for example, 2 kbar. [0013] Still further, the present invention provides a method for growth a gallium-containing nitride crystal, e.g., GaN. The method includes providing gallium-containing source material. In a specific embodiment, the method also includes providing a mineralizer and providing at least a first seed plate and a second seed plate. In a specific embodiment, the first seed plate has a first side having a first a-plane crystallographic orientation and a second side has a second a-plane crystallographic orientation. In a specific embodiment, the second seed plate has a first side having a first a-plane crystallographic orientation and a second side has a second a-plane crystallographic orientation. In a specific embodiment, the method includes supporting the first seed plate and the second seed plate. Each of the first seed plate and the second seed plate has a length of at least 1 centimeters according to a specific embodiment. In a specific embodiment, the method includes placing the source material, mineralizer, and the seed plates in a sealable container and introducing a nitrogen-containing solvent in the sealable container. In a preferred embodiment, the method includes processing the source material, mineralizer, and seed plates contained in the sealable container in a supercritical fluid at a temperature higher than about 400 degrees Celsius and a pressure higher than about 2 kbar. The method causes any spatial portion of the first side or the second side of the first seed plate or the first side or the second side of the second seed plate to change in character from an a-plane characteristic to an m-plane orientation characteristic. Preferably, the method also generally thickens each of the seed plates by way of crystal growth. [0014] Moreover, the present invention provides a process for growing a crystalline gallium- containing nitride, e.g., GaN. The process includes providing high pressure apparatus comprising a sealable container with gallium-containing feedstock in one zone and at least one seed in another zone. The process also includes introducing a solvent capable of forming a supercritical fluid into at least the one zone and the other zone and maintaining a pressure at or above about seven (7) atmospheres within the one zone and the other zone during introduction of the solvent into the one zone and the other zone. The method processes one or more portions of the gallium-containing feedstock in the supercritical fluid to provide a supercritical solution comprising at least gallium containing species at a first temperature. In a specific embodiment, the process also includes growing crystalline gallium-containing nitride material from the supercritical solution on the seed at a second temperature, which is characterized to cause the gallium containing species to form the crystalline gallium containing nitride material on the seed.

[0015] In still other embodiments, the present invention provides a process for growing a crystalline gallium-containing nitride. The process includes providing an autoclave comprising gallium-containing feedstock in one zone and at least one seed in another zone. The process also includes introducing a first solvent capable of forming a supercritical fluid into at least the one zone and the other zone. The process includes maintaining a pressure at or above about seven (7) atmospheres within the one zone and the other zone during introduction of the solvent into the one zone and the other zone. In a specific embodiment, the process includes processing one or more portions of the gallium-containing feedstock in the supercritical fluid to provide a supercritical solution comprising at least gallium containing species at a first temperature. In a specific embodiment, the process grows crystalline gallium-containing nitride material from the supercritical solution on the seed at a second temperature, which is characterized to cause the gallium containing species to form the crystalline gallium containing nitride material on the seed. In a specific embodiment, the process includes removing thermal energy from the autoclave to form a second solvent from the supercritical solution and removing the second solvent from the autoclave through an outlet.

[0016] In yet alternative embodiments, the present invention provides a process for growing a crystalline gallium-containing nitride. The process includes providing an autoclave comprising gallium-containing feedstock in a basket structure in one zone, at least one seed in another zone and a solvent capable of forming a supercritical fluid. In a preferred embodiment, the basket structure is configured to substantially prevent one or more solid portions of the feedstock from being transported from the one zone to the other zone. The method also includes processing one or more portions of the gallium-containing feedstock in the supercritical fluid to provide a supercritical solution comprising at least gallium containing species at a first temperature. The process also flows one or more portions of the supercritical solution containing the gallium containing species from the one zone through a portion of the basket into the other zone. The process includes growing crystalline gallium-containing nitride material from the supercritical solution on the seed at a second temperature, which is characterized to cause the gallium containing species to form the crystalline gallium containing nitride material on the seed.

[0017] Still further, the present invention provides an alternative process for growing a crystalline gallium-containing nitride. The process includes providing a high pressure apparatus comprising gallium-containing feedstock in one zone, at least one seed in another zone, an azide mineralizer, and at least one metal. In one or more embodiments, the azide mineralizer and the metal are provided in a predetermined ratio such that nitrogen generated by decomposition of the azide mineralizer and hydrogen generated by reaction of the metal with a supercritical fluid are in a ratio of approximately 1 :3, but can be others. In a specific embodiment, the process includes processing one or more portions of the gallium-containing feedstock in the supercritical fluid to provide a supercritical solution comprising at least gallium containing species at a first temperature. The process also grows crystalline gallium-containing nitride material from the supercritical solution on the seed at a second temperature, which is characterized to cause the gallium containing species to form the crystalline gallium containing nitride material on the seed.

[0018] In other embodiments, the present invention provides a process for growing a crystalline gallium-containing nitride. The process includes providing a high pressure apparatus comprising gallium-containing feedstock in one zone, at least one seed in another zone, an azide mineralizer, at least one metal, and a catalyst within a vicinity of either or both the one zone or/and the other zone. In a specific embodiment, the azide mineralizer and the metal are provided in a predetermined ratio such that nitrogen generated by decomposition of the azide mineralizer and a hydrogen gas species generated by reaction of at least the metal with a supercritical ammonia are in a ratio of approximately 1 :3 and greater, but can be other ratios. The process also processes one or more portions of the gallium-containing feedstock in the supercritical ammonia to provide a supercritical ammonia solution comprising at least gallium containing species at a first temperature and grows crystalline gallium-containing nitride material from the supercritical ammonia solution on the seed at a second temperature, which is characterized to cause the gallium containing species to form the crystalline gallium containing nitride material on the seed. The process also includes generating the hydrogen gas species from at least the reaction between the metal and the supercritical ammonia fluid and processing the hydrogen gas species using at least the catalyst to convert the hydrogen gas species and a nitrogen gas species to the supercritical ammonia fluid.

[0019] Benefits are achieved over pre-existing techniques using the present invention. In particular, the present invention enables a cost-effective high pressure apparatus for growth of crystals such as GaN, AlN, InN, InGaN, and AlInGaN and others. In a specific embodiment, the present method and apparatus can operate with components that are relatively simple and cost effective to manufacture. Depending upon the embodiment, the present apparatus and method can be manufactured using conventional materials and/or methods according to one of ordinary skill in the art. The present apparatus and method enable cost-effective crystal growth and materials processing under extreme pressure and temperature conditions in batch volumes larger than 0.3 liters, larger than 1 liter, larger than 3 liters, larger than 10 liters, larger than 30 liters, larger than 100 liters, and larger than 300 liters according to a specific embodiment.

Depending upon the embodiment, one or more of these benefits may be achieved. These and other benefits may be described throughout the present specification and more particularly below.

[0020] The present invention achieves these benefits and others in the context of known process technology. However, a further understanding of the nature and advantages of the present invention may be realized by reference to the latter portions of the specification and attached drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figures Ia and Ib are crystal growth frame structures according to embodiments of the present invention.

[0022] Figures 2a, 2b, and 2c are crystal growth seed rack structures according to embodiments of the present invention.

[0023] Figures 3a and 3b are simplified diagrams illustrating processing methods for crystal growth apparatus according to embodiments of the present invention. [0024] Figures 4a, 4b, and 4c are simplified diagrams illustrating crystal growth processes according to embodiments of the present invention.

[0025] Figure 5 is a simplified diagram of flow chart illustrating a crystal growth process according to an embodiment of the present invention. [0026] Figures 6a and 6b are simplified diagrams illustrating a recycling operation for crystal growth according to embodiments of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0027] According to the present invention, techniques related to processing of materials for growth of crystal are provided. More particularly, the present invention provides a method for obtaining a gallium-containing nitride crystal by an ammonobasic or ammonoacidic technique, but there can be others. In other embodiments, the present invention provides an apparatus for large scale processing of nitride crystals, but it would be recognized that other crystals and materials can also be processed. Such crystals and materials include, but are not limited to, GaN, AlN, InN, InGaN, AlGaN, and AlInGaN, and others for manufacture of bulk or patterned substrates. Such bulk or patterned substrates can be used for a variety of applications including optoelectronic devices, lasers, light emitting diodes, solar cells, photoelectrochemical water splitting and hydrogen generation, photodetectors, integrated circuits, and transistors, among other devices.

[0028] In the present invention the following definitions apply according to one or more embodiments. Such definitions are not intended to be limiting, but should be helpful to the reader. Of course, there can be other variations, modifications, and alternatives.

[0029] Gallium-containing nitride means a nitride of gallium and optionally other element(s) of group XIII (according to IUPAC, 1989). It includes, but is not restricted to, the binary compound GaN, ternary compounds such as AlGaN, InGaN and also AlInGaN, where the ratio of the other elements of group XIII to Ga can vary in a wide range. Of course, there can be other variations, modifications, and alternatives.

