CN102144052A - Process for large-scale ammonothermal manufacturing of gallium nitride boules - Google Patents

Abstract

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

Description

The method of extensive ammonia hot preparation gan crystal bar

The cross reference of related application

The application requires following commonly assigned U.S. Provisional Application: 61/087 of submission on August 7th, 2008,122,61/087 of submission on August 7th, 2008,135,61/086 of submission on August 7th, 2008,801,61/086 of submission on August 7th, 2008,800,61/086 of submission on August 7th, 2008,799 right of priority is incorporated it into this paper by reference.

The research of subsidizing about federal government or develop the rights statement of obtained invention

Inapplicable

The reference of " sequence table " submitted on the CD, form or computer program inventory annex

Inapplicable

Background of invention

In general, the present invention relates to be used for the processing of the material of growing crystal.More specifically, the invention provides and a kind ofly obtain to contain gallium nitride crystalline method, but other can be arranged by ammonia alkali or propylhomoserin technology.In other embodiments, the invention provides a kind of device that is used for handling on a large scale element nitride crystal, but it should be understood that also and can handle other crystal and material.This crystalloid and material include but not limited to GaN, AlN, InN, InGaN, AlGaN and AlInGaN and are used to prepare other crystal and the material of bulk or patterned substrate.This class bulk or patterned substrate can be used for various application, comprise opto-electronic device, laser apparatus, photodiode, solar cell, water photoelectrolysis and devices such as hydrogen manufacturing, photodetector, unicircuit and transistor.

The crystalline material of nitrogen gallium is as the starting point of making conventional opto-electronic device such as blue light-emitting diode and laser apparatus.This class opto-electronic device is generally made forming on sapphire different with sedimentary nitride layer or the silicon carbide substrates.In metal-organic chemical vapor deposition (MOCVD) method of routine, the deposition of GaN is carried out in gas phase from ammonia and organometallic compound.Though success, the conventional growth velocity that obtains makes it be difficult to provide the course of blocks of GaN material.In addition, dislocation desity is also high, makes the poor-performing of opto-electronic device.

Propose other technology and be used to obtain the bulk-shaped monocrystal gan.This class technology comprises that use adopts halogenide and hydride and be called the epitaxial deposition [people such as " Growth and characterization of freestanding GaN substrates " K.Motoku of hydride gas-phase epitaxy (HVPE) in gas phase, Journal of Crystal Growth 237-239,912 (2002)].Unfortunately, there is shortcoming in the HVPE technology.Sometimes, because problems such as dislocation desity, stress, the quality of bulk-shaped monocrystal gan is normally not enough for high-quality laser diode.

Proposed to use the technology of supercritical ammine.Peters has described the ammonia thermal synthesis [J.Cryst.Growth 104,411418 (1990)] of aluminium nitride.Especially, R.

Pointed out that Deng the people by obtaining thin brilliant gan from the synthetic of gallium and ammonia, condition is that described ammonia comprises alkali metal ammonia compound (KNH ₂Or LiNH ₂).These and other technology is at " AMMONO method of BN, AlN, and GaN synthesis and crystal growth ", Proc.EGW-3, Warsaw, Jun.2224,1998, MRS Internet Journal of Nitride Semiconductor Research Http:// nsr.mij.mrs.Org/3/25People such as " Crystal growth of gallium nitride in supercritical ammonia " J.W.Kolis, J.Cryst.Growth 222,431 434 (2001) and J.W.Kolis et al., Mat.Res.Soc.Symp.Proc.Vol.495,367 372 (1998) middle descriptions.But use these overcritical ammonia process, fail to obtain the mass preparation of bulk-shaped monocrystal.

At United States Patent (USP) 6,656,615 and 7,335,262 and D ' Evelyn at United States Patent (USP) 7,078, hot crystal growing apparatus of conventional ammonia and the method for GaN has been discussed in 731 and 7,101,433.These methods can be used for less GaN crystalline growth.Unfortunately, these class methods have limitation for mass preparation.Internal diameter is the conventional equipment of 40mm can be used for growing a GaN crystal than minor diameter, but is not suitable for extensive growing GaN crystal bar (boule).In addition, may be enough with the silk seed crystal that suspends routinely that passes single laser boring for small-crystalline, but for mass preparation probably slowly and inefficiency.Also there is other limitation.

As can be seen from the above, the technology that is used for extensive crystal growth is needs highly.

Summary of the invention

According to the present invention, provide the technology relevant with the processing of the material that is used for growing crystal.More specifically, the invention provides and a kind ofly obtain to contain gallium nitride crystalline method, but other can be arranged by the ammonia alkali technology.In other embodiments, the invention provides a kind of device that is used for handling on a large scale element nitride crystal, but it should be understood that also and can handle other crystal and material.This crystalloid and material include but not limited to GaN, AlN, InN, InGaN, AlGaN and AlInGaN and are used to prepare other crystal and the material of bulk or patterned substrate.This class bulk or patterned substrate can be used for various application, comprise opto-electronic device, laser apparatus, photodiode, solar cell, water photoelectrolysis and devices such as hydrogen manufacturing, photodetector, unicircuit and transistor.

In a specific embodiment, the invention provides the method that a kind of growth contains gallium nitride crystal such as GaN.Described method comprises providing and contains the gallium source material and mineralizer is provided.In a specific embodiment, described method comprises provides at least two seed crystal plates, comprises the first seed crystal plate and the second seed crystal plate.Described method comprises that the described first seed crystal plate of support and the second seed crystal plate are in the first location and the second position of seed crystal frame.In a preferred embodiment, the described first seed crystal plate and the second seed crystal plate have the crystallographic orientation that is equal to substantially in five degree.According to a specific embodiment, all has for example at least 1 centimetre length in the first seed crystal plate and the second seed crystal plate.Described method comprises described source material, mineralizer and seed crystal plate is placed sealable container (for example autoclave, box (capsule)) and introduce nitrogen-containing solvent to described sealable container.In a specific embodiment, described method is included in the supercutical fluid in being higher than 400 degrees centigrade temperature approximately for example and being higher than pack processing under the pressure of 2 kilobars approximately for example and is contained in described source material, mineralizer and seed crystal plate in the described sealable container.Certainly, other variation, change and replacement scheme can be arranged.

In an alternate particular, the invention provides a kind of growth and contain gallium nitride crystalline method.Described method comprises providing and contains the gallium source material and mineralizer is provided.Described method also comprises provides at least the first seed crystal plate and the second seed crystal plate.In a specific embodiment, the described first seed crystal plate has first side that first crystallographic orientation is arranged and second side that second crystallographic orientation is arranged.In a specific embodiment, the described second seed crystal plate has first side that first crystallographic orientation is arranged and second side that second crystallographic orientation is arranged.In a specific embodiment, described method comprises that also supporting first side that the described first seed crystal plate and the second seed crystal plate make first seed crystal separates predetermined gap towards first side of second seed crystal and between first side of first side of first seed crystal and second seed crystal.Described method comprises described source material, mineralizer and seed crystal plate is placed sealable container.Described method is introduced nitrogen-containing solvent and be contained in described source material, mineralizer and seed crystal plate in the described sealable container in approximately for example being higher than 400 degrees centigrade temperature and being higher than pack processing under the pressure of 2 kilobars approximately for example in supercutical fluid in described sealable container.

In addition, the invention provides the method that a kind of growth contains gallium nitride crystal such as GaN.Described method comprises providing and contains the gallium source material.In a specific embodiment, described method also comprises to be provided mineralizer and provides at least the first seed crystal plate and the second seed crystal plate.In a specific embodiment, the described first seed crystal plate has first side that the first a-face crystallographic orientation is arranged and second side of the second a-face crystallographic orientation is arranged.In a specific embodiment, the described second seed crystal plate has first side that the first a-face crystallographic orientation is arranged and second side of the second a-face crystallographic orientation is arranged.In a specific embodiment, described method comprises the described first seed crystal plate of support and the second seed crystal plate.According to a specific embodiment, described first seed crystal and the second seed crystal plate all have at least 1 centimetre length.In a specific embodiment, described method comprises described source material, mineralizer and seed crystal plate is placed sealable container and introduce nitrogen-containing solvent to described sealable container.In a preferred embodiment, described method is included in the supercutical fluid in being higher than about 400 degrees centigrade temperature and being higher than pack processing under the pressure of about 2 kilobars and is contained in described source material, mineralizer and seed crystal plate in the described sealable container.Any space segment that described method makes described first side of described first side of the described first seed crystal plate or second side or the described second seed crystal plate or second side in nature from a-face feature to m-planar orientation characteristic change.Preferred described method also makes each seed crystal plate thickening by crystal growth usually.

In addition, the invention provides the method that a kind of crystalline of growing contains gallium nitride such as GaN.Described method comprises provides the high-tension unit that comprises sealable container, and described sealable container has: in a district contain gallium material and another the district at least one seed crystal.Described method also comprises to be introduced the solvent that can form supercutical fluid and pressure in a described district and another district is remained on or is higher than about seven (7) individual normal atmosphere in a described at least district and another district.Described method is handled described one or more part that contains gallium material and is comprised the supercritical solution that contains the gallium material at least under first temperature to be provided in described supercutical fluid.In a specific embodiment, described method also is included under second temperature on described seed crystal and contains the gallium nitride material by described supercritical solution growth crystalline, it is characterized in that making the described gallium material that contains to form crystalline contain the gallium nitride material on described seed crystal.

In other embodiments, the invention provides the method that a kind of crystalline of growing contains gallium nitride.Described method comprises provides autoclave, and described autoclave comprises in a district and contains gallium material and comprise at least one seed crystal in another district.Described method also comprises in a described at least district and another district introduces first solvent that can form supercutical fluid.Described method is included in the pressure that makes in the process of introducing described solvent in a described district and another district in a described district and another district and remains on or be higher than about seven (7) individual normal atmosphere.In a specific embodiment, described method is included in the described supercutical fluid to be handled described one or more part that contains gallium material and comprises the supercritical solution that contains the gallium material at least under first temperature to be provided at.In a specific embodiment, described method is in containing the gallium nitride material by described supercritical solution growth crystalline under second temperature on described seed crystal, it is characterized in that making the described gallium material that contains to form crystalline contain the gallium nitride material on described seed crystal.In a specific embodiment, described method comprise from described autoclave remove heat energy with form by described supercritical solution second solvent and by the outlet remove described second solvent from described autoclave.

In another alternate embodiment, the invention provides the method that a kind of crystalline of growing contains gallium nitride.Described method comprises provides autoclave, and described autoclave comprises in the basket structure in a district and contains gallium material, comprises at least one seed crystal in another district, and comprises the solvent that can form supercutical fluid.In a preferred embodiment, described basket structure construction is transported to described another district for one or more solid part that prevents raw material substantially from a described district.Described method also is included in the described supercutical fluid to be handled described one or more part that contains gallium material comprise the supercritical solution that contains the gallium material at least to provide under first temperature.Described method also makes flow through from the described district part of described basket of described one or more part that comprises the supercritical solution that contains the gallium material enter described another district.Described method is included under second temperature on described seed crystal and contains the gallium nitride material by described supercritical solution growth crystalline, it is characterized in that making the described gallium material that contains to form crystalline contain the gallium nitride material on described seed crystal.

In addition, the invention provides the alternative method that a kind of crystalline of growing contains gallium nitride.Described method comprises provides high-tension unit, and described high-tension unit comprises in a district and contains gallium material, comprises at least one seed crystal in another district, and comprises trinitride mineralizer and at least a metal.In one or more embodiment, described trinitride mineralizer and described metal provide nitrogen that the decomposition that makes by described trinitride mineralizer generates with predetermined ratio and are about 1: 3 by the ratio of the hydrogen of the reaction generation of described metal and supercutical fluid, but can be other.In a specific embodiment, described method is included in the described supercutical fluid to be handled described one or more part that contains gallium material comprise the supercritical solution that contains the gallium material at least to provide under first temperature.Described method is also in containing the gallium nitride material by described supercritical solution growth crystalline under second temperature on described seed crystal, it is characterized in that making the described gallium material that contains to form crystalline contain the gallium nitride material on described seed crystal.

In other embodiments, the invention provides the method that a kind of crystalline of growing contains gallium nitride.Described method comprises provides high-tension unit, described high-tension unit comprises in a district and contains gallium material, in another district, comprise at least one seed crystal, and comprise trinitride mineralizer, at least a metal and catalyzer in arbitrary or the two the vicinity in a described district and/or described another district.In a specific embodiment, described trinitride mineralizer and described metal provide nitrogen that the decomposition that makes by described trinitride mineralizer generates with predetermined ratio and are about 1: 3 and Geng Gao by the ratio of the hydrogen material of the reaction generation of described at least metal and supercritical ammine, but can be other ratios.Described method is also handled described one or more part that contains gallium material to comprise the supercritical ammine solution that contains the gallium material at least and in containing the gallium nitride material by described supercritical ammine solution growth crystalline under second temperature on described seed crystal providing under first temperature in described supercritical ammine, it is characterized in that making the described gallium material that contains to form crystalline contain the gallium nitride material on described seed crystal.Described method also comprise at least by the reaction between described metal and described supercritical ammine fluid generate the hydrogen material and at least with the described hydrogen material of described catalyst treatment so that described hydrