JP2011530471A - Manufacturing method of gallium nitride bowl by large-scale ammonothermal method - Google Patents

Abstract

  This is a large-scale manufacturing method of a gallium nitride bowl. Large area single crystal seed plates are suspended in a rack, placed in a large diameter autoclave or internal heating high pressure apparatus with ammonia and mineralizer, and grown by ammonothermal methods. The orientation and mounting arrangement of the seed is selected to provide efficient utilization of the seed plate and the mass in the heat sterilizer or high pressure apparatus. This method is scalable to very large chunks and is cost effective.

Description

[Cross-reference of related applications]
This application is filed by the same applicant as US provisional application 61 / 087,122 filed August 7, 2008, US provisional application 61 / 087,135 filed August 7, 2008, 8 August 2008. United States provisional application 61 / 086,801 filed on May 7, US provisional application 61 / 086,800 filed August 7, 2008, United States provisional application 61/08, filed August 7, 2008 No. 086,799 claims priority and is incorporated herein by reference.
[Statement on rights to inventions made under research and development funded by the federal government]

N / A [Refer to “Sequence Listing”, Table, or Computer Program List Submitted by Compact Disc]

  Not applicable

  The present invention generally relates to processing materials for crystal growth. More specifically, the present invention provides a method for obtaining gallium-containing nitride crystals by ammonobase or ammonoacid technology, but others are also available. In other embodiments, the present invention provides an apparatus for large scale processing of nitride crystals, but it will be appreciated that other crystals and materials may be processed. Such crystals and materials include gallium nitride (GaN), aluminum nitride (AlN), indium nitride (InN), indium gallium nitride (InGaN), aluminum gallium nitride (AlGaN) for the manufacture of bulk and patterned substrates. ) And aluminum indium gallium nitride (AlInGaN) and others. Such bulk and patterned substrates are among other devices optoelectronic devices, lasers, LEDs (Light Emitting Diodes), solar cells, photoelectrochemical water splitting and hydrogen generation, photodetectors, integrated circuits, And used in a variety of applications, including transistors.

  Gallium nitride containing crystalline material serves as a starting point for the manufacture of conventional optoelectronic devices, such devices include blue LEDs and lasers. Such optoelectronic devices are commonly manufactured on a sapphire or silicon carbide substrate having a composition different from that of the deposited nitride layer. In conventional metal organic chemical vapor deposition (MOCVD), GaN is deposited using ammonia or an organometallic compound in the gas phase. Although such techniques have been successful, such conventional growth rates have made it difficult to provide a bulk layer of GaN material. In addition, since the dislocation density is high, the performance of the optoelectronic device is degraded.

  Other techniques have been proposed to obtain bulk single crystal gallium nitride. Such techniques include those using epitaxial growth using a halogen compound and a hydride in the gas phase, which is called a halogenated vapor phase epitaxy method (HVPE) (Growth and characterization of freezing GaN substrates, K. Motoku et al., Journal of Crystal Growth 237-239, 912 (2002)). Unfortunately, there are several drawbacks to this HVPE method. Sometimes the quality of bulk single crystal gallium nitride is generally insufficient for high quality laser diodes. This is due to problems such as transition density and pressure.

A technique using supercritical ammonia has also been proposed. Peter et al. Describe the synthesis of aluminum nitride using the ammonothermal method (see J. Cryst. Growth 104, 411-418 (1990)). R. Dwilinski et al. Show that microcrystalline gallium nitride can be produced by the synthesis of gallium and ammonia, particularly on the condition that ammonia contains an alkali metal amide (KNH ₂ or LiNH ₂ ). These techniques are 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 and “Crystal growth of gallium nitride in supercritical ammonia” J. Org. W. Kolis et al. , J. et al. Cryst. Growth 222, 431-434 (2001), and Mat. Res. Soc. Symp. Proc. 495, 367-372 (1998) by J. et al. W. Kolis et al. It is described in. However, even when these supercritical ammonia processes are used, it is not possible to produce a large-scale bulk single crystal.

  Dwillinski in US Pat. No. 6,656,615 and US Pat. No. 7,335,262, D′ Eveln in US Pat. No. 7,078,731 and US Pat. No. 7,101,433 We discuss GaN crystal growth method and apparatus by ammonothermal method. These methods are useful for growing relatively small GaN crystals. Unfortunately, these methods have limitations for large scale production. A conventional apparatus having an inner diameter of 40 mm is useful for growing a GaN crystal having a small diameter, but is not suitable for growing a large-scale GaN bowl (such as an ingot). In addition, the traditional method of hanging a seed crystal using a wire and passing through a single hole drilled with a laser is suitable for small crystals, but seems to be ineffective for large-scale manufacturing. . Other restrictions may also exist.

  From the above, it is considered that a technique for large-scale crystal growth is highly desired.

  According to the present invention, a technique related to processing of a substance for crystal growth is provided. More specifically, the present invention provides a method for obtaining gallium-containing nitride crystals by ammonobase technology, but others can also be provided. In other embodiments, the present invention provides an apparatus for large scale processing of nitride crystals, but it will also be understood that other crystals and materials may be processed. Such crystals and materials include, but are not limited to, GaN, AlN, InN, InGaN, AlGaN and AlInGaN, and others for the production of bulk or patterned substrates. Such bulk and patterned substrates are among other devices optoelectronic devices, lasers, LEDs (Light Emitting Diodes), solar cells, photoelectrochemical water splitting and hydrogen generation, photodetectors, integrated circuits, And used in a variety of applications, including transistors.

  In certain embodiments, the present invention provides a method for growing a gallium-containing nitride crystal, such as GaN. The method includes preparation of a gallium-containing source material and preparation of a mineralizer. In certain embodiments, the method includes providing at least two seed plates, the two seed plates including a first seed plate and a second seed plate. The method includes supporting a first seed plate and a second seed plate at 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 a crystal orientation substantially equal to within 5 degrees. According to certain embodiments, each of the first seed plate and the second seed plate has a length of at least 1 centimeter, for example. The method includes installing a source material, a mineralizer and a seed plate in a sealable container, and introducing a nitrogen-containing solvent into the sealable container. In certain embodiments, the method includes source material, mineralizer and seed plate contained in a sealable container in supercritical fluid, for example, at a temperature greater than about 400 ° C., such as at a pressure greater than about 2 kbar. Processing. Of course, there can be other variations, modifications, and alternatives.

  In another particular embodiment, the present invention provides a method for growing a gallium-containing nitride crystal. The method includes providing a 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 certain embodiments, the first seed plate has a first side having a first crystal orientation and a second side having a second crystal orientation. In certain embodiments, the second seed plate has a first side having a first crystal orientation and a second side having a second crystal orientation. In a specific embodiment, the first side surface of the first seed crystal faces the first side surface of the second seed crystal, and the first side surface and the second seed crystal of the first seed crystal. The first side surface includes supporting the first seed plate and the second seed plate so as to be disposed with a predetermined gap therebetween. The method includes placing the source material, mineralizer and seed plate in a sealable container. This method introduces a nitrogen-containing solvent into a sealable container and the source contained in the sealable container in a supercritical liquid at a temperature, for example, greater than about 400 ° C. and a pressure, for example, greater than about 2 kbar. Process material, mineralizer and seed plate.

  Furthermore, the present invention provides a method for growing gallium-containing nitride crystals, such as GaN. The method includes providing a gallium-containing source material. In certain embodiments, the method also includes providing a mineralizer and providing at least a first seed plate and a second seed plate. In certain embodiments, the first seed plate has a first side surface having a first a-plane crystal orientation and a second side surface having a second a-plane crystal orientation. In certain embodiments, the second seed plate has a first side surface having a first a-plane crystal orientation and a second side surface having a second a-plane crystal orientation. In certain embodiments, the method includes supporting a first seed plate and a second seed plate. According to certain embodiments, each of the first seed plate and the second seed plate has a length of at least 1 centimeter. In certain embodiments, the method includes installing the source material, mineralizer and seed plate in a sealable container and introducing a nitrogen-containing solvent into the sealable container. In a preferred embodiment, the method treats source material, mineralizer and seed plate contained in a sealable container in supercritical fluid at a temperature above about 400 ° C. and a pressure above about 2 kbar. Including. In this method, any spatial portion on 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 is converted from the a-plane characteristic to the m-plane orientation characteristic. Change its characteristics. Preferably, the method generally thickens each of the seed plates by crystal growth.

  Furthermore, the present invention provides a method for growing a crystalline gallium-containing nitride, such as GaN. The method includes providing a high pressure device having a sealable container with a gallium-containing source in one area and at least one species in another area. This method involves introducing a solvent capable of forming a supercritical fluid into at least one zone and other zones, and while introducing the solvent into one zone and other zones. And maintaining the pressure in these areas and other areas above about 7 atmospheres. The method treats one or more portions of the gallium-containing raw material in the supercritical liquid to prepare a supercritical solution containing at least a gallium-containing species at a first temperature. In certain embodiments, the method includes growing a crystalline gallium-containing nitride material from a supercritical solution on the seed at a second temperature. This second temperature is characterized as such that the gallium-containing species forms a crystalline gallium-containing nitride material on the seed.

  In yet another embodiment, the present invention provides a method for growing crystalline gallium-containing nitride. The process includes providing an autoclave having a gallium-containing source in one area and at least one species in another area. The method also includes introducing a first solvent capable of forming a supercritical fluid into at least one zone and the other zone. The method includes maintaining the pressure in one area and the other area above about 7 atmospheres while introducing the solvent into the one area and the other area. Certain embodiments include treating one or more portions of the gallium-containing source in the supercritical fluid to prepare a supercritical solution comprising at least a gallium-containing species at a first temperature. In certain embodiments, the method grows a crystalline gallium-containing nitride material from a supercritical solution on the seed at a second temperature. This second temperature is characterized as such that the gallium-containing species forms a crystalline gallium-containing nitride material on the seed. In certain embodiments, the method removes thermal energy from the autoclave, forms a second solvent from the supercritical solution, and removes the second solvent from the autoclave through a drain. Including.

  In yet another embodiment, the present invention provides a method for growing crystalline gallium-containing nitride. The method provides a pressure sterilizer having a solvent capable of forming a gallium-containing source in a basket structure in one zone, at least one species in another zone, and a supercritical fluid. Including doing. In a preferred embodiment, the basket structure is configured to substantially prevent one or more solid portions of the raw material from moving from one zone to another. The method also includes providing a supercritical solution including at least a gallium-containing species at a first temperature by treating one or more portions of the gallium-containing source in the supercritical liquid. This method allows one or more portions of a supercritical solution containing a gallium-containing species to flow from one zone through a portion of the basket to another region. The method includes growing a crystalline gallium-containing nitride material from a supercritical solution on the seed at a second temperature. This second temperature is characterized as such that the gallium-containing species forms a crystalline gallium-containing nitride material on the seed.

  Furthermore, the present invention provides another method for growing crystalline gallium-containing nitride. The method includes providing a high pressure apparatus having a gallium-containing source in one area, at least one species, an azide mineralizer, and at least one metal in another area. In one or more embodiments, the azide mineralizer and metal have a ratio of nitrogen produced by decomposition of the azide mineralizer to hydrogen produced by the reaction of the metal and the supercritical fluid of approximately 1: 3. Thus, it is prepared at a predetermined ratio, but may be other. In certain embodiments, the method includes providing a supercritical solution comprising at least a gallium-containing species at a first temperature by treating one or more portions of the gallium-containing source in the supercritical liquid. This method also grows a crystalline gallium-containing nitride material from a supercritical solution on the seed at a second temperature. This second temperature is characterized as such that the gallium-containing species forms a crystalline gallium-containing nitride material on the seed.

  In another embodiment, the present invention provides a method for growing crystalline gallium-containing nitride. This method comprises a gallium-containing source in one zone, at least one species in another zone, an azide mineralizer, at least one metal, and / or one zone and / or another zone. Providing a high pressure device having a catalyst in the vicinity thereof. In certain embodiments, the azide mineralizer and the metal have a ratio of nitrogen generated by decomposition of the azide mineralizer to hydrogen gas species generated by the reaction of at least the metal and supercritical ammonia is approximately 1: 3. As described above, preparation is made at a predetermined ratio. Other ratios may be used. The method treats one or more portions of a gallium-containing source in supercritical ammonia to prepare a supercritical ammonia solution containing at least a gallium-containing species at a first temperature, and at a second temperature, Crystalline gallium-containing nitride material is grown from a supercritical ammonia solution on the seed. This second temperature is characterized as such that the gallium-containing species forms a crystalline gallium-containing nitride material on the seed. This method generates hydrogen gas species from a reaction between at least a metal and a supercritical ammonia solution, and treats the hydrogen gas species using at least a catalyst, and converts the hydrogen gas species and nitrogen gas species into supercritical ammonia. Converting to a liquid.

  By using the present invention, benefits over existing technologies are achieved. In particular, the present invention makes it possible to provide a cost-effective high-pressure apparatus for the growth of crystals such as GaN, AlN, InN, InGaN and AlInGaN and others. In certain embodiments, the method and apparatus are operable with relatively simple and cost-effective parts to manufacture. In some embodiments, the apparatus and method can be manufactured using conventional materials and / or methods by those having ordinary technical knowledge. The present apparatus and method can provide cost-effective crystal growth and materials. This crystal growth and material, in certain embodiments, is greater than 0.3 liters, greater than 1 liter, greater than 3 liters, greater than 10 liters, greater than 30 liters, greater than 100 liters, and greater than 300 liters. Process in batch volume under extreme pressure and temperature conditions. In some embodiments, one or more of these benefits are achieved. These and other benefits may be described throughout this specification and more specifically below.

The present invention realizes these benefits and others in the context of known processing techniques. 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.

1 is a crystal growth framework structure according to an embodiment of the present invention. 1 is a crystal growth framework structure according to an embodiment of the present invention. 3 is a crystal growth seed rack structure according to an embodiment of the present invention. 3 is a crystal growth seed rack structure according to an embodiment of the present invention. 3 is a crystal growth seed rack structure according to an embodiment of the present invention. FIG. 6 is a simplified diagram illustrating a processing method for a crystal growth apparatus according to an embodiment of the present invention. FIG. 6 is a simplified diagram illustrating a processing method for a crystal growth apparatus according to an embodiment of the present invention. It is the simplified figure explaining the crystal growth method by the embodiment of the present invention. It is the simplified figure explaining the crystal growth method by the embodiment of the present invention. It is the simplified figure explaining the crystal growth method by the embodiment of the present invention. FIG. 3 is a simplified flowchart illustrating a crystal growth method according to an embodiment of the present invention. It is the simplified figure explaining the reuse process of crystal growth by the embodiment of the present invention. It is the simplified figure explaining the reuse process of crystal growth by the embodiment of the present invention.

  According to the present invention, a technique related to processing of a material for crystal growth is provided. More specifically, the present invention provides a method for obtaining gallium-containing nitride crystals by ammonobase or ammonoacid technology, although other methods are possible. In other embodiments, the present invention provides an apparatus for large scale processing of nitride crystals, but it should be considered that other crystals and materials can also be processed. Such crystals and materials include gallium nitride (GaN), aluminum nitride (AlN), indium nitride (InN), indium gallium nitride (InGaN), aluminum gallium nitride (AlGaN) for the manufacture of bulk and patterned substrates. ) And aluminum indium gallium nitride (AlInGaN) and others. Such bulk and patterned substrates are among other devices optoelectronic devices, lasers, LEDs (Light Emitting Diodes), solar cells, photoelectrochemical water splitting and hydrogen generation, photodetectors, integrated circuits, And used in a variety of applications, including transistors.

  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 taken as useful to the reader. Of course, there can be other variations, modifications, and alternatives.

  By gallium-containing nitride is meant nitrides of elements belonging to gallium and any other group 13 (according to IUPAC 1989). It includes, but is not limited to, binary compounds such as GaN and ternary compounds such as AlGaN, InGaN and AlInGaN. Also, the ratio of other elements belonging to Group 13 to Ga can vary over a wide range. Of course, there can be other variations, modifications, and alternatives.

  By autoclaver is meant a closed container having a reaction chamber in which an ammonobase or ammonoacid treatment according to the invention is carried out. As conventionally used in the art, closed is understood to mean hermetically sealed and hermetic in the usual sense. It is understood that the autoclave is extremely heated as conventionally used in the art. That is, in a normal sense, the heating is performed so that the temperature of the inner wall of the autoclave is substantially the same as the temperature of the supercritical fluid adjacent to the autoclave wall. Of course, there can be other variations, modifications, and alternatives.

  By high-pressure apparatus is meant an apparatus that can include a supercritical ammonia and gallium-containing nitride growth environment at a temperature of about 100 ° C. to about 800 ° C. and a pressure of about 1 kbar to about 10 kbar. In one embodiment, the high pressure device includes an autoclave as described in US Pat. No. 7,335,262, which is hereby incorporated by reference in its entirety. In other embodiments, the high pressure device is a high pressure device with internal heating, as described in US Pat. No. 7,125,453, and US patent application 2006/0177362 A1 and US serial number 12 / 133,364. These patents and patent applications are hereby incorporated by reference in their entirety. Of course, there can be other variations, modifications, and alternatives.

In the following description, the apparatus will be described as being vertically oriented. In other embodiments, the device is instead oriented horizontally oriented or at an oblique angle between vertical and horizontal. And it may be swung so as to promote the convection of the supercritical fluid inside the high pressure apparatus. The method may be used in conjunction with a sealable container and high pressure device. Examples of typical applicable devices are US Pat. Nos. 7,101,433, 7,125,453 and 7,160,388, and US patent applications 61 / 073,687, 12 / 133,365. And 12 / 133,364, which are hereby incorporated by reference in their entirety. Reference should also be made to FIG. According to an embodiment of the present invention, FIG. 5 lists general steps for performing crystal growth processing. As shown, FIG. 5 is merely exemplary and should not unduly limit the scope of this claim. Those skilled in the art will appreciate other variations, modifications, and alternatives.

  A schematic diagram of the framework for seed crystals and raw material is shown in FIGS. 1A and 1B. This framework allows the seed crystals and raw materials to be put into an arrangement suitable for crystal growth before being placed inside the high pressure apparatus and in a form convenient for subsequent processing. The framework should retain good stiffness under crystal growth conditions and be chemically inert to the crystal growth environment. This does not contribute to contamination of the grown crystal and does not suffer significant corrosion. The materials of the framework structure and its constituent elements are copper, copper base alloy, gold, gold base alloy, silver, silver base alloy, palladium, platinum, iridium, ruthenium, rhodium, osmium, titanium, vanadium, chromium, iron, iron One or more of a base alloy, nickel, nickel base alloy, zirconium, niobium, molybdenum, tantalum, tungsten, rhenium, silica, alumina, combinations thereof, and the like may be included. Iron-based alloys that can be used to form the framework include, but are not limited to, stainless steel. Nickel-based alloys that can be used to form the framework include, but are not limited to, Inconel, Hastelloy and the like. Again, there can be other variations, modifications, and alternatives. In some embodiments, the framework components are manufactured from an alloy having at least two elements for increased hardness and creep resistance. The framework and its components may consist of wire, wire cloth or wire mesh, foil, plate, sheet, square bar, round bar, rectangular bar, tube, screw bar, and fastener. The skeleton and its components may be attached using welding, arc welding, resistance welding, brazing, clamping, attachments, and the like. The attachment uses a fastener such as at least one of a screw, a bolt, a screw rod, and a nut.

  The framework may include as its components, a baffle, a raw material basket, a rack for suspending the seed crystal plate, and means for attaching at least two of the above-described components. In embodiments, as shown in FIG. 1A, the basket is located below the baffle and the seed rack is located on the baffle so that the crystal to be grown increases in solubility with increasing temperature. Located above. In other embodiments, as shown in FIG. 1B, the basket is positioned above the baffle so that it is suitable when the crystal being grown decreases in solubility with increasing temperature (ie, regressive solid solubility). The seed rack is located below the baffle. The volume of the crystal growth region, ie, the region containing the seed rack, may be larger than the nutrient region, ie, the region containing the basket. In certain embodiments, the volume ratio of the crystal growth region to the nutrient region may be between 1 and 5. In other embodiments, this ratio may be between 1.25 and 3, or between 1.5 and 2.5. The overall diameter and height of the skeleton is selected to fit snugly inside the high pressure device. This maximizes utilization of the available volume and optimizes fluid dynamics. The skeleton diameter is 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, and 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 skeleton to its diameter is 1 to 2, 2 to 4, 4 to 6, 6 to 8, 8 to 10, 10 to 12, 12 to 15, 15 to 20, or greater than 20 It may be a thing.

  The baffle provides a means for dividing the high pressure device into which the skeleton is inserted into two separate areas and includes one or more disks. The two regions are fluidly connected to each other because the baffle has a plurality of through holes or openings. Therefore, a part of the cross-sectional area of the baffle is open. In certain embodiments, the baffle has a partially open area from about 0.5% to about 30%, although other percentages may be used. In other embodiments, it has a partially open area between 2% and 20% or between 5% and 15%. While allowing the solvent and supercritical fluid under high pressure and high temperature (HPHT) conditions to move freely through the through holes in the baffle through the high pressure device, the baffle has at least one (or more) It serves the purpose of confining (many) source material to a particular region or end of the chamber 108. In many cases, this feature is particularly beneficial for applications such as crystal growth. That is, in such applications, the supercritical fluid moves at least one material or nutrient from one region of the chamber defined by the baffle arrangement to another region where seed crystal growth occurs. In certain embodiments, the baffle diameter is equal to the maximum diameter of the entire skeleton. In other embodiments, the baffle diameter is slightly smaller than the maximum diameter of the entire framework, thereby providing an annular space through which liquid can flow under crystal growth conditions. The baffle diameter may be smaller by 0.5 inches or less than the maximum diameter of the entire skeleton. The baffle opening should be large enough so that it does not clog easily. In one particular embodiment, the diameter of the baffle opening is between 0.020 inches and 0.5 inches. In other embodiments, the diameter of the baffle opening is between 0.050 inches and 0.25 inches. In one particular embodiment, the baffle has a single disk that is 0.020 inches to 0.5 inches thick. In other embodiments, the baffle has a single disk that is 0.050 inches to 0.25 inches thick. In some embodiments, the baffle has two, three or more disks. In some multiple disk embodiments, one or more openings of the multiple disks are located on top of each other. In other multiple disk embodiments, one or more openings of the multiple disks are not located on top of each other. Thus, the effective partial opening in the multiple disk baffle embodiment is the partial opening area of each disk as the upper boundary and the product of the partial opening areas of each disk. It may be located between.

  The raw material basket provides a convenient means for transporting raw materials, including source material and mineralizer, to the high pressure apparatus. This allows easy fluid coupling from the region between the source material particles inside the basket and the crystal growth region, and removes unconsumed source material from the reactor as a result of the growth run. In one embodiment, the basket may consist of a wire mesh or wire cloth, as schematically shown in the figure. 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. good. The wire mesh or wire cloth may be housed in a skeleton having a larger diameter wire and optionally attached to the skeleton. This can provide improved mechanical support. In other embodiments, the basket may consist of foil or plate with a plurality of through holes or openings. The size of the opening in the wire mesh, wire cloth, foil or plate is such that the raw material particles are in the middle of crystal growth even after a significant part of the raw material has been etched and / or consumed by the crystal growth operation. Should be small enough not to pass through the opening. In certain embodiments, the opening in the wire mesh, wire cloth, foil or plate has a diameter between 0.005 inches and 0.5 inches. In other embodiments, the opening has a diameter between 0.010 inches and 0.125 inches or between 0.025 inches and 0.080 inches. In some embodiments, a hollow tube having an opening covered by a wire mesh is placed inside the basket prior to input of raw materials. This improves the fluid connection between the region between the raw material particles inside the basket and the crystal growth region. A suitable configuration of such an interior space is taught by US Pat. No. 3,245,760, which is hereby incorporated by reference in its entirety.

In some embodiments, the source material is placed in the basket prior to placing the seed crystal on the seed rack. This minimizes the possibility of the latter being damaged. The source material may be supplied in various forms. In some embodiments, the source material may consist of a single crystal or a bulk or grain polycrystalline material. In other embodiments, the source material consists of a mass of sintered polycrystalline material. In the case of gallium nitride, the source material is derived from a monocrystalline or polycrystalline GaN byproduct deposited on a wall or a variety of surfaces using a hydride vapor phase epitaxy (HVPE) reactor. Also good. In other specific embodiments, the source material comprises a single crystal or polycrystalline GaN plate grown on a substrate by HVPE. In another particular embodiment, the source material is derived from sintered GaN powder, as disclosed in US Pat. No. 6,861,130. This patent is incorporated herein by reference in its entirety. In another particular embodiment, the source material is derived from a polycrystalline GaN plate consisting of a columnar microstructure as disclosed in US patent application 2007 / 0142204A1. This application is incorporated herein by reference in its entirety. The source material may include oxygen at a concentration lower than 10 ¹⁹ cm ⁻³ , lower than 10 ¹⁸ cm ⁻³ , or lower than 10 ¹⁷ cm ⁻³ . The source material has a concentration of 10 ¹⁶ cm ⁻³ to 10 ²¹ cm ⁻³ , an n-type dopant such as Si or O, a p-type dopant such as Mg or Zn, a compensating dopant such as Fe or Co, or Fe Magnetic dopants such as Ni, Co or Mn may be included. In one particular embodiment, the source material particle size distribution is between about 0.020 inches and about 5 inches. In other embodiments, the particle size distribution of the source material is between about 0.050 inches and about 0.5 inches. In a preferred embodiment, the total surface area of the source material is at least a multiple of 3 greater than the total surface area of all the seed plates placed in the seed rack.

  In some embodiments, the source material comprises a metal that melts at high temperatures, such as gallium or indium. In some embodiments, the mineralizer comprises a metal that melts at high temperatures, such as sodium, potassium, or lithium. If placed in direct contact with the inner surface of the autoclave or capsule, the metal may form an alloy and damage the autoclave or capsule intact. Thus, in some embodiments, at least one crucible is disposed within or closest to the raw material basket and includes at least one metal. The crucible should be chemically inert with respect to the supercritical liquid crystal growth environment and should not react or become alloyed with at least one metal. In one particular embodiment, the crucible consists of molybdenum, tantalum, niobium, iridium, platinum, palladium, gold, silver or tungsten. In other embodiments, the crucible consists of alumina, magnesia, calcia, zirconia, yttria, aluminum nitride or gallium nitride. The crucible may be made of sintered or other polycrystalline material.

  The seed rack provides a convenient means for transferring seed crystals or seed plates to the high pressure apparatus. This allows easy fluid connection between the seed crystal or seed plate and the nutrient region on the other side of the baffle, and removes crystals grown as a result of the growth run from the reactor. Seed racks should be easy to load and unload, should allow efficient use of available crystal growth, and should minimize crystal breakage and other yield losses. .

In a preferred embodiment, the seed crystal or seed plate consists of gallium nitride. In other embodiments, the seed crystal or seed plate may comprise aluminum nitride, sapphire, silicon carbide, MgAl ² O ⁴ spinel, zinc oxide, or the like. The seed plate has a minimum lateral dimension of at least 1 centimeter. In some embodiments, the seed plate has a maximum lateral dimension of at least 2 centimeters and a minimum lateral dimension of at least 1 centimeter. In other embodiments, the seed plate has a minimum lateral dimension of at least 3 centimeters, at least 4 centimeters, at least 5 centimeters, at least 6 centimeters, at least 8 centimeters, or at least 10 centimeters Have In some embodiments, the seed plate is a bulk single crystal of gallium nitride. In some embodiments, the seed plate is prepared from crystals grown by hydride vapor phase epitaxy. In other embodiments, the seed plate is prepared from crystals grown by an ammonothermal method. In yet another embodiment, the seed plate is prepared from crystals grown from a solvent in a solvent. In one particular embodiment, the seed plate was prepared by the method disclosed in US Patent Application No. 61 / 078,704, which is incorporated herein by reference. In some embodiments, the dislocation density of the large-area surfaces of the seed plates is about 10 ⁶ cm- ² smaller. In some embodiments, the dislocation density of the large-area surfaces of the seed plates is about ¹⁰ 5 cm- ² less than about ¹⁰ 4 cm- ² is less than about ¹⁰ 3 cm- ² less than or about ¹⁰ 2 cm -Less than ² . In some embodiments, the full width at half maximum of the X-ray diffraction line corresponding to the crystal orientation of the large area surface is less than 300 seconds (arc seconds), less than 150 seconds (arc seconds), and more than 100 seconds (arc seconds). Small or less than 50 seconds (arc seconds).

Gallium nitride is a hexagonal wurtzite structure crystal (space group P6 ₃ mc; point group 6 mm) having a characteristic growth sector. Under certain growth conditions, growth occurs in the + c direction, -c direction, m direction, a direction, and other crystal orientations at different rates. In general, the fast growing direction tends to grow out of its presence, thereby terminating the resulting crystal primarily by facets associated with the slow growing direction. The facets most commonly generated by the ammonothermal method are the c-planes (0 0 0 1) and (0 0 0 -1) and the m-plane {1 -1 0 0}. Other surfaces, such as a-plane {1 1 -2 0} and semipolar {1 -1 0 -1}, occur less frequently or in a smaller area. Manufacturing efficiency is increased by using seed crystals or plates that are already large in relatively slow growth dimensions and by performing dominant crystal growth in a relatively fast growth direction. In a preferred embodiment, the large area surface of the seed plate is stable under preselected growth conditions. That is, this growth condition is (0 0 0 1), (0 0 0 -1), {1 -1 0 0}, {1 1 -2 0} or {1 -1 0 -1 } Promoted by selecting an orientation seed plate.

  In addition, the characteristics of impurity incorporation differ between one growth sector and another growth sector. For example, according to the work of Journal of Crystal Grout, Volume 230, pp. 442-447 (2001) by Freyssinet and colleagues, the concentration of free carriers caused by point defects has been increased by specific techniques. In the unintentionally doped bulk GaN crystals + c and -c growth sectors are significantly different. Similar results have been reported by other authors. That is, a general tendency is reported that the [0 0 0 −1] or −c growth sector has a higher impurity concentration than the [0 0 0 1] or + c growth sector. The incorporation of different impurities is undesirable for at least two reasons. First, the presence of a concentration gradient within the crystal makes it more difficult for the crystal manufacturer to maintain a constant product specification. Second, the presence of a concentration gradient within the crystal creates a burden (typically, impurities in GaN cause a slight increase in lattice constant). This burden can cause bowing, cracking, metastasis and other adverse effects. Manufacturing efficiency, including yield, product quality, and product consistency, can be improved by suppressing dominant crystal growth from occurring within only one growth sector.

  In one or more embodiments, it is desired that growth production occurs predominantly in the m-plane. For example, under certain growth conditions, crystal growth occurs more rapidly in the a direction than in the m direction, and more rapidly in the m direction than in the + c or −c direction. Under such predetermined growth conditions, the spontaneously nucleated grown crystal has the shape of a hexagonal platelet, which is larger than the large c facet, the long m-plane end and the diameter. Has a small thickness. Growth in the m direction is preferred because of improved crystal quality, reduced impurity incorporation, or conversely, increased ability to incorporate dopants such as Al or In or bandgap modifications. Growth in the m direction is also ideal for the manufacture of m-plane wafers. Both m-plane seeds or opposing faces on the seed plate constitute m-planes, and the use of such seed crystals will produce growth in a single crystal growth sector.

  In embodiments, the seed crystal is attached to a seed rack, as schematically shown in FIGS. 2A and 2B. Individual seed crystals may be selected or cut to have substantially the same height, so that a plurality of seed crystals may be placed adjacent to each other in a row of seed racks. The seed crystal may have a rectangular large-area surface. The seed crystal may be disposed between the upper seed rack bar and the lower seed rack bar, or may be fixed in place by a clip. When the clip stands independently and is loosened, the clip may fix the seed crystal with a spring force based on the fact that the seed crystal is thicker than the distance between the opposing faces of the clip. In other embodiments, the seed crystal may be attached to the clip by a fastener, such as a threaded rod with nuts at both ends, located adjacent to the clip, seed crystal and seed rack. In still other embodiments, the clip is first attached to the seed crystal and then attached to the seed rack. In some embodiments, the clip has at least one opening through which the crystal can grow, thereby minimizing the burden and occurrence of defects. In still other embodiments, the seed rack may have indentations, slots, cavities, and the like, into which both ends of the seed crystal slide. The foil piece is disposed between the seed crystal and the indentation in the seed rack, thereby facilitating removal after crystal growth. In a preferred embodiment, each of the seed crystals is attached to the seed rack in at least two locations, thereby minimizing the possibility of seed or crystal breakage before, during and after crystal growth, Also, the seed crystal is accurately held at a desired position in the reaction furnace. Adjacent seed crystals or seed plates may be separated by a crystal separation plate. The crystal separation plate may have a hole that slides above the seed rack bar, or may have a slot that is open at one end so as to slide above the seed rack bar. You may have the same thing.

  In some embodiments, the holes or slots are provided in seed crystals or seed plates, which are suspended from the seed rack by at least one wire or elongated foil. In some embodiments, the seed crystal is suspended by at least two wires or elongated foils. Holes or slots in seed crystals or seed plates are formed by laser drilling or laser cutting, ultrasonic drilling, mechanical drilling or milling, grinding, polishing, electrical discharge machining, water jet cutting, or the like. Also good.

  In embodiments, it is desired that growth production occurs predominantly on the a-plane. Growth in the a direction may provide a convenient means for preparing a semipolar substrate direction. Growth in the a-direction is preferred because of improved crystal quality, reduced impurity incorporation, or conversely, increased ability to incorporate dopants such as Al or In or bandgap modifications. Both a-plane seeds or opposing faces on the seed plate constitute the a-plane, and the use of such seeds will produce growth in a single crystal growth sector.

  In other embodiments, the fabrication of growth is on the c-plane, ie in the + c direction ([0 0 0 1] Ga polarity direction) or the −c direction ([0 0 0 −1] N polarity direction). In either case, it is desired to occur predominantly. For example, under certain growth conditions, crystal growth occurs more rapidly in the + c or −c direction than in the m direction. Under such predetermined growth conditions, the grown crystal that spontaneously nucleates has the shape of a hexagonal column, prism, or needle, which has a small c facet and a long m-plane termination side. It has a length smaller than the end and diameter. Growth in the + c or -c direction is preferred because of improved crystal quality, reduced impurity incorporation, or conversely, increased ability to incorporate dopants such as Al or In or bandgap modifications. Growth in the + c or -c direction is also ideal for the production of c-plane wafers. The c-plane seeds or the opposing faces on the seed plate constitute different planes, and the use of such seed crystals alone will produce growth in two distinct crystal growth sectors. Growth in a single crystal growth sector may be achieved by successively stacking pairs of seed crystals or seed plates in the c-plane direction with similar faces adjacent to each other. For example, two c-plane seeds or -c faces of a seed plate may be adjacent to each other such that two c-plane seeds or + c faces of a seed plate face outward and a single Growth is caused to occur in the crystal direction. Conversely, the two c-plane seeds or the + c planes of the seed plates may be adjacent to each other so that the -c planes of the two c-plane seeds or seed plates face outward and a single Growth is caused to occur in the crystal direction. Multiple pairs of seed crystals may be placed in direct contact with each other or separated by a crystal separation plate. If a seed or seed plate pair grows together during a growth run, it may be separated after the run if desired, or used as a seed or seed twin in the next run May be left together to be The c-plane oriented twins are those on which both large area planes constitute the + c or -c plane and are suitable for use as seeds. This is because growth on a large area plane occurs only in a single crystal direction. At least one twin contact or stacking fault is oriented substantially parallel to the large area surface and may be present in the twin.

  In still other embodiments, it is desired that growth fabrication occurs predominantly on the semipolar {1 -1 0 -1} plane. This growth in the semipolar direction is preferred because of improved crystal quality, reduced impurity incorporation, or conversely, increased ability to incorporate dopants such as Al or In or bandgap modifications. Growth perpendicular to the {1 -1 0 -1} plane is also ideal for the production of {1 -1 0 -1} oriented wafers. Opposite faces on the {1 -1 0 -1} direction seed crystal or seed plate constitute different faces, and the use of such seed crystals alone will produce growth in two distinct crystal growth sectors. . Growth in a single crystal growth sector consists of successive pairs of seed crystals or seed plates in the {1 -1 0 -1} direction with faces in the {1 -1 0 1} direction adjacent to each other. It may be realized by stacking. Multiple pairs of seed crystals may be placed in direct contact with each other or separated by a crystal separation plate. If a seed or seed plate pair grows together during a growth run, it may be separated after the run if desired, or used as a seed or seed twin in the next run May be left together to be The {1 -1 0 -1} -oriented twin crystal is one in which both large-area planes constitute the {1 -1 0 -1} plane, and is suitable for use as a seed. This is because growth on a large area plane occurs only in a single crystal direction. At least one twin contact is oriented substantially parallel to the large area surface and may be present in the twin.

  More generally, the production of growth is a semipolar (h k i l) plane (i = − (h + k), l is non-zero, and at least one of h and k is non-zero) It may be desired to occur predominantly above. This growth in the semipolar direction is preferred because of improved crystal quality, reduced impurity incorporation, or conversely, increased ability to incorporate dopants such as Al or In or bandgap modifications. Opposite faces on the seed crystal or seed plate in the (h k i l) direction constitute different faces, and the use of such seed crystals alone will produce growth in two distinct crystal growth sectors. Growth in a single crystal growth sector is achieved by sequentially stacking pairs of seed crystals or seed plates in the (h k i l) direction with faces in the (h k i l) direction facing each other. It may be realized. This causes the (h k i −1) faces of the two seed crystals or seed plates to face outward and cause growth in a single crystal direction. Multiple pairs of seed crystals may be placed in direct contact with each other or separated by a crystal separation plate. If a seed or seed plate pair grows together during a growth run, it may be separated after the run if desired, or used as a seed or seed twin in the next run May be left together to be A semipolar twin is one in which both large area surfaces constitute the same semipolar orientation and is suitable for use as a seed. This is because growth on a large area plane occurs only in a single crystal direction.

  In some embodiments, the seed crystal or seed plate has a rectangular or substantially rectangular shape. The substantially rectangular shape is particularly suitable for an m-plane or a-plane seed plate. In some embodiments, the seed crystal or seed plate corners are rounded or chamfered, thereby minimizing the possibility of breakage. The rectangular shape is convenient for mounting inside the high-pressure crystal growth reactor and for efficiently using space. In other embodiments, the seed crystal or seed plate has a hexagonal or substantially hexagonal shape. The hexagonal shape is particularly convenient when a seed crystal or seed plate in the c-plane direction is used. In still other embodiments, the seed crystal or seed plate has a circular, elliptical, generally circular, or generally elliptical shape.

  In some embodiments, particularly in the case of non-rectangular seed crystals or seed plates, the seeds may be arranged in a non-rectangular dense manner, as shown in FIG. 2C. Rather than constructing as a linear array of bars arranged in multiple layers stacked vertically, the seed rack is cut out prepared in a regular pattern of hexagons, circles, rectangles or other shapes It may have a honeycomb type arrangement. The honeycomb structure may be formed from the sheet by electrical discharge machining, water jet cutting, milling, drilling, or the like. Alternatively, the honeycomb structure may be manufactured from a folded pseudo horizontal bar fitted with a vertical reinforcement structure.

  In some embodiments, particularly those involving the use of autoclaves as high pressure devices, the skeleton further includes a set of stacked disks or baffles on top of it. The stacked disk or baffle reduces convective heat transfer from the supercritical fluid during crystal growth to the top of the autoclave. Thereby, the sealing material of the autoclave is set to a temperature lower than the upper end inside the autoclave. In other embodiments, one or more disks or baffles are placed on the skeleton after the latter is inserted into the high pressure device.

After the skeleton is loaded with seed crystals and raw materials, the skeleton is placed inside a sealable container. This sealable container may be a component of an autoclave or capsule designed for use with high pressure devices with internal heating. At least one mineralizer may be added. Mineralizers are alkali metals such as Li, Na, K, Rb or Cs, alkaline earth metals such as Mg, Ca, Sr or Ba, alkali or alkaline earth hydrides, amides, imides, amideimides, nitridings Or azide. Mineralizers include ammonium halides such as NH ₄ F, NH ₄ Cl, NH ₄ Br or NH ₄ I, gallium halides such as GaF ₃ , GaCl ₃ , GaBr ₃ or GaI ₃ , or HF, HCl , HBr, HI, Ga, and NH ₃ may be included in any compound that can be formed by one or more reactions. Mineralizers may include other alkali, alkaline earth or ammonium salts, other halides, urea, sulfur or sulfide salts, or phosphorus or phosphorus containing salts. The mineralizer may be provided as a metal, as a free powder, as a granule, or as at least one compressed body or tablet. The mineralizer may be added to the raw material basket, placed in a crucible, or placed directly in a high pressure device or capsule. In a preferred embodiment, the mineralizer is added to the high pressure device or capsule without being exposed to air as inside the glove box.

  A getter may also be added to the reaction mixture. The getter preferably reacts with residual or incidental oxygen or moisture present to improve the purity and transparency of the grown GaN crystal. The getter comprises at least one of alkaline earth metals, Sc, Ti, V, Cr, Y, Zr, Nb, Hf, Ta, W, rare earth metals and their nitrides, amides, imides, amideimides or halides. Have.

  In some embodiments, at least one of the mineralizer and getter is disposed within the crucible at the location within the raw material basket or closest to the raw material basket.

The use of metal precursors for raw materials, mineralizers, and / or getters is convenient in several ways. For example, high purity metals are typically commercially available and require no further synthesis. However, in addition to the complexity of properly supporting metals that melt under reaction conditions (eg, Ga, Na, K), the use of pure metals may produce undesirable gases such as hydrogen. For example, under ammonothermal method reaction conditions, the metals described below may undergo one or more of the following reactions.
Ga + NH ₃ = GaN + 3/2 H ₂
Na + NH ₃ = NaNH ₂ + 1/2 H ₂
K + NH ₃ = KNH ₂ + 1/2 H _{2
Mg + 2NH 3 = Mg (NH} 2) 2 + H 2
_{3Mg + 2NH 3 = Mg 3 N} 2 + 3H 2
Y + 3NH ₃ = Y (NH ₂ ) ₃ + 3/2 H ₂
Y + NH ₃ = YN + 3/2 H ₂

  The presence of hydrogen in the supercritical fluid solvent may reduce the solubility of the gallium-containing species, and may further make the metals that make up the autoclave walls fragile.

The use of azide as a mineralizer is convenient. The reason for this is that azides are highly commercially available, can be further purified, and are considerably less hygroscopic than, for example, alkali metals or amides, or alkaline earth nitrides. The use of an azide mineralizer is suggested by Dwilinski of US Pat. No. 7,364,619, which is incorporated herein by reference in its entirety. However, azides generally decompose under reaction conditions and produce undesirable gases such as nitrogen:
_{3NaN 3 + 2NH 3 = 3NaNH 2} + 4N 2

In a preferred embodiment, these two effects are combined to cancel each other. Metals including raw materials, mineralizers and getters are added with the azide mineralizer precursor so that H ₂ and N ₂ are produced in a ratio of approximately 3: 1. The reaction vessel further includes a means for catalyzing the formation of NH ₃ from H ₂ and N ₂ . Catalysis of the reaction between H ₂ and N ₂ liberated in the reaction of metal and ammonia to form ammonia and the decomposition of azide, respectively, are added by the walls of the autoclave or It is carried out by the catalyst. The added catalyst may consist of powders, granules, foils, coatings, bulk materials or porous pellets. The added catalyst is at least one of iron, cobalt, nickel, titanium, molybdenum, tungsten, aluminum, potassium, cesium, calcium, magnesium, barium, zirconium, osmium, uranium or lanthanoid, ruthenium, platinum, palladium or rhodium. You may have one. For example, 1 mole of NaN ₃ added would produce 4/3 moles of N ₂ . The latter can be offset by adding 8/3 moles of Ga metal. This appears to produce 8/3 ra 3/2 moles = 4 moles of H ₂ , ie three times the number of moles of N ₂ from NaN ₃ .

  The sealable container is then closed and sealed with the exception of connections to gas, liquid or vacuum manifolds. In one embodiment, the sealable container includes an autoclave as taught in US Pat. No. 7,335,262, which is hereby incorporated by reference in its entirety. In other embodiments, the sealable container is a metal can as described in US Pat. No. 7,125,453, a container as described in US Patent Application No. 2007/0234946, or “ Including capsules as described in US patent application Ser. No. 12 / 133,365 entitled “Improved Capsules and Methods of Using Supercritical Fluids for High Pressure Processing”. All of these patents and patent applications are incorporated herein by reference in their entirety. The inner diameter of the autoclave or capsule is 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, It may be 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 spacing between the inner diameter of the autoclave or capsule and the outline of the skeleton may be 0.005 inches to 1 inch, or 0.010 inches to 0.25 inches. The ratio between the inner height of the autoclave or capsule and its inner diameter is 1 to 2, 2 to 4, 4 to 6, 6 to 8, 8 to 10, 10 to 12, 12 to 15, 15 to 20, Or it may be larger than 20.

  In some embodiments, the autoclave or capsule is evacuated to remove air, moisture, and other volatile contaminants. In some embodiments, the high pressure device is heated to a temperature of about 25 ° C. to about 500 ° C. during evacuation. In some embodiments, the autoclave or capsule is heated using the same heating element used during high pressure processing. In certain embodiments, the capsule is heated by being placed inside a pressure device with internal heating and heated using a heater for the latter.

  In other embodiments, as shown in FIGS. 3A and 3B, an autoclave or capsule containing a filled skeleton may be used to remove air, moisture, and other volatile contaminants. Purged. Purging provides superior removal of air, moisture, and other volatile contaminants compared to exhaust due to limited conductivity of tubes or long holes reaching the interior of an autoclave or capsule To do. Then, according to certain embodiments, the autoclave or capsule is connected to a gas source using at least one fill or purge tube, preferably without exposing the contents of the capsule to air. The gas source may consist of at least one of nitrogen, argon, hydrogen, helium and solvent vapor, among others. In some embodiments, both the first fill or purge tube and the second fill or purge tube are connected to a gas source and / or an exhaust tube. In other embodiments, the inner purge tube is positioned inside the fill or outer purge tube and is positioned so that one end is closest to the bottom end of the autoclave or capsule. Inner purge pipe and outer purge pipe are copper, copper base alloy, gold, gold base alloy, silver, silver base alloy, palladium, platinum, iridium, ruthenium, rhodium, osmium, iron, iron base alloy, nickel, nickel base alloy , Molybdenum, and combinations thereof. The iron-base alloy used to form the inner and outer purge tubes includes, but is not limited to, stainless steel. Nickel-based alloys used to form the inner and outer purge tubes include, but are not limited to, Inconel, Hastelloy and the like. As shown, the outer diameter of the inner purge tube is at least 0.010 inches smaller than the inner diameter of the fill or outer purge tube. According to certain embodiments, the inner purge tube is connected to the fill or outer purge tube by tee fitting or other suitable technique. As a result, the purge gas introduced through the inner purge pipe is discharged near the bottom end of the autoclave or the capsule, and is outside the inner purge pipe and the tee fitting, and the annular space in the filling or outer purge pipe Pass through the length of the autoclave or capsule before being discharged through, providing for efficient removal of gas phase contaminants. The junction between the tee fitting and the inner purge tube may be a slide seal, for example an O-ring or a differentially evacuated set of Teflon seals or O-rings. The purge gas flow rate may range from 0.05 to 10 standard liters per minute. In order to remove water and other absorbed contaminants more efficiently, the autoclave or capsule may be heated to a temperature of, for example, 25 ° C. to 500 ° C. during the purge operation. After stopping the purge gas flow, a solvent vapor, such as gas phase ammonia, may be flowed through the autoclave or capsule to remove most or all of the purge gas.

Then, in certain embodiments, a gas inlet, such as a second fill or purge tube, is connected to a source of liquid solvent. The autoclave or capsule and filling tube may be cooled, or the liquid solvent transport mechanism and transfer line may be heated. Thereby, the former is made to be 1 to 50 ° C. lower than the latter. The liquid solvent is then introduced into the autoclave or capsule at a rate of 0.1 to 1000 grams / minute. At room temperature, the vapor pressure of ammonia is about 10 atmospheres. Thus, depending on the temperature of the solvent source, the pressure of the mechanism during solvent delivery may be greater than 7 atmospheres, greater than 8 atmospheres, greater than 9 atmospheres, or greater than 10 atmospheres. In certain embodiments, the purge outlet is closed and the solvent vapor on the liquid must be liquefied during the filling operation. In this embodiment, the autoclave or capsule may be actively cooled to dissipate the heat released by the liquefaction of the solvent vapor. In another embodiment, a check valve is attached to the purge exhaust port. Thus, when the pressure exceeds a predetermined threshold, the remaining purge gas and solvent vapor are discharged, while air and other gases do not flow back into the autoclave. The amount of solvent in the autoclave or capsule may be measured using a liquid transport mechanism that can accurately measure and control the mass of the liquid being transported. An example of a suitable device for the delivery of accurately metered high purity liquid ammonia is iCon Dynamics, LLC. InScale ^™ system manufactured by In some embodiments, the amount of ammonia delivered to the autoclave or capsule is metered by a decrease in the weight of at least one ammonia supply cylinder. If solvent gas can be evacuated during the filling of the liquid and ammonia is the solvent, the amount of solvent released is first confined in the aqueous solution, then the pH change, and It may be measured by measuring the amount subtracted from the total liquid delivered to measure the amount of liquid in the autoclave or capsule. A similar method for measuring the amount of solvent released may be performed when the solvent is not ammonia.

  In another embodiment, the solvent is delivered to the autoclave or capsule as a vapor at elevated pressure. A gas inlet, such as a second fill or purge tube, is then connected to a gas phase solvent source. The autoclave or capsule and fill tube may be cooled, or the solvent transport mechanism and transfer line may be heated. As a result, the former is set to a temperature lower by 1 to 50 ° C. than the latter. The gas phase solvent is then introduced into the autoclave or capsule at a rate of 0.1 to 1000 grams / min and can be liquefied in the autoclave or capsule. The solvent vapor pressure should be higher than the equilibrium vapor pressure at the autoclave or capsule temperature. Depending on the temperature of the autoclave or capsule and the solvent delivery mechanism, the pressure during solvent delivery is greater than 7 atmospheres, greater than 8 atmospheres, greater than 9 atmospheres, or greater than 10 atmospheres. In some embodiments, the purge outlet is closed and the solvent vapor on the liquid during the filling operation must be liquefied. In this embodiment, the autoclave or capsule may be actively cooled to dissipate the heat released by the liquefaction of the solvent vapor. In another embodiment, a check valve is attached to the purge exhaust port. Thus, when the pressure exceeds a predetermined threshold, the remaining purge gas and solvent vapor are discharged, while air and other gases do not flow back into the autoclave. The amount of solvent in the autoclave or capsule may be measured using a vapor transport mechanism equipped with a mass flow meter. In some embodiments, the amount of ammonia delivered to the autoclave or capsule is metered by a decrease in the weight of at least one ammonia supply cylinder. If solvent gas can be evacuated during the filling of the liquid and ammonia is the solvent, the amount of solvent released can be changed by changing the pH after first confining it in a solution containing water. , And by measuring the amount subtracted from the total liquid transported to measure the amount of liquid in the capsule. A similar method for measuring the amount of solvent released may be performed when the solvent is not ammonia.

  Following autoclaving or capsule filling, if there is an inner purge tube, it may be removed. In some embodiments, the inner purge tube is removed after the purge step and before the filling step. The gate valve to the autoclave or the filling tube to the capsule is then sealed. Once sealed, the interior of the autoclave or capsule is substantially free of air and at least one material contained therein can be processed with reduced risk of contamination. Of course, there can be other variations, modifications, and alternatives.

In some embodiments, the autoclave is then heated to crystal growth conditions. In other embodiments, the capsule is placed inside an autoclave, a pressure device with internal heating, or other high pressure device, and heated to crystal growth conditions. In certain embodiments, the thermal cycle includes a pre-reaction section to form a mineralizer, polycrystalline gallium nitride, dissolved gallium-containing composite, or the like. In certain embodiments, the atmosphere in the autoclave may be changed during execution. For example, excess H ₂ formed by the reaction of gallium metal and ammonia may flow out through a gate valve or be diffusible through a heated palladium film. Excess nitrogen formed by decomposition of the azide mineralizer may flow out through the gate valve. Additional ammonia may be added to replenish the solvent in the high pressure apparatus.

  Suitable thermal cycles for crystal growth are described in US Pat. Nos. 6,656,615 and 7,078,731, which are hereby incorporated by reference in their entirety. Most of the crystals grow perpendicular to the large diameter surface, but may grow somewhat in the horizontal direction. With the possible exception of c-planes or {1 −1 0 a1} species stacked in series, the crystal separators prevent the crystals from growing towards each other.

After performing crystal growth for a predetermined time, the autoclave or high-pressure apparatus is cooled. If the autoclave or capsule is cooled to below 100 ° C, below 75 ° C, below 50 ° C, or below 35 ° C, the valve to the autoclave is opened or the capsule is evacuated. Ammonia is removed. In one embodiment, gaseous ammonia can be drained from the autoclave or capsule and bubbled into an acidic aqueous solution to be chemically captured. In other embodiments, gas phase ammonia passes through the flame to burn ammonia, forming H ₂ O and N ₂ . In a preferred embodiment, ammonia is captured for reuse or reuse, as illustrated in FIGS. 6A and 6B.

As shown in FIG. 6A, as appropriate for single-ended autoclaves or capsules, ammonia may be removed as either liquid or gas. To remove the ammonia as a liquid, the inner purge tube (see FIG. 3A3B) is reinserted into the outer purge or fill tube, and the outlet of the inner purge tube is connected to the receiving / purification tank. With the purge gas exhaust connection (see FIGS. 3A and 3B) closed, the valve in the line reaching the inner purge pipe is opened, allowing liquid ammonia to pass through the inner purge pipe in the autoclave / It is possible to flow into the purification tank. Otherwise, the valve is closed. During the ammonia transfer operation, the receiving / purification tank may be cooled, for example by cold water, and in addition or alternatively, the autoclave or capsule and the transfer line may be heated. This maintains that the vapor pressure of ammonia in the autoclave is high compared to the vapor pressure in the receiving / purification tank. The temperature difference between the autoclave or capsule and the receiving / purification tank may be kept between 1 and 50 ° C. In other embodiments, ammonia is removed as a gas. The autoclave or capsule outlet is connected to a liquefier above the receiving / purification tank and to an open valve. The gaseous ammonia enters the liquefier and liquefies in the heat exchanger, for example at a pressure of about 100 to 250 pounds per square inch. The autoclave and transfer line may be heated to a temperature higher than the liquefier by 1 to 50 ° C. For example, surplus gases such as N ₂ and H ₂ may be released by being exhausted towards a gas scrubber and / or a flame.

  As shown in FIG. 6B, the ammonia may be removed as a liquid, suitable for a double-ended autoclave or capsule. A port on the bottom end of the autoclave or a filling tube on the bottom end of the capsule is connected to the receiving / purification tank and an open valve, allowing liquid ammonia to flow into the receiving / purification tank And Otherwise, the valve is closed. During the ammonia transfer operation, the receiving / purification tank may be cooled, for example by cold water, and in addition or alternatively, the autoclave and transfer line may be heated. This maintains that the vapor pressure of ammonia in the autoclave is high compared to the vapor pressure in the receiving / purification tank. The temperature difference between the autoclave and the receiving / purification tank may be kept between 1 and 50 ° C.

  For reuse purposes, a substance for purification, such as sodium metal, may be placed in the receiving / purification tank. Sodium reacts with excess oxygen and / or water in ammonia and recovers to very high purity. After a period of 1 hour to 30 days, ammonia may be transferred to the delivery tank. In a preferred embodiment, this transfer is performed in the gas phase via a liquefier so that the material to be purified remains in the receiving / purification tank. Liquid ammonia may be transferred from the delivery tank to the autoclave via a dip tube for the next crystal growth run. In other embodiments, gas phase ammonia may be transferred from the delivery tank to an autoclave or capsule for subsequent crystal growth runs.

  After cooling, removal of ammonia, and opening of the high pressure apparatus and capsule by autoclave or internal heating, the framework is removed from the autoclave or capsule and the grown crystals are removed from the seed rack. If necessary, the portion of the clip that has grown too much by the crystalline material may be removed by etching in a suitable acid such as at least one of hydrochloric acid, sulfuric acid, nitric acid, and hydrofluoric acid. good.

  As summarized in FIGS. 4A, 4B and 4C, the crystal is sliced in a preselected orientation. In one embodiment, the seed crystal has an m-plane orientation and is sliced into an m-plane orientation wafer, as shown in FIG. 4A. In other embodiments, as shown in FIG. 4B, the seed crystal is in the + c or −c orientation (or the bicrystal described above) and sliced into a c-plane oriented wafer. In other embodiments, the seed crystals are {1 −1 0 −1} oriented and sliced into {1 −1 0 a1} oriented wafers. In another embodiment, the seed crystal has an m-plane orientation and is sliced at an angle of about 28 degrees with respect to a large area m-plane to prepare a semipolar wafer of {1 -1 0 a1} orientation. The In other embodiments, the seed crystals are {1 -1 0 -1} oriented and about 18.8 for a large area surface to prepare a semipolar wafer of {1 -1 0 a2} orientation. Sliced at a degree angle. In other embodiments, the seed crystals are {1 -1 0 -1} orientation, and about 29.9 for a large area surface to prepare a semipolar wafer of {1 -1 0 a3} orientation. Sliced at a degree angle. In other embodiments, the seed crystals are {1 -1 0 -1} orientation, and about 26.2 for a large area surface to prepare a semipolar wafer of {1 1 -2 a2} orientation. Sliced at a degree angle. In another embodiment, the seed crystal is c-plane oriented and sliced at an angle of about 32 degrees with respect to the large-area c-plane to prepare a {1 -1 0 a3} -oriented semipolar wafer. . In another embodiment, the seed crystal is m-plane oriented and sliced at an angle of about 42.5 degrees to a large area m-plane to prepare a semipolar wafer with {1 1 -2 a 2} orientation. Is done. In yet another embodiment, the seed crystal is c-plane oriented and at an angle of about 43.2 degrees with respect to the large-area c-plane to prepare a semipolar wafer of {1 -1 0 a2} orientation. Sliced. In yet another embodiment, the seed crystal is c-plane oriented and at an angle of about 62.0 degrees with respect to the large-area c-plane to prepare a semipolar wafer of {1 -1 0 a1} orientation. Sliced. In another embodiment, the seed crystal is c-plane oriented and sliced at an angle of about 58.4 degrees relative to a large area c-plane to prepare a {1 1 -2 a 2} -oriented semipolar wafer. Is done. In another embodiment, the seed crystal is c-plane oriented and sliced at an angle of about 90.0 degrees with respect to a large area c-plane to prepare a non-polar wafer of {1 -1 0 0} orientation. The In another embodiment, the seed crystal is c-plane oriented and sliced at an angle of about 90.0 degrees with respect to the large-area c-plane to prepare a {1 1 -2 0} -oriented non-polar wafer. The

  In another embodiment, the seed crystal has a crystal orientation such that at least one large surface is a relatively fast growing surface. In one particular embodiment, the seed crystal has an a-plane orientation. In other embodiments, the seed crystal has a semipolar orientation. In a specific embodiment, the orientation of the seed crystal is {1 -1 0 a 1}, {1 -1 0 a 2}, {1 -1 0 a 3} or {1 1 -2 a 2}. In some embodiments, the two seed crystals are arranged together sequentially so that the opposing faces of the seed crystals mounted together have equal crystal orientation. The use of a fast growing orientation allows the production of high quality crystals to be overall faster. As shown in FIG. 4C, in certain embodiments, the seed is a-plane orientation. The initial rapid growth in the a direction becomes slower as m-planes are formed near the upper and lower ends of the crystal. At the end of the crystal growth cycle, the crystal is terminated by four large area m-plane facets, as shown at the end of FIG. 4C. As a shape, the m-plane facet is about 58% of the length of the first 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 may be sliced at other angles to produce multiple c-plane wafers, a-plane wafers, or semipolar wafers. Semipolar wafers are {1 -1 0 a 1} orientation, {1 -1 0 a 2} orientation, {1 -1 0 a 3} orientation, {2 0 -2 a 1} orientation, {1 1 -2 A)} orientation, or more generally (h k i l) orientation (i = − (h + k), l is non-zero, and at least one of h and k is non-zero) , May be included.

  After slicing, the crystal wafer may be rough polished, polished and chemically mechanically polished by generally known methods.

  The crystal wafer is useful as a substrate for manufacturing the following optoelectronics and electronic devices. That is, at least one of LED (Light Emitting Diodes), laser diode, photodetector, avalanche photodiode, transistor, rectifier, thyristor; transistor, rectifier, Schottky rectifier, thyristor, pin diode, metal- Semiconductor-metal diode, high electron mobility transistor, metal-semiconductor field effect transistor, metal-oxide field effect transistor, power MOS (Metal Oxide Semiconductor) field effect transistor, power MIS (Metal Insulator Semiconductor) field effect transistor, bipolar junction Transistors, metal-insulator field effect transistors, heterojunction bipolar transistors, transistors -Insulated gate bipolar transistors, power vertical junction field effect transistors, cascade switches, internal subband emitters, quantum well infrared photodetectors and quantum dot infrared photodetectors, solar cells, and for photoelectrochemical water splitting and hydrogen generation At least one of the diodes.

  In certain embodiments, any of the sequential steps described above provide a method in accordance with certain embodiments of the present invention. In certain embodiments, the present invention provides a method and resulting crystalline material provided by a pressure device having a basket structure. Other means may be provided in which some steps are added, one or more steps are omitted, or one or more steps are provided in different procedures without departing from the scope of this claim. .

While the above is a complete description of a particular embodiment, various modifications, alternative constructions, and equivalents may be used. Therefore, the above description and description should not be taken as limiting the scope of the invention which is defined by the appended claims.

Claims (50)

Preparing a gallium-containing source material;
Preparing 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 on a first site and a second site of a seed rack, wherein the first seed plate and the second seed plate are 5 degrees; Having a crystal orientation substantially equal to within, each of the first seed plate and the second seed plate having a length;
Installing the source material, the mineralizer and the seed plate in a sealable container;
Introducing a nitrogen-containing solvent into the sealable container; and at a temperature and pressure, the source material, the mineralizer and the seed plate contained in the sealable container in a supercritical liquid Including processing,
A method for growing a gallium-containing nitride crystal.   Each of the first seed plate and the second seed plate has a first side surface and a second side surface, and the first side surface and the second side surface are substantially equal to within 5 degrees. Having a crystal orientation, each of the first seed plate and the second seed plate has a length of at least 1 centimeter, the temperature is greater than about 400 ° C., and the pressure is greater than about 2 kbar. The method of claim 1, wherein the method is high. Either the first seed plate or the second seed plate is characterized by a maximum lateral dimension of at least 2 centimeters and a minimum lateral dimension of at least 1 centimeter, and the sealable container is autoclaved The method of claim 1, wherein the method is a container or a capsule. The method of claim 1, further comprising increasing the thickness of at least one of the seed plates by at least 1 millimeter. The method of claim 4, wherein the thickness of at least one of the seed plates is increased by at least 2 millimeters. The method of claim 1, wherein at least one of the surfaces of at least one of the seed plates has a crystal orientation within 5 degrees from the {1 −1 0 0} m plane.   The method of claim 6, wherein the seed plate is substantially rectangular.   The method of claim 1, wherein at least one of the surfaces of at least one of the seed plates has a crystal orientation within 5 degrees from a {1 -1 0 a1} semipolar plane.   The method of claim 8, wherein the seed plate is substantially rectangular. The method of claim 1, wherein the large area surface of the seed plate has a crystal orientation within 5 degrees from the (0 0 0 1) Ga polar c-plane.   The method of claim 1, wherein the large area surface of the seed plate has a crystal orientation within 5 degrees from the (0 0 0 -1) N polar c-plane.   Further comprising slicing a bowl derived from either the first seed plate or the second seed plate to prepare at least one of an m-plane, a-plane, c-plane, or semipolar substrate. The method of claim 1. Preparing a gallium-containing source material;
Preparing a mineralizer,
Providing at least a first seed plate and a second seed plate,
The first seed plate has a first side surface having a first crystal orientation and a second side surface having a second crystal orientation;
The second seed plate has a first side surface having a first crystal orientation and a second side surface having a second crystal orientation;
The second side surface of the first seed plate and the second side surface of the second seed plate have a crystal orientation substantially equal to within 5 degrees and have a minimum lateral dimension of at least 1 centimeter Have
Supporting the first seed plate and the second seed plate, whereby the first side surface of the first seed crystal faces the first side surface of the second seed crystal; The first side surface of the first seed crystal and the first side surface of the second seed crystal are arranged with a predetermined gap therebetween,
Installing the source material, the mineralizer and the seed plate in a sealable container;
Introducing the nitrogen-containing solvent into the sealable container, and the source material contained in the sealable container in supercritical fluid at a temperature greater than about 400 ° C. and a pressure greater than about 2 kbar; Treating the mineralizer and the seed plate,
A method for growing a gallium-containing nitride crystal.   Each of the first side and the second side of each of the first seed plate and the second seed plate has a maximum lateral dimension of at least 2 centimeters and a minimum lateral dimension of at least 1 centimeter. 14. The method of claim 13, comprising:   14. The method of claim 13, further comprising increasing each of the first thickness of the first seed plate and the second thickness of the second seed plate by at least 1 millimeter. 14. The method of claim 13, further comprising increasing each of the first thickness of the first seed plate and the second thickness of the second seed plate by at least 2 millimeters.   14. The method of claim 13, wherein each of the second side faces outward and has a crystal orientation within 5 degrees from the (0 0 0 1) Ga polar c-plane.   14. The method of claim 13, wherein each of the second side faces outward and has a crystal orientation within 5 degrees from the (0 0 0 -1) Ga polar c-plane.   14. The method of claim 13, wherein each of the second side faces outward and has a crystal orientation within 5 degrees from a {1 -1 0 -1} semipolar plane.   Further comprising slicing a bowl derived from either the first seed plate or the second seed plate to prepare at least one of an m-plane, a-plane, c-plane, or semipolar substrate. The method of claim 13. A method for growing crystalline gallium-containing nitride using one or more seed racks, comprising:
Providing a high pressure apparatus having a seed rack apparatus, a gallium-containing source in one area, and at least one seed in the seed rack apparatus in another area, and a sealable container.
Introducing a solvent capable of forming a supercritical fluid into at least one of the zones and the other zone;
Treating one or more portions of the gallium-containing raw material in the supercritical fluid to prepare a supercritical solution containing at least a gallium-containing species at a first temperature; and at a second temperature on the seed Growing a crystalline gallium-containing nitride material from the supercritical solution, wherein the second temperature is such that the gallium-containing species forms the crystalline gallium-containing nitride material on the species. A growth method, including being characterized.   The seed rack is copper, copper base alloy, gold, gold base alloy, silver, silver base alloy, palladium, platinum, iridium, ruthenium, rhodium, osmium, titanium, vanadium, chromium, iron, iron base alloy, nickel, nickel The method of claim 21, comprising at least one of a base alloy, zirconium, niobium, molybdenum, tantalum, tungsten, rhenium, silica, alumina, and combinations thereof.   The method of claim 21, wherein the sealable container in the high pressure apparatus has an inner diameter greater than 75 mm. A method for growing crystalline gallium-containing nitride, comprising:
Providing a high pressure device having a sealable container with a gallium-containing source in one area and at least one species in another area;
Introducing a solvent capable of forming a supercritical fluid into at least one of the zones and the other zone;
Maintaining the pressure in the one zone and the other zone at about 7 atmospheres or more while introducing the solvent into the one zone and the other zone;
Treating one or more portions of the gallium-containing raw material in the supercritical fluid to prepare a supercritical solution containing at least a gallium-containing species at a first temperature; and at a second temperature on the seed Growing a crystalline gallium-containing nitride material from the supercritical solution, wherein the second temperature is such that the gallium-containing species forms the crystalline gallium-containing nitride material on the species. A growth method, including being characterized.   25. The method of claim 24, wherein the introduction of the solvent occurs when the solvent is substantially liquid.   25. The method of claim 24, further comprising purging the sealable container prior to introducing the solvent.   25. The method of claim 24, wherein the sealable container has an inner diameter greater than 75 mm. A method for growing crystalline gallium-containing nitride, comprising:
Providing an autoclave having a gallium-containing source in one zone and at least one species in another zone;
Introducing a first solvent capable of forming a supercritical fluid into at least the one and the other zones;
Maintaining the pressure in the one zone and the other zone at about 7 atmospheres or more while introducing the solvent into the one zone and the other zone;
Treating one or more portions of the gallium-containing raw material in the supercritical fluid to prepare a supercritical solution containing at least a gallium-containing species at a first temperature; and at a second temperature on the seed Growing a crystalline gallium-containing nitride material from the supercritical solution, wherein the second temperature is such that the gallium-containing species forms the crystalline gallium-containing nitride material on the species. Is characterized by
Removing the thermal energy from the autoclave, forming a second solvent from the supercritical solution, and removing the second solvent from the autoclave through a drain. .   30. The method of claim 28, further comprising transferring the second solvent from the drain to a purification process.   29. The method of claim 28, further comprising moving the second solvent from the drain to a purification process to reuse the second solvent.   Moving the second solvent from the drain to the refining process to reuse the second solvent; refining the second solvent in the refining process to form a third solvent; And transferring the third solvent to the autoclave.   32. The method of claim 31, wherein the third solvent is substantially the same as the first solvent.   30. The method of claim 28, wherein the second solvent comprises a hydrogen species, a nitrogen species, one or more trace metals, and a dissolving mineralizer. Wherein the first solvent is substantially NH _3, The method of claim 28. A method for growing crystalline gallium-containing nitride, comprising:
Providing an autoclave with a gallium-containing source in a basket structure in one zone, at least one species in another zone, and a solvent capable of forming a supercritical fluid. The basket structure is configured to substantially prevent one or more solid portions of the raw material from moving from the one area to the other area;
Preparing a supercritical solution containing at least a gallium-containing species at a first temperature by treating one or more portions of the gallium-containing raw material in the supercritical fluid;
Flowing one or more portions of the supercritical solution comprising a gallium-containing species from the one area through a portion of the basket to the other region, and at a second temperature, the Growing a crystalline gallium-containing nitride material from a supercritical solution, wherein the second temperature is such that the gallium-containing species forms the crystalline gallium-containing nitride material on the species; A growth method comprising being characterized. And at least one crucible in which at least one of gallium metal and alkali metal is disposed in the one region,
The basket structure is made of copper, copper base alloy, gold, gold base alloy, silver, silver base alloy, palladium, platinum, iridium, ruthenium, rhodium, osmium, titanium, vanadium, chromium, iron, iron base alloy, nickel, 36. The method of claim 35, comprising one or more support structures comprising one or more materials selected from nickel-based alloys, zirconium, niobium, molybdenum, tantalum, tungsten, rhenium, silica, alumina, and combinations thereof.   37. The method 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 method of claim 37, wherein the autoclave has an inner diameter greater than 75 mm. 37. The method of claim 36, wherein the gallium-containing source has at least one dopant with a concentration between 10 ^{< 16} > cm ^<-3 > and 10 ^{< 21} > cm ^<-3 >.   40. The method of claim 39, wherein the dopant comprises at least one of Si, O, Mg, Zn, Fe, Ni, Co, or Mn.   The framework is further configured to move the basket structure, baffle and seed rack to the autoclave before starting crystal growth, and at the end of crystal growth execution. 37. The method of claim 36, configured to move the basket structure, the baffle and the growth crystal out of the autoclave.   37. The method of claim 36, wherein the gallium-containing source comprises gallium nitride having a particle size distribution between 0.020 inches and 5 inches.   38. The method of claim 36, further comprising getter material and / or structure in the vicinity of either or both of the one area and / or the other area.   The getter is at least one of alkaline earth metals, Sc, Ti, V, Cr, Y, Zr, Nb, Hf, Ta, W, rare earth metals and their nitrides, amides, imides, amideimides or halides. 44. The method of claim 43, comprising: A method for growing crystalline gallium-containing nitride, comprising:
Providing a high pressure apparatus having a gallium-containing raw material in one zone, at least one species in another zone, an azide mineralizer, and at least one metal, the azide mineralizer and the The metal is prepared at a predetermined ratio such that the ratio of nitrogen generated by the decomposition of the azide mineralizer and hydrogen generated by the reaction of the metal and the supercritical liquid is approximately 1: 3.
Treating one or more portions of the gallium-containing raw material in the supercritical fluid to prepare a supercritical solution containing at least a gallium-containing species at a first temperature; and at a second temperature on the seed Growing a crystalline gallium-containing nitride material from the supercritical solution, wherein the second temperature is such that the gallium-containing species forms the crystalline gallium-containing nitride material on the species. A growth method, including being characterized.   46. The method of claim 45, further comprising providing a catalyst in the vicinity of at least the one zone or the other zone of the high pressure apparatus to convert nitrogen and hydrogen to ammonia.   The catalyst has at least one of iron, cobalt, nickel, titanium, molybdenum, tungsten, aluminum, potassium, cesium, calcium, magnesium, barium, zirconium, osmium, uranium or lanthanoid, ruthenium, platinum, palladium or rhodium. 48. The method of claim 46. A method for growing crystalline gallium-containing nitride, comprising:
A gallium-containing source in one zone, at least one species in another zone, an azide mineralizer, at least one metal, and in the vicinity of one or both of the one zone and / or the other zone. A high pressure apparatus having a catalyst, wherein the azide mineralizer and the metal are produced by a reaction of nitrogen produced by decomposition of the azide mineralizer and at least the metal and supercritical ammonia. Prepared at a predetermined ratio so that the ratio with the hydrogen gas species is about 1: 3 or more,
Treating one or more portions of the gallium-containing raw material in the supercritical ammonia to prepare a supercritical ammonia solution containing at least a gallium-containing species at a first temperature; and at a second temperature, the species Growing a crystalline gallium-containing nitride material from the supercritical ammonia solution above, wherein the second temperature is such that the gallium-containing species forms the crystalline gallium-containing nitride material on the species It is characterized as
At least from the reaction between the metal and the supercritical ammonia solution, the hydrogen gas species is generated,
A growth method comprising treating the hydrogen gas species with at least the catalyst and converting the hydrogen gas species and nitrogen gas species into the supercritical ammonia liquid.   49. The method of claim 48, wherein the ratio of approximately 1: 3 ranges from about 0.8: 3 to 1: 3.8.   The catalyst has at least one of iron, cobalt, nickel, titanium, molybdenum, tungsten, aluminum, potassium, cesium, calcium, magnesium, barium, zirconium, osmium, uranium or lanthanoid, ruthenium, platinum, palladium or rhodium. 49. The method of claim 48.