[0030] Autoclave means a closed container which has a reaction chamber where the ammonobasic or ammonoacidic process according to the present invention is carried out. As conventionally used in the art, closed is understood to mean sealed and gas tight in the ordinary meaning. As conventionally used in the art, an autoclave is understood to be externally heated, that is, so that the temperature of the inner walls of the autoclave is approximately equal to the temperature of the supercritical fluid proximate to the autoclave walls in the ordinary meaning. Of course, there can be other variations, modifications, and alternatives.

[0031] High pressure apparatus means an apparatus capable of containing supercritical ammonia and a growth environment for gallium-containing nitride at temperatures between about 100 degrees Celsius and about 800 degrees Celsius and pressures between about 1 kilobar (kbar) and about 10 kbar. In one embodiment, the high pressure apparatus comprises an autoclave, as described by U.S. Patent No. 7,335,262, which is hereby incorporated by reference in its entirety. In another embodiment, the high pressure apparatus is an internally heated high pressure apparatus, as described in U.S. Patent No. 7,125,453, and in U.S. Patent Applications 2006/0177362Al and U.S. SerialNo. 12/133,364, which are hereby incorporated by reference in their entirety. Of course, there can be other variations, modifications, and alternatives.

[0032] In the discussion that follows, the present apparatus is described as being vertically oriented. In another embodiment, the apparatus is instead horizontally oriented or oriented at an oblique angle intermediate between vertical and horizontal, and may be rocked so as to facilitate convection of the supercritical fluid within the high pressure apparatus. The present methods may be used in conjunction with a sealable container and high pressure apparatus. Examples of representative applicable apparatus are described in U.S. Patent Nos. 7,101,433, 7,125,453, and 7,160,388, and in U.S. Patent Application Nos. 61/073,687, 12/133,365 and 12/133,364, all of which are hereby incorporated by reference in their entirety. Reference should also be made to Figure 5, which lists the general steps for carrying out a process of crystal growth according to an embodiment of the present invention. As shown, Figure 5 is merely an illustration and should not unduly limit the scope of the claims herein. One of ordinary skill in the art would recognize other variations, modifications, and alternatives.

[0033] A schematic of a frame for seed crystals and raw material is shown in Figures Ia and Ib. The frame enables seed crystals and raw material to be loaded into a suitable configuration for crystal growth prior to placement inside a high pressure apparatus and in a form that is convenient for subsequent handling. The frame should retain good rigidity under crystal growth conditions and be chemically inert to the crystal growth environment, neither contributing contamination to the growing crystals nor undergoing significant corrosion. The materials of construction of the frame and the components thereof may include one or more of copper, copper-based alloy, gold, gold-based alloy, silver, silver-based alloy, palladium, platinum, iridium, ruthenium, rhodium, osmium, titanium, vanadium, chromium, iron, iron- based alloy, nickel, nickel-based alloy, zirconium, niobium, molybdenum, tantalum, tungsten, rhenium, silica, alumina, combinations thereof, and the like. Iron-base alloys that may be used to form the frame include, but are not limited to, stainless steels. Nickel-base alloys that may be used to form the frame include, but are not limited to, inconel, hastelloy, and the like. Again, there can be other variations, modifications, and alternatives. In some embodiments, the components of the frame are fabricated from an alloy comprising at least two elements, for increased hardness and creep resistance. The frame and its components may comprise wire, wire cloth or mesh, foil, plate, sheet, square bar, round bar, rectangular bar, tubing, threaded rod, and fasteners. The frame and its components may be attached by means of welding, arc welding, resistance welding, brazing, clamping, attachment by means of fasteners such as at least one of screws, bolts, threaded rod, and nuts, and the like.

[0034] The frame may include, as components, a baffle, a raw material basket, and a rack for suspending seed crystal plates, plus a means for attaching at least two of the aforementioned components. In one set of embodiments, illustrated in Figure Ia, appropriate for the case where the crystal to be grown has a solubility that increases with increasing temperature, the basket is positioned below the baffle and the seed rack is positioned above the baffle. In another set of embodiments, illustrated in Figure Ib, appropriate for the case where the crystal to be grown has a solubility that decreases with increasing temperature, i.e., retrograde solubility, the basket is positioned above the baffle and the seed rack is positioned below the baffle. A larger volume may be provided for the crystal growing region, that is, the region containing the seed rack, than for the nutrient region, that is, the region containing the basket. In one specific embodiment, the ratio of the volumes of the crystal growing region and the nutrient region is between 1 and 5. In other embodiments, this ratio is between 1.25 and 3, or between 1.5 and 2.5. The overall diameter and height of the frame are chosen for a close fit within the high pressure apparatus, so as to maximize the utilization of the available volume and optimize the fluid dynamics. The diameter of the frame may be between 1 inch and 2 inches, between 2 inches and 3 inches, between 3 inches and 4 inches, between 4 inches and 6 inches, between 6 inches and 8 inches, between 8 inches and 10 inches, between 10 inches and 12 inches, between 12 inches and 16 inches, between 16 inches and 24 inches, or greater than 24 inches. The ratio of the overall height of the frame to its diameter may be between 1 and 2, between 2 and 4, between 4 and 6, between 6 and 8, between 8 and 10, between 10 and 12, between 12 and 15, between 15 and 20, or greater than 20. [0035] The baffle provides a means for dividing the high pressure apparatus into which the frame is to be inserted into two separate regions, and comprises one or more disks. The two regions are in fluid communication with each other, as the baffle has a plurality of through- holes, or openings. Thus, a fraction of the cross-sectional area of the baffle is open. In a specific embodiment, the baffle has a fractional open area of between about 0.5% and about 30%, but can also have other percentages. In other embodiments, the baffle has a fractional open area between 2% and 20%, or between 5% and 15%. Baffle serves the purpose of confining the at least one (or more) source material to a specific region or end of chamber 108 while permitting solvent and, under high pressure high temperature (HPHT) conditions, supercritical fluid, to migrate throughout the high pressure apparatus by passing freely through through-holes in baffle. Often times, this feature is particularly useful in applications such as crystal growth, in which the supercritical fluid transports the at least one material, a nutrient material, from one region of the chamber, defined by placement of baffle, to another region where crystal growth on seed crystals take place. In one specific embodiment, the diameter of the baffle is equal to the maximum diameter of the overall frame. In other embodiments, the diameter of the baffle is slightly less than the maximum diameter of the overall frame, providing an annular space through which fluid can flow under crystal growth conditions. The diameter of the baffle may be less than the maximum diameter of the overall frame by 0.5 inch or less. The openings in the baffle should be large enough so as not to clog readily. In one specific embodiment, the diameters of the openings in the baffle are between 0.020 inch and 0.5 inch. In another embodiment, the diameters of the openings in the baffle are between 0.050 inch and 0.25 inch. In one specific embodiment, the baffle comprises a single disk with a thickness between 0.020 inch and 0.5 inch. In another embodiment, the baffle comprises a single disk with a thickness between 0.050 inch and 0.25 inch. In some embodiments, the baffle comprises two disks, three disks, or more. In some multi-disk embodiments one or more of the openings in the disks lie above one another. In other multi-disk embodiments, one or more of the openings in the disks do not lie above one another. The effective fractional open area in multi-disk baffle embodiments may therefore lie between the fractional open area of each disk, as an upper bound, and the product of the fractional open areas of each disk. [0036] The raw material basket provides a convenient means for transferring the raw material, including source material and mineralizer, into the high pressure apparatus, for permitting facile fluid communication from the region between source material particles within the basket and the crystal growth region, and for removing un-consumed source material from the reactor at the conclusion of a growth run. In one embodiment, the basket comprises wire mesh or wire cloth, as indicated schematically in the Figures. The diameter of the wire in the mesh or cloth may be between 0.001 inch and 0.25 inch, between 0.005 inch and 0.125 inch, or between 0.010 inch and 0.080 inch. The wire mesh or wire cloth may be contained within and, optionally, attached to a frame comprising larger-diameter wire so as to provide improved mechanical support. In another embodiment, the basket comprises foil or plate with a plurality of through-holes or openings. The size of the openings in the wire mesh, wire cloth, or foil or plate should be small enough so that raw material particles do not pass through them during crystal growth, even after a significant portion of the raw material has been etched and/or consumed by the crystal growth operation. In one specific embodiment, the openings in the wire mesh, wire cloth, or foil or plate have a diameter between 0.005 inch and 0.5 inch. In other embodiments, the openings have a diameter between 0.010 inch and 0.125 inch, or between 0.025 inch and 0.080 inch. In some embodiments, hollow pipes, with openings that are covered by wire mesh, are placed within the basket prior to loading of the raw material so as to improve fluid communication between the region between raw material particles within the basket and the crystal growth region. Suitable configurations for such hollow pipes are taught by U.S. Patent No. 3,245,760, which is hereby incorporated by reference in its entirety.

[0037] In some embodiments, the source material is placed in the basket prior to placement of seed crystals on the seed rack, so as to minimize the likelihood of breakage of the latter. The source material may be supplied in various forms. In some embodiments, the source material comprises single crystals or chunks or grit of poly crystalline material. In other embodiments, the source material comprises chunks of sintered polycrystalline material. In the case of gallium nitride, the source material may be derived from by-product single- or poly-crystalline GaN deposited on the wall or miscellaneous surfaces with a hydride vapor phase epitaxy (HVPE) reactor. In another specific embodiment, the source material comprises plates of single- or poly-crystalline GaN grown on a substrate by HVPE. In another specific embodiment, the source material is derived from sintered GaN powder, as disclosed by US patent 6,861,130, which is hereby incorporated by reference in its entirety. In another specific embodiment, the source material is derived from polycrystalline GaN plates comprising a columnar microstructure, as disclosed by US patent application 2007/0142204A1, which is hereby incorporated by reference in its entirety. The source material may contain oxygen at a concentration below 10¹⁹ cm^"3, belowlO¹⁸ cm^"3, or below 10¹⁷ cm^"3. The source material may contain an n-type dopant, such as Si or O, a p-type dopant, such as Mg or Zn, a compensatory dopant, such as Fe or Co, or a magnetic dopant, such as Fe, Ni, Co, or Mn, at concentrations between 10¹⁶ cm^"3 and 10²¹ cm^"3. In one specific embodiment, the particle size distribution of the source material lies between about 0.020 inch and about 5 inches. In another embodiment, the particle size distribution of the source material lies between about 0.050 inch and about 0.5 inch. In a preferred embodiment, the total surface area of the source material is greater, by at least a factor of three, than the total surface area of all the seed crystal plates that are placed in the seed rack.

[0038] In some embodiments, the source material comprises a metal that will become molten at elevated temperatures, for example, gallium or indium. In some embodiments, the mineralizer comprises a metal that will become molten at elevated temperatures, for example, sodium, potassium, or lithium. If placed in direct contact with the inner surface of an autoclave or a capsule, the metal may form an alloy, compromising the integrity of the autoclave or capsule. In some embodiments, therefore, at least one crucible is placed within or proximate to the raw material basket and contains at least one metal. The crucible should be chemically inert with respect to the supercritical fluid crystal growth environment and should not react or alloy with the at least one metal. In one specific embodiment, the crucible comprises molybdenum, tantalum, niobium, iridium, platinum, palladium, gold, silver, or tungsten. In another specific embodiment, the crucible comprises alumina, magnesia, calcia, zirconia, yttria, aluminum nitride or gallium nitride. The crucible may comprise a sintered or other poly crystalline material.

[0039] The seed rack provides a convenient means for transferring the seed crystals or plates into the high pressure apparatus, for permitting facile fluid communication between the seed crystals or plates and the nutrient region on the other side of the baffle, and for removing the grown crystals from the reactor at the conclusion of a growth run. The seed rack should be easy to load and unload, enable efficient usage of the available crystal growth volume, and minimize breakage and other yield losses of the crystals.

[0040] In preferred embodiments, the seed crystals or plates comprise gallium nitride. In other embodiments, the seed crystals or plates may comprise aluminum nitride, sapphire, silicon carbide, MgAl₂O₄ spinel, zinc oxide, or the like. The seed plates have a minimum lateral dimension of at least one centimeter. In some embodiments, the seed plates have a maximum lateral dimension of at least two centimeters and a minimum lateral dimension of at least one centimeter. In other embodiments, the seed plates have minimum lateral dimensions of at least three centimeters, at least four centimeters, at least five centimeters, at least six centimeters, at least eight centimeters, or at least ten centimeters. In some embodiments, the seed plates are bulk single crystals of gallium nitride. In some embodiments the seed plates are prepared from crystals that were grown by hydride vapor phase epitaxy. In other embodiments, the seed plates are prepared from crystals that were grown ammonothermally. In still other embodiments, the seed plates are prepared from crystals that were grown from solution in a flux. In one specific embodiment, the seed plates are prepared by the method disclosed in U.S. Patent Application No. 61/078,704, which is incorporated by reference herein. In some embodiments, the dislocation density at the large-area surfaces of the seed plates is less than about 10⁶ cm^"2. In some embodiments, the dislocation density at the large-area surfaces of the seed plates is less than about 10⁵ cm^"2, less than about 10⁴ cm^"2, less than about 10³ cm^"2, or less than about 10² cm^"2. In some embodiments, the full width at half maximum of the x-ray diffraction line corresponding to the crystallographic orientation of the large-area face is less than 300 arc seconds, less than 150 arc seconds, less than 100 arc seconds, or less than 50 arc seconds.

[0041] Gallium nitride is a hexagonal, wurtzite-structure crystal (space group Poync; point group 6mm) with distinct growth sectors. Under a given set of growth conditions, growth occurs at different rates in the +c direction, the -c direction, the m directions, the a directions, and in other crystallographic directions. In general, fast-growing directions tend to grow themselves out of existence, so that the resulting crystals are terminated mainly by facets associated with the slower-growing directions. The most commonly occurring facets under ammonothermal growth conditions are c-plane (0 0 0 1) and (0 0 0 -1), and m-plane {1 -1 0 0}. Other planes, for example, a-plane {1 1 -2 0} and semi-polar {1 -1 0 -1} occur less frequently or with smaller areas. Manufacturing efficiency is enhanced by using seed crystals or plates that are already large in a relatively slow-growing dimension, and performing the predominant crystal growth in a relatively faster growing direction. In preferred embodiments, the large area faces of the seed plates are stable under the pre-selected growth conditions, i.e., do not facet, which is facilitated by selecting seed plates with (0 0 0 1), (0 0 0 -1), {1 -1 0 0}, {1 1 -2 0}, or {1 -1 0 -1} orientations. [0042] In addition, the tendency for impurity uptake differs from one growth sector to another. For example, as shown by Frayssinet and co-workers, writing in the Journal of Crystal Growth, volume 230, pages 442-447 (2001), the concentration of free carriers, caused by point defects, is markedly different in the +c and -c growth sectors of unintentionally-doped bulk GaN crystals grown by a particular technique. Similar results have been reported by other authors, with the general tendency that the [0 0 0 -1], or -c, growth sector incorporates a higher impurity concentration than does the [0 0 0 1], or +c, growth sector. Differential impurity uptake is undesirable for at least two reasons. First, the presence of concentration gradients within crystals makes it more difficult for the crystal manufacturer to maintain consistent product specifications. Second, the presence of concentration gradients within the crystal generates strain (typically, impurities in GaN cause a slight increase in the lattice constants), which can lead to bow, cracking, dislocation generation, and other detrimental effects. Manufacturing efficiency, including yield, product quality, and product consistency, is enhanced by restricting the predominant crystal growth to occur in only one growth sector.

[0043] In one or more embodiments, manufacturing growth is desired to occur predominantly on m planes. For example, under a predetermined set of growth conditions crystal growth may occur more rapidly in the a direction than in the m direction, and more rapidly in the m direction than in the +c or -c directions. Under such a predetermined set of growth conditions, spontaneously nucleated and grown crystals will take the shape of hexagonal platelets, with large c facets and long m-plane-terminated side edges and a thickness that is less than the diameter. Growth in the m direction could also be preferred by virtue of improved crystallographic quality, reduced impurity incorporation, or, conversely, by increased capability for incorporation of dopants or band-gap modifiers such as Al or In. Growth in the m direction may also be ideal for producing m-plane -oriented wafers. Opposite faces on an m-plane oriented seed crystal or plate will both constitute m planes, so use of such a seed crystal would produce growth in a single crystallographic growth sector.

[0044] In one set of embodiments, the seed crystals are attached to the seed rack as shown schematically in Figures 2a and 2b. Individual seed crystals may be selected or cut to have approximately the same height, so that multiple seed crystals may be placed adjacent to one another in a tier of the seed rack. The seed crystals may have rectangular large-area faces. The seed crystals may be placed between upper and lower seed rack bars and held in place by means of clips. The clips may clamp the seed crystals by spring force, by virtue of the seed crystal being thicker than the separation between opposite sides of the clip when the latter is free standing and relaxed. In an alternative set of embodiments, the seed crystal is affixed to the clip by virtue of a fastener positioned proximate to the clip, seed crystal, and seed rack, such as a length of threaded rod with nuts on opposite ends. In yet another set of embodiments the clips are attached to the seed crystals first and then attached to the seed rack. In some embodiments, the clips have at least one opening through which the crystal can grow, so as to minimize strain and defect generation. In still another set of embodiments, the seed rack comprises recesses, slots, hollows, or the like, into which opposite ends of the seed crystals are slid. Pieces of foil may be placed between the seed crystals and the recesses in the seed rack so as to facilitate removal after crystal growth. In preferred embodiments, each seed crystal is attached to the seed rack in at least two positions, so as to minimize the likelihood of seed or crystal breakage before, during, or after crystal growth, and to hold the seed crystals accurately in the desired positions in the reactor. Adjacent seed crystals or plates may be separated by a crystal separator plate. The crystal separator plates may have holes that slide over the seed rack bar(s), may have slots that are open on one side so as to slide over the seed rack bar, or the like.

[0045] In some embodiments, holes or slots are provided in the seed crystals or plates, and the seed crystals or plates are suspended from the seed rack by at least one wire or foil strip. In some embodiments, the seed crystals are suspended by at least two wires or foil strips. The holes or slots in the seed crystals or plates may be formed by laser drilling or cutting, by ultrasonic drilling, by mechanical drilling or milling, by grinding, by sanding, by electric discharge machining, by water jet cutting, or the like.

[0046] In one set of embodiments, manufacturing growth is desired to occur predominantly on a planes. Growth in the a direction may provide a useful means for preparing semi-polar substrate orientations. Growth in the a direction could also be preferred by virtue of improved crystallographic quality, reduced impurity incorporation, or, conversely, by increased capability for incorporation of dopants or band-gap modifiers such as Al or In. Opposite faces on an a- plane oriented seed crystal or plate will both constitute a planes, so use of such a seed crystal would produce growth in a single crystallographic growth sector.

[0047] In another set of embodiments, manufacturing growth is desired to occur predominantly on c planes, either in the +c direction (the [0 0 0 1] Ga-polar direction) or -c direction (the [0 0 0 -1] N-polar direction). For example, under a predetermined set of growth conditions crystal growth may occur more rapidly in the +c or -c direction than in the m direction. Under such a predetermined set of growth conditions, spontaneously nucleated and grown crystals will take the shape of hexagonal pillars, prisms, or needles, with small c facets and long m-plane-terminated side edges and a length that is less than the diameter. Growth in the +c or -c direction could also be preferred by virtue of improved crystallographic quality, reduced impurity incorporation, or, conversely, by increased capability for incorporation of dopants or band-gap modifiers such as Al or In. Growth in the +c or -c direction may also be ideal for producing c-plane-oriented wafers. Opposite faces on an c-plane oriented seed crystal or plate constitute different planes, so use of such a seed crystal alone would produce growth in two distinct crystallographic growth sectors. Growth in a single crystallographic growth sector may be achieved by stacking pairs of c-plane-oriented seed crystals or plates back to back, with like faces facing one another. For example, the -c face of two c-plane-oriented seed crystals or plates could be faced proximate to one another, so that the +c faces of the two c-plane-oriented seed crystals or plates face outward and would yield growth in a single crystallographic orientation. Conversely, the +c face of two c-plane-oriented seed crystals or plates could be faced proximate to one another, so that the -c faces of the two c-plane-oriented seed crystals or plates face outward and would yield growth in a single crystallographic orientation. The pairs of seed crystals could be placed in direct contact with one another or could be separated by a crystal separator plate. If the pairs of seed crystals or plates grew together during a growth run they could be separated after the run, if desired, or could be left together for use as a seed (bi- )crystal in a subsequent run. A c-plane-oriented bi-crystal, on which both large-area faces constitute +c or -c surfaces, is suitable for use as a seed, as growth on the large area faces will occur in only a single crystallographic direction. At least one contact twin or stacking fault, oriented substantially parallel to the large-area surfaces, may be present in the bi-crystal.

[0048] In yet another set of embodiments, manufacturing growth is desired to occur predominantly on the semi-polar {1 -1 0 -1} plane. Growth in this semipolar direction could be preferred by virtue of improved crystallographic quality, reduced impurity incorporation, or, conversely, by increased capability for incorporation of dopants or band-gap modifiers such as Al or In. Growth perpendicular to the {1 -1 0 -1} plane may also be ideal for producing {1 -1 0 -l}-oriented wafers. Opposite faces on an {1 -1 0 -1} -oriented seed crystal or plate constitute different planes, so use of such a seed crystal alone would produce growth in two distinct crystallographic growth sectors. Growth in a single crystallographic growth sector may be achieved by stacking pairs of {1 -1 0 -l}-oriented seed crystals or plates back to back, with the {1 -1 0 1} -oriented faces facing one another. The pairs of seed crystals could be placed in direct contact with one another or could be separated by a crystal separator plate. If the pairs of seed crystals or plates grew together during a growth run they could be separated after the run, if desired, or could be left together for use as a seed (bi-)crystal in a subsequent run. A (I -I O - 1} -oriented bi-crystal, on which both large-area faces constitute {1 -1 0 -1} surfaces, is suitable for use as a seed, as growth on the large area faces will occur in only a single crystallographic direction. At least one contact twin, oriented substantially parallel to the large-area surfaces, may be present in the bi-crystal.

[0049] More generally, manufacturing growth may be desired to occur predominantly on a semi-polar (h k i I) plane, where where i=-(h+k), / is nonzero and at least one of A and k are nonzero. Growth in this semipolar direction could be preferred by virtue of improved crystallographic quality, reduced impurity incorporation, or, conversely, by increased capability for incorporation of dopants or band-gap modifiers such as Al or In. Opposite faces on an (h k i /)-oriented seed crystal or plate constitute different planes, so use of such a seed crystal alone would produce growth in two distinct crystallographic growth sectors. Growth in a single crystallographic growth sector may be achieved by stacking pairs of (h k i /)-oriented seed crystals or plates back to back, with the (h k i /)-oriented faces placed proximate to one another, so that the (h k i -I) faces of the two seed crystals or plates face outward and would yield growth in a single crystallographic orientation. The pairs of seed crystals could be placed in direct contact with one another or could be separated by a crystal separator plate. If the pairs of seed crystals or plates grew together during a growth run they could be separated after the run, if desired, or could be left together for use as a seed (bi-)crystal in a subsequent run. A semi-polar bi-crystal, on which both large-area faces constitute the same semi-polar orientation, is suitable for use as a seed, as growth on the large area faces will occur in only a single crystallographic direction. [0050] In some embodiments, the seed crystals or plates have a rectangular or approximately rectangular shape. An approximately rectangular shape may be particularly appropriate for m- plane or a-plane seed plates. In some embodiments, the corners of the seed crystals or plates are rounded or chamfered so as to minimize the likelihood of breakage. Rectangular shapes are convenient for mounting and for efficiently utilizing space within the high pressure crystal growth reactor. In other embodiments, the seed crystals or plates have a hexagonal or approximately hexagonal shape. A hexagonal shape may be particularly convenient when working with c-plane -oriented seed crystals or plates. In still other embodiments, the seed crystals or plates have a circular, oval, or approximately circular or oval shape.

[0051] In some embodiments, particularly those with non-rectangular seed crystals or plates, the seeds may be arranged in a non-rectangular, close-packed way, as shown in Figure 2c.

Rather than comprising linear arrays of bars arranged into multiple tiers stacked vertically, the seed rack may comprise a honeycomb-type arrangement, with hexagonal, circular, rectangular or other shape cutouts arranged in a regular pattern. The honeycomb structure may be formed from a sheet by wire electric discharge machining, water-jet cutting, milling, drilling, or the like. Alternatively, the honeycomb structure may be fabricated from bent quasi-horizontal bars attached with vertical reinforcement structures. [0052] In some embodiments, particularly those involving the use of an autoclave as the high pressure apparatus, the frame further comprises a set of stacked disks or baffles on the top end of the frame. The stacked disks or baffles reduce convective heat transfer from the supercritical fluid during crystal growth to the upper end of the autoclave so that the seal of the autoclave may be at a reduced temperature relative to the upper end of the interior of the autoclave. In other embodiments, one or more disks or baffles are placed on top of the frame after insertion of the latter into a high pressure apparatus.

[0053] After loading the frame with seed crystals and raw material, the frame is placed inside a sealable container. The sealable container may constitute an autoclave or a capsule designed for use with an internally-heated high pressure apparatus. At least one mineralizer may be added. The mineralizer may comprise an alkali metal such as Li, Na, K, Rb, or Cs, an alkaline earth metal, such as Mg, Ca, Sr, or Ba, or an alkali or alkaline earth hydride, amide, imide, amido-imide, nitride, or azide. The mineralizer may comprise an ammonium halide, such as NH₄F, NH₄Cl, NH₄Br, or NH₄I, a gallium halide, such as GaF₃, GaCl₃, GaBr₃, GaI₃, or any compound that may be formed by reaction of one or more of HF, HCl, HBr, HI, Ga, and NH₃. The mineralizer may comprise other alkali, alkaline earth, or ammonium salts, other halides, urea, sulfur or a sulfide salt, or phosphorus or a phosphorus-containing salt. The mineralizer may be provided as a metal, a loose powder, as granules, or as at least one densified compact or pill. The mineralizer may be added to the raw material basket, may be placed in a crucible, or may be placed directly in the high pressure apparatus or capsule. In a preferred embodiment, the mineralizer is added to the high pressure apparatus or capsule in the absence of exposure to air, such as inside a glove box.

[0054] A getter may also be added to the reaction mix. The getter preferentially reacts with residual or adventitious oxygen or moisture present, improving the purity and transparency of the grown GaN crystals. The getter may comprise at least one of an alkaline earth metal, Sc, Ti, V, Cr, Y, Zr, Nb, Hf, Ta, W, a rare earth metal, and their nitrides, amides, imides, amido- imides, or halides. [0055] In some embodiments, at least one of the mineralizer and the getter are placed in crucibles within or proximate to the raw material basket.

[0056] The use of metallic precursors for the raw material, mineralizer, and/or getter is convenient in some respects. For example, the metal is typically available commercially in high purity, and no further synthesis is required. However, in addition to the complexity of suitably supporting a metal that melts under reaction conditions (e.g., Ga, Na, K), the use of a pure metal may generate undesirable gases, such as hydrogen. For example, under ammonthermal reaction conditions the metals listed below will undergo one or more of the following reactions: Ga + NH₃ = GaN + 3/2 H₂

Na + NH₃ = NaNH₂ + 1/2 H₂

K + NH₃ = KNH₂ + 1/2 H₂

Mg + 2NH₃ = Mg(NH₂)₂ + H₂

3Mg + 2NH₃ = Mg₃N₂ + 3H₂ Y + 3NH₃ = Y(NH₂)₃ + 3/2 H₂

Y + NH₃ = YN + 3/2 H₂

[0057] The presence of hydrogen in the supercritical fluid solvent may decrease the solubility of gallium-containing species and, further, may embrittle the metal constituting the autoclave walls. [0058] The use of azides as mineralizers is convenient in that they are often available commercially in high purity, can be purified further, and are considerably less hygroscopic than the alkali metals or amides or the alkaline earth nitrides, for example. Use of azide mineralizers is suggested by Dwiliήski in U.S. Patent No. 7,364,619, which is hereby incorporated by reference in its entirety. However, azides typically decompose under reaction conditions, generating undesirable gases, such as nitrogen:

3NaN₃ + 2NH₃ = 3NaNH₂ + 4N₂

[0059] In a preferred embodiment, these two effects are combined so as to cancel each other out. Metals, including raw materials, mineralizers, and getters, are added together with azide mineralizer precursors such that H₂ and N₂ are generated in approximately a 3:1 ratio. The reaction container further comprises means for catalyzing NH₃ formation from H₂ and N₂.

Catalysis of the reaction between H₂ and N₂ liberated in the reaction of the metal with ammonia and decomposition of the azide, respectively, to re-form ammonia may be performed by the autoclave walls or by added catalyst. The added catalyst may comprise powder, granules, foil, a coating, bulk material, or a porous pellet. The added catalyst may comprise at least one of iron, cobalt, nickel, titanium, molybdenum, tungsten, aluminum, potassium, cesium, calcium, magnesium, barium, zirconium, osmium, uranium or a lanthanide, ruthenium, platinum, palladium, or rhodium. For example, a mole of added NaN₃ will generate 4/3 mole of N₂. The latter can be counterbalanced by also adding 8/3 moles of Ga metal, which will generate 8/3 x 3/2 mole = 4 moles OfH₂, viz., three times the number of moles of N₂ from NaN₃.

[0060] The sealable container is then closed and sealed except for a connection to a gas, liquid, or vacuum manifold. In one embodiment, the sealable container comprises an autoclave, as taught by U.S. Patent No. 7,335,262, which is hereby incorporated by reference in its entirety. In another embodiment, the sealable container comprises a metal can, as discussed by U.S. Patent No. 7,125,453, a container, as discussed by U.S. Patent Application No.

2007/0234946, or a capsule, as discussed by U.S. Patent Application No. 12/133,365, entitled "Improved capsule for high pressure processing and method of use for supercritical fluids," all of which are hereby incorporated by reference in their entirety. The inner diameter of the autoclave or capsule may be between 1 inch and 2 inches, between 2 inches and 3 inches, between 3 inches and 4 inches, between 4 inches and 6 inches, between 6 inches and 8 inches, between 8 inches, and 10 inches, between 10 inches and 12 inches, between 12 inches and 16 inches, between 16 inches and 24 inches, or greater than 24 inches. The clearance between the inner diameter of the autoclave or capsule and the outer diameter of the frame may be between 0.005 inch and 1 inch, or between 0.010 inch and 0.25 inch. The ratio of the inner height of the autoclave or capsule to its inner diameter may be between 1 and 2, between 2 and 4, between 4 and 6, between 6 and 8, between 8 and 10, between 10 and 12, between 12 and 15, between 15 and 20, or greater than 20.

[0061] In some embodiments, the autoclave or capsule is evacuated, so as to remove air, moisture, and other volatile contaminants. In some embodiments, the high pressure apparatus or capsule is heated during evacuation, to a temperature between about 25 degrees Celsius and about 500 degrees Celsius. In some embodiments, the autoclave or capsule are heated using the same heating elements that are used during high pressure processing. In one specific embodiment, the capsule is heated by placing it inside an internally-heated pressure apparatus and heated using the heater for the latter. [0062] In another set of embodiments, the autoclave or capsule containing the filled frame is purged to remove air, moisture, and other volatile contaminants, as shown in Figures 3a and 3b. Purging may provide for superior removal of air, moisture, and other volatile contaminants, relative to evacuation, because of the limited conductance through a tube or long hole to the interior of the autoclave or capsule. The autoclave or capsule is then coupled to a gas source by means of at least one fill tube or purge tube, preferably without exposing the contents of the capsule to air according to a specific embodiment. The gas source may comprise at least one of nitrogen, argon, hydrogen, helium, and solvent vapor, among others. In an embodiment, both a first fill or purge tube and a second fill or purge tube are coupled to a gas source and/or exhaust. In another embodiment, an inner purge tube is placed inside the fill or outer purge tube and positioned so that one end is proximate to the bottom end of the autoclave or capsule. The inner purge tube and outer purge tube may be fabricated from at least one of copper, copper- based alloy, gold, gold-based alloy, silver, silver-based alloy, palladium, platinum, iridium, ruthenium, rhodium, osmium, iron, iron-based alloy, nickel, nickel-based alloy, molybdenum, and combinations thereof. Iron-base alloys that may be used to form the inner purge tube or outer purge tube include, but are not limited to, stainless steels. Nickel-base alloys that may be used to form the inner purge tube or outer purge tube include, but are not limited to, inconel, hastelloy, and the like. The outer diameter of the inner purge tube may be less than the inner diameter of the fill or outer purge tube by at least 0.010 inch, as shown. The inner purge tube may be coupled to the fill or outer purge tube by means of a tee fitting or other suitable technique, so that purge gas introduced through the inner purge tube will exit near the bottom end of the autoclave or capsule, pass through the length of the autoclave or capsule before exhausting though the annular space in the fill or outer purge tube outside the inner purge tube and the tee fitting, providing for efficient removal of gas phase contaminants according to a specific embodiment. The interface between the tee fitting and the inner purge tube may be a sliding seal, for example, an O-ring or a differentially-pumped set of Teflon seals or O-rings. The rate of flow of the purge gas may be in the range between 0.05 and 10 standard liters per minute. The autoclave or capsule may be heated, for example, to a temperature between 25 degrees Celsius and 500 degrees Celsius during the purge operation, in order to more efficiently remove water and other adsorbed contaminants. After shutting off flow of the purge gas, solvent vapor, for example, gas phase ammonia, may be flowed through the autoclave or capsule in order to remove most or all of the purge gas. [0063] In a specific embodiment, the inlet of the gas flow, for example, the second fill tube or the purge tube is then coupled to a source of liquid solvent. The autoclave or capsule and fill tube(s) may be cooled, or the liquid solvent delivery system and transfer lines heated, so that the former are cooler by between one and 50 degrees Celsius than the latter. Liquid solvent is then introduced into the autoclave or capsule at a rate between 0.1 and 1000 grams per minute. At room temperature, the vapor pressure of ammonia is approximately 10 atmospheres. Depending on the temperature of the solvent source, therefore, the system pressure during solvent delivery may be above 7 atmospheres, above 8 atmospheres, above 9 atmospheres, or above 10 atmospheres. In one embodiment, the purge exhaust is closed and the solvent vapor above the liquid is forced to condense into liquid during the filling operation. In this embodiment, the autoclave or capsule may be actively cooled in order to dissipate the heat released by condensation of the solvent vapor. In another embodiment, the purge exhaust is fitted with a check valve so that residual purge gas or solvent vapor is allowed to exit when the pressure exceeds a predetermined threshold, but air or other gases are not allowed to flow backward into the autoclave. The quantity of solvent in the autoclave or capsule may be determined by using a liquid delivery system with the capability for accurately monitoring and controlling the mass of liquid delivered. An example of suitable equipment for delivery of precision-metered, high-purity liquid ammonia is the InScale™ system manufactured by iCon Dynamics, LLC. In some embodiments, the amount of ammonia delivered to the autoclave or capsule is quantified by the loss in weight of at least one ammonia supply cylinder. If solvent gas is allowed to exhaust during liquid filling, in the case where ammonia is the solvent, the quantity of vented solvent may be determined by trapping it in aqueous solution and measuring the change in pH and this quantity subtracted from the total liquid delivered to determine the quantity of liquid in the autoclave or capsule. An analogous method for determining the quantity of vented solvent may be performed in cases where the solvent is different from ammonia.

[0064] In an alternative embodiment, the solvent is delivered to the autoclave or capsule as a vapor at elevated pressure. The inlet of the gas flow, for example, the second fill tube or the purge tube is then coupled to a source of vapor-phase solvent. The autoclave or capsule and fill tube(s) may be cooled, or the solvent delivery system and transfer lines heated, so that the former are cooler by between one and 50 degrees Celsius than the latter. Vapor-phase solvent is then introduced into the autoclave or capsule at a rate between 0.1 and 1000 grams per minute and allowed to condense in the autoclave or capsule. The pressure of the solvent vapor should be higher than the equilibrium vapor pressure at the temperature of the autoclave or capsule. Depending on the temperature of the autoclave or capsule and of the solvent delivery system, the pressure during solvent delivery may be above 7 atmospheres, above 8 atmospheres, above 9 atmospheres, or above 10 atmospheres. In one embodiment, the purge exhaust is closed and the solvent vapor above the liquid is forced to condense into liquid during the filling operation. In this embodiment, the autoclave or capsule may be actively cooled in order to dissipate the heat released by condensation of the solvent vapor. In another embodiment, the purge exhaust is fitted with a check valve so that residual purge gas or solvent vapor is allowed to exit when the pressure exceeds a predetermined threshold, but air or other gases are not allowed to flow backward into the autoclave. The quantity of solvent in the autoclave or capsule may be determined by using a vapor delivery system equipped with a mass flow meter. In some embodiments, the amount of ammonia delivered to the autoclave or capsule is quantified by the loss in weight of at least one ammonia supply cylinder. If solvent gas is allowed to exhaust during liquid filling, in the case where ammonia is the solvent, the quantity of vented solvent may be determined by trapping it in aqueous solution and measuring the change in pH and this quantity subtracted from the total liquid delivered to determine the quantity of liquid in the capsule. An analogous method for determining the quantity of vented solvent may be performed in cases where the solvent is different from ammonia. [0065] Following filling of the autoclave or capsule, the inner purge tube, if present, may be removed. In some embodiments, the inner purge tube is removed after the purging step but before the filling step. A gate valve to the autoclave, or the fill tube(s) to the capsule, are then sealed. Once sealed, the interior of the autoclave or of the capsule is substantially air-free, and the at least one material contained therein can be processed with reduced risk of contamination. Of course, there can be other variations, modifications, and alternatives.

[0066] In some embodiments, the autoclave is then heated to crystal growth conditions. In other embodiments, the capsule is placed inside an autoclave, an internally-heated pressure apparatus, or other high pressure apparatus, and heated to crystal growth conditions. In some embodiments, the thermal cycle includes a pre-reaction segment to form mineralizer, polycrystalline gallium nitride, dissolved gallium containing complexes, or the like. In some embodiments, the atmosphere in the autoclave may be modified during the run. For example, excess H₂ formed by reaction of gallium metal with ammonia may be bled off through the gate valve or allowed to diffuse through a heated palladium membrane. Excess nitrogen formed by decomposition of an azide mineralizer may be bled off through the gate valve. Additional ammonia may be added to replenish the solvent in the high pressure apparatus.

[0067] Suitable thermal cycles for crystal growth are discussed by U.S. Patent Nos. 6,656,615 and 7,078,731, which are hereby incorporated by reference in their entirety. The crystals grow predominantly perpendicular to the large-diameter faces, but may also grow somewhat in lateral directions as well. With the possible exception of c-plane or {1 -1 0 ±1} seeds stacked back-to- back, the crystals are prevented from growing into one another by the crystal separator plates.

[0068] After performing crystal growth for a predetermined period of time, the autoclave or high pressure apparatus is cooled. When the autoclave or capsule has cooled to below 100 degrees Celsius, below 75 degrees Celsius, below 50 degrees Celsius, or below 35 degrees Celsius, a valve to the autoclave is opened, or the capsule is vented, and the ammonia is removed. In one embodiment, gas-phase ammonia is allowed to exit the autoclave or capsule and is bubbled through an acidic aqueous solution in order to be chemically trapped. In another embodiment, gas phase ammonia is passed through a flame so as to burn the ammonia, forming H₂O and N₂. In a preferred embodiment, illustrated in Figures 6a and 6b, the ammonia is trapped for recycling and reuse.

[0069] Referring to Figure 6a, appropriate for a single-ended autoclave or capsule, the ammonia may be removed as either a liquid or a gas. To remove the ammonia as a liquid, the inner purge tube (see Figures 3a 3b) is re-inserted into the outer purge or fill tube and the outlet of the inner purge tube connected to the Receiving/Purification tank. Keeping the purge gas exhaust connection (see Figures 3 a and 3b) closed, a valve in the line to the inner purge tube is opened, allowing liquid ammonia to flow through the inner purge tube in the autoclave into the Receiving/Purification tank, which is otherwise closed. The Receiving/Purification tank may be cooled, for example, by chilled water, and/or the autoclave or capsule and transfer line may be heated during the ammonia transfer operation, so as to maintain a higher vapor pressure of ammonia in the autoclave as compared to the vapor pressure in the Receiving/Purification tank. The temperature differential between the autoclave or capsule and the Receiving/Purification tank may be held between one and 50 degrees Celsius. In another embodiment, the ammonia is removed as a vapor. The outlet of the autoclave or capsule is connected to a condenser above the Receiving/Purification tank and a valve opened. Gas-phase ammonia enters the condenser and condenses into liquid in a heat-exchanger, for example, a chilled-water-cooled coil, at a pressure between about 100 and 250 pounds per square inch. The autoclave and transfer line may be heated to a temperature that is higher than the condenser by between one and 50 degrees Celsius. Residual gases, for example, N₂ and H₂, may be released by venting to a scrubber and/or a flame. [0070] Referring to Figure 6b, appropriate for a double-ended autoclave or capsule, the ammonia may be removed as a liquid. A port on the bottom end of the autoclave or a fill tube on the bottom end of the capsule is connected to the Receiving/Purification tank and a valve opened, allowing liquid ammonia to flow into the Receiving/Purification tank, which is otherwise closed. The Receiving/Purification tank may be cooled, for example, by chilled water, and/or the autoclave and transfer line may be heated during the ammonia transfer operation, so as to maintain a higher vapor pressure of ammonia in the autoclave as compared to the vapor pressure in the Receiving/Purification tank. The temperature differential between the autoclave and the Receiving/Purification tank may be held between one and 50 degrees Celsius.

[0071] For recycling purposes, a purifying agent, for example, sodium metal, may be placed in the receiving/purification tank. The sodium will react with residual oxygen and/or water in the ammonia, restoring a very high degree of purity. After a period of one hour to thirty days, the ammonia may be transferred to a delivery tank. In a preferred embodiment, the transfer is performed through the gas phase, via a condenser, so as to leave the purifying agent in the receiving/purification tank. Liquid ammonia may be delivered from the delivery tank, via a dip tube, to the autoclave for the next crystal growth run. In an alternative embodiment, vapor- phase ammonia may be delivered from the delivery tank to an autoclave or capsule for the next crystal growth run. [0072] After cooling, removal of the ammonia, and opening of the autoclave or internally- heated high pressure apparatus and capsule, the frame is removed from the autoclave or capsule, and the grown crystals are removed from the seed rack. If necessary, portions of the clips that have been overgrown by crystalline material may be removed by etching in an appropriate acid, such as at least one of hydrochloric acid, sulfuric acid, nitric acid, and hydrofluoric acid.

[0073] The crystals are sliced into pre-selected orientations, as summarized in Figures 4a, 4b, and 4c. In one embodiment, the seed crystals have an m-plane orientation and are sliced into m-plane -oriented wafers, as shown in Figure 4a. In another embodiment, the seed crystals are +c or -c oriented (or are bi-crystals, as described above), and are sliced into c-plane-oriented wafers, as shown in Figure 4b. In another embodiment, the seed crystals are {1 -1 0 -1} oriented and are sliced into {1 -1 0 ±1} -oriented wafers. In another embodiment, the seed crystals are m-plane oriented, and slices are made at an angle of approximately 28 degrees with respect to the large-area m plane to prepare semi-polar wafers with a {1 -1 O ±l} orientation. In another embodiment, the seed crystals are {1 -1 0 -1} oriented, and slices are made at an angle of approximately 18.8 degrees with respect to the large area plane to prepare semi-polar wafers with a {1 -1 0 ±2} orientation. In another embodiment, the seed crystals are {1 -1 0 -1} oriented, and slices are made at an angle of approximately 29.9 degrees with respect to the large area plane to prepare semi-polar wafers with a {1 -1 0 ±3} orientation. In another embodiment, the seed crystals are {1 -1 0 -1} oriented, and slices are made at an angle of approximately 26.2 degrees with respect to the large area plane to prepare semi-polar wafers with a {1 1 -2 ±2} orientation. In another embodiment, the seed crystals are c-plane oriented, and slices are made at an angle of approximately 32 degrees with respect to the large-area c plane to prepare semi- polar wafers with a {1 -1 0 ±3} orientation. In another embodiment, the seed crystals are m- plane oriented, and slices are made at an angle of approximately 42.5 degrees with respect to the large-area m plane to prepare semi-polar wafers with a {1 1 -2 ±2} orientation. In still another embodiment, the seed crystals are c-plane oriented, and slices are made at an angle of approximately 43.2 degrees with respect to the large-area c plane to prepare semi-polar wafers with a {1 -1 0 ±2} orientation. In yet another embodiment, the seed crystals are c-plane oriented, and slices are made at an angle of approximately 62.0 degrees with respect to the large-area c plane to prepare semi-polar wafers with a {1 -1 O ±l} orientation. In still another embodiment, the seed crystals are c-plane oriented, and slices are made at an angle of approximately 58.4 degrees with respect to the large-area c plane to prepare semi-polar wafers with a {1 1 -2 ±2} orientation. In another embodiment, the seed crystals are c-plane oriented, and slices are made at an angle of approximately 90.0 degrees with respect to the large-area c plane to prepare non-polar wafers with a {1 -1 0 0} orientation. In another embodiment, the seed crystals are c-plane oriented, and slices are made at an angle of approximately 90.0 degrees with respect to the large-area c plane to prepare non-polar wafers with a {1 1 -2 0} orientation.

[0074] In other embodiments, the seed crystals have a crystallographic orientation such that at least one large face is a relatively fast-growing face. In one specific embodiment, the seed crystal has an a-plane orientation. In other embodiments, the seed crystal has a semi-polar orientation. In specific embodiments, the orientation of the seed crystal is {1 -1 0 ±1}, {1 -1 0 ±2}, {1 -1 0 ±3}, or {1 1 -2 ±2}. In some embodiments, two seed crystals are placed together back-to-back, so that opposite faces of the co-mounted seed crystals have an equivalent crystallographic orientation. The use of fast-growing orientations may allow for an overall faster production rate of high quality production crystals. In one specific embodiment, shown in Figure 4c, the seeds are a-plane oriented. Initially rapid growth in the a direction slows as m- planes form near the top and bottom edges of the crystals. At the end of the crystal growth cycle, the crystal is terminated by four large-area m-plane facets, shown in edge section in Figure 4c. From geometry, the m-plane facets are approximately 58% of the length of the initial a-plane seed plate. The crystal may be sliced at an angle to produce a plurality of m- plane crystals. In other embodiments, the crystal is sliced at other angles to produce c-plane wafers, a-plane wafers, or semi-polar wafers. The semi-polar wafers may have a {1 -1 O ±l} orientation, a {1 -1 0 ±2} orientation, a {1 -1 0 ±3} orientation, a {2 0 -2 ±1} orientation, a {1 1 -2 ±2} orientation, or, more generally, a (h k i I) orientation, where i=-(h+k), / is nonzero and at least one of A and k are nonzero.

[0075] After slicing, the crystal wafers may be lapped, polished, and chemical-mechanically polished by methods that are known in the art.

[0076] The crystal wafers are useful as substrates for fabrication into optoelectronic and electronic devices such as at least one of a light emitting diode, a laser diode, a photodetector, an avalanche photodiode, a transistor, a rectifier, and a thyristor; one of a transistor, a rectifier, a Schottky rectifier, a thyristor, a p-i-n diode, a metal-semiconductor-metal diode, high-electron mobility transistor, a metal semiconductor field effect transistor, a metal oxide field effect transistor, a power metal oxide semiconductor field effect transistor, a power metal insulator semiconductor field effect transistor, a bipolar junction transistor, a metal insulator field effect transistor, a heterojunction bipolar transistor, a power insulated gate bipolar transistor, a power vertical junction field effect transistor, a cascade switch, an inner sub-band emitter, a quantum well infrared photodetector, a quantum dot infrared photodetector, a solar cell, and a diode for photoelectrochemical water splitting and hydrogen generation. [0077] In a specific embodiment, any of the above sequence of steps provides a method according to an embodiment of the present invention. In a specific embodiment, the present invention provides a method and resulting crystalline material provided by a pressure apparatus having a basket structure. Other alternatives can also be provided where steps are added, one or more steps are removed, or one or more steps are provided in a different sequence without departing from the scope of the claims herein.

[0078] While the above is a full description of the specific embodiments, various modifications, alternative constructions and equivalents may be used. Therefore, the above description and illustrations should not be taken as limiting the scope of the present invention which is defined by the appended claims.

Claims

WHAT IS CLAIMED IS:

1. A method for growth of a gallium-containing nitride crystal, the method comprising: providing gallium-containing source material; providing a mineralizer; providing at least two seed plates, including a first seed plate and a second seed plate; supporting the first seed plate and the second seed plate in a first site and a second site of a seed rack, the first seed plate and the second seed plate having substantially an equivalent crystallographic orientation to within five degrees, each of the first seed plate and the second seed plate having a length; placing the source material, mineralizer, and seed plates in a sealable container; introducing a nitrogen containing solvent into the sealable container; and processing the source material, mineralizer, and seed plates contained in the sealable container in a supercritical fluid at a temperature and a pressure.

2. The method of claim 1 wherein each of the first seed plate and the second seed plate comprise a first side and second side, the first side and the second side having the equivalent crystallographic orientation to within five degrees; wherein each of the first seed plate and the second seed plate having the length of at least 1 centimeter; and wherein the temperature is higher than about 400 degrees Celsius and the pressure is higher than about 2 kbar.

3. The method of claim 1 wherein either the first seed plate or the second seed plate is characterized by a maximum lateral dimension of at least two centimeters and a minimum lateral dimension of at least one centimeter; wherein the sealable container is an autoclave or a capsule.

4. The method of claim 1 further comprising increasing the thickness of at least one of the seed plates by at least 1 millimeter.

5. The method of claim 4 wherein the thickness of at least one of the seed plates is increased by at least 2 millimeters.

6. The method of claim 1 wherein at least one of the surfaces of at least one of the seed plates has a crystallographic orientation within five degrees of the {1 -1 0 0} m-plane.

7. The method of claim 6 wherein the seed plate has a substantially rectangular shape.

8. The method of claim 1 wherein at least one of the surfaces of at least one of the seed plates has a crystallographic orientation within five degrees of the {1 -1 O ±l} semi-polar plane.

9. The method of claim 8 wherein the seed plate has a substantially rectangular shape.

10. The method of claim 1 wherein the large-area surfaces of the seed plates have a crystallographic orientation within five degrees of the (0 0 0 1) Ga-polar c- plane.

11. The method of claim 1 wherein the large-area surfaces of the seed plates have a crystallographic orientation within five degrees of the (0 0 0 -1) N-polar c- plane.

12. The method of claim 1 further comprising slicing a boule derived from either the first seed plate or the second seed plate to prepare at least one of m-plane, a-plane, c-plane, or semi-polar substrates.

13. A method for growth a gallium-containing nitride crystal comprising: providing gallium-containing source material; providing a mineralizer; providing at least a first seed plate and a second seed plate, the first seed plate having a first side having a first crystallographic orientation and a second side having a second crystallographic orientation, the second seed plate having a first side having a first crystallographic orientation and a second side having a second crystallographic orientation, the second side of the first seed plate and the second side of the second seed plate having an equivalent crystallographic orientation to within five degrees and have a minimum lateral dimension of at least 1 centimeter; supporting the first seed plate and the second seed plate such that the first side of the first seed crystal faces the first side of the second seed crystal and spaced by a predetermined gap between the first side of the first seed crystal and the first side of the second seed crystal; placing the source material, mineralizer, and the seed plates in a sealable container; introducing a nitrogen-containing solvent in the sealable container; and processing the source material, mineralizer, and seed plates contained in the sealable container in a supercritical fluid at a temperature higher than about 400 degrees Celsius and a pressure higher than about 2 kbar.

14. The method of claim 13 wherein either the first side or the second side of respective first seed plate or second seed plate has a maximum lateral dimension of at least two centimeters and a minimum lateral dimension of at least one centimeter.

15. The method of claim 13 further comprising increasing a first thickness of the first seed plate and a second thickness of a second seed plate by at least 1 millimeter each.

16. The method of claim 13 further comprising increasing a first thickness of the first seed plate and a second thickness of a second seed plate by at least 2 millimeter each.

17. The method of claim 13 wherein each of the second sides, which is outward facing, has a crystallographic orientation within five degrees of the (0 0 0 1) Ga- polar c-plane.

18. The method of claim 13 wherein each of the second sides, which is outward facing, has a crystallographic orientation within five degrees of the (0 0 0 -1) N- polar c-plane.

19. The method of claim 13 wherein each of the second sides, which is outward facing, has a crystallographic orientation within five degrees of the {1 -1 0 -1} semi- polar plane.

20. The method of claim 13 further comprising slicing a boule derived from either the first seed plate or the second seed plate to prepare at least one of m-plane, a- plane, c-plane, or semi-polar substrates.

21. A process for growing a crystalline gallium-containing nitride using one or more seed racks, the process comprising: providing a high pressure apparatus comprising a sealable container with a seed rack device, gallium-containing feedstock in one zone, and at least one seed in the seed rack device in another zone; introducing a solvent capable of forming a supercritical fluid into at least the one zone and the other zone; processing one or more portions of the gallium-containing feedstock in the supercritical fluid to provide a supercritical solution comprising at least gallium containing species at a first temperature; and growing crystalline gallium-containing nitride material from the supercritical solution on the seed at a second temperature, the second temperature being characterized to cause the gallium containing species to form the crystalline gallium containing nitride material on the seed.

22. The process of claim 21 wherein the seed rack comprises at least one of copper, copper-based alloy, gold, gold-based alloy, silver, silver-based alloy, palladium, platinum, iridium, ruthenium, rhodium, osmium, titanium, vanadium, chromium, iron, iron- based alloy, nickel, nickel-based alloy, zirconium, niobium, molybdenum, tantalum, tungsten, rhenium, silica, alumina, and combinations thereof.

23. The process of claim 21 wherein the sealable container within the high pressure apparatus has an inner diameter greater than 75 mm.

24. A process for growing a crystalline gallium-containing nitride, the process comprising: providing high pressure apparatus comprising a sealable container with gallium-containing feedstock in one zone and at least one seed in another zone; introducing a solvent capable of forming a supercritical fluid into at least the one zone and the other zone; maintaining a pressure at or above about seven (7) atmospheres within the one zone and the other zone during introduction of the solvent into the one zone and the other zone; processing one or more portions of the gallium-containing feedstock in the supercritical fluid to provide a supercritical solution comprising at least gallium containing species at a first temperature; and growing crystalline gallium-containing nitride material from the supercritical solution on the seed at a second temperature, the second temperature being characterized to cause the gallium containing species to form the crystalline gallium containing nitride material on the seed.

25. The process of claim 24 wherein the introduction of the solvent occurs while the solvent is substantially in liquid form.

26. The process of claim 24 further comprising purging the sealable container prior to introducing the solvent.

27. The process of claim 24 wherein the sealable container has an inner diameter greater than 75 mm.

28. A process for growing a crystalline gallium-containing nitride, the process comprising: providing an autoclave comprising gallium-containing feedstock in one zone and at least one seed in another zone; introducing a first solvent capable of forming a supercritical fluid into at least the one zone and the other zone; maintaining a pressure at or above about seven (7) atmospheres within the one zone and the other zone during introduction of the solvent into the one zone and the other zone; processing one or more portions of the gallium-containing feedstock in the supercritical fluid to provide a supercritical solution comprising at least gallium containing species at a first temperature; growing crystalline gallium-containing nitride material from the supercritical solution on the seed at a second temperature, the second temperature being characterized to cause the gallium containing species to form the crystalline gallium containing nitride material on the seed; removing thermal energy from the autoclave to form a second solvent from the supercritical solution; and removing the second solvent from the autoclave through an outlet.

29. The process of claim 28 further comprising transferring the second solvent from the outlet to a purification process.

30. The process of claim 28 further comprising transferring the second solvent from the outlet to a purification process to recycle the second solvent.

31. The process of claim 28 further comprising transferring the second solvent from the outlet to a purification process to recycle the second solvent; purifying the second solvent in the purification process to form a third solvent; and transferring the third solvent to the autoclave.

32. The process of claim 31 wherein the third solvent is substantially the same as the first solvent.

33. The process of claim 28 wherein the second solvent comprises a hydrogen species, nitrogen species, one or more trace metals, and dissolved mineralizer.

34. The process of claim 28 wherein the first solvent is substantially NH₃.

35. A process for growing a crystalline gallium-containing nitride, the process comprising: providing an autoclave comprising gallium-containing feedstock in a basket structure in one zone, at least one seed in another zone and a solvent capable of forming a supercritical fluid, the basket structure being configured to substantially prevent one or more solid portions of the feedstock from being transported from the one zone to the other zone;; processing one or more portions of the gallium-containing feedstock in the supercritical fluid to provide a supercritical solution comprising at least gallium containing species at a first temperature; flowing one or more portions of the supercritical solution containing the gallium containing species from the one zone through a portion of the basket into the other zone; and growing crystalline gallium-containing nitride material from the supercritical solution on the seed at a second temperature, the second temperature being characterized to cause the gallium containing species to form the crystalline gallium containing nitride material on the seed.

36. The process of claim 35 further comprising at least one crucible, in which at least one of gallium metal and an alkali metal is placed in the one zone; and wherein the basket structure comprises one or more support structures made of one or more materials selected from copper, copper-based alloy, gold, gold-based alloy, silver, silver-based alloy, palladium, platinum, iridium, ruthenium, rhodium, osmium, titanium, vanadium, chromium, iron, iron-based alloy, nickel, nickel-based alloy, zirconium, niobium, molybdenum, tantalum, tungsten, rhenium, silica, alumina, and combinations thereof

37. The process of claim 36 wherein the crucible comprises at least one of molybdenum, tantalum, niobium, iridium, platinum, palladium, gold, silver, tungsten, alumina, magnesia, calcia, zirconia, yttria, aluminum nitride or gallium nitride.

38. The process of claim 37 wherein the autoclave has an inner diameter greater than 75 mm.

39. The process of claim 36 wherein the gallium-containing feedstock comprises at least one dopant at a concentration between 10¹⁶ cm^"3 and 10²¹ cm^"3.

40. The process of claim 39 wherein the dopant comprises at least one of Si, O, Mg, Zn, Fe, Ni, Co, or Mn,.

41. The process of claim 36 further comprising a frame, wherein the frame configured for transporting the basket structure, a baffle, and a seed rack into the autoclave before commencing crystal growth and configured for transporting the basket structure, the baffle, and the grown crystals out of the autoclave at the conclusion of a crystal growth run.

42. The process of claim 36 wherein the gallium-containing feedstock comprises gallium nitride with a particle size distribution between 0.020 inch and 5 inches.

43. The process of claim36, further incorporating a getter material and/or structure within a vicinity of either or both the one zone or/and the other zone.

44. The process of claim 43 wherein the getter comprises at least one of at least one of an alkaline earth metal, Sc, Ti, V, Cr, Y, Zr, Nb, Hf, Ta, W, a rare earth metal, and their nitrides, amides, imides, amido-imides, or halides.

45. A process for growing a crystalline gallium-containing nitride, the process comprising: providing a high pressure apparatus comprising gallium-containing feedstock in one zone, at least one seed in another zone, an azide mineralizer, and at least one metal, the azide mineralizer and the metal being provided in a predetermined ratio such that nitrogen generated by decomposition of the azide mineralizer and hydrogen generated by reaction of the metal with a supercritical fluid are in a ratio of approximately 1 :3; processing one or more portions of the gallium-containing feedstock in the supercritical fluid to provide a supercritical solution comprising at least gallium containing species at a first temperature; and growing crystalline gallium-containing nitride material from the supercritical solution on the seed at a second temperature, the second temperature being characterized to cause the gallium containing species to form the crystalline gallium containing nitride material on the seed.

46 . The process of claim 45 further comprising providing a catalyst in a vicinity of at least one zone or the other zone of the high pressure apparatus to convert the nitrogen and hydrogen to ammonia.

47. The process of claim 46 wherein the catalyst comprises at least one of iron, cobalt, nickel, titanium, molybdenum, tungsten, aluminum, potassium, cesium, calcium, magnesium, barium, zirconium, osmium, uranium or a lanthanide, ruthenium, platinum, palladium, or rhodium.

48. A process for growing a crystalline gallium-containing nitride, the process comprising: providing a high pressure apparatus comprising gallium-containing feedstock in one zone, at least one seed in another zone, an azide mineralizer, at least one metal, and a catalyst within a vicinity of either or both the one zone or/and the other zone, the azide mineralizer and the metal being provided in a predetermined ratio such that nitrogen generated by decomposition of the azide mineralizer and a hydrogen gas species generated by reaction of at least the metal with a supercritical ammonia are in a ratio of approximately 1 :3 and greater; processing one or more portions of the gallium-containing feedstock in the supercritical ammonia to provide a supercritical ammonia solution comprising at least gallium containing species at a first temperature; growing crystalline gallium-containing nitride material from the supercritical ammonia solution on the seed at a second temperature, the second temperature being characterized to cause the gallium containing species to form the crystalline gallium containing nitride material on the seed; generating the hydrogen gas species from at least the reaction between the metal and the supercritical ammonia fluid; and processing the hydrogen gas species using at least the catalyst to convert the hydrogen gas species and a nitrogen gas species to the supercritical ammonia fluid.

49. The process of claim 48 wherein the ratio of approximately 1 :3 ranges from about 0.8:3 to 1 :3.8.

50. The process of claim 48 wherein the catalyst comprises at least one of iron, cobalt, nickel, titanium, molybdenum, tungsten, aluminum, potassium, cesium, calcium, magnesium, barium, zirconium, osmium, uranium or a lanthanide, ruthenium, platinum, palladium, or rhodium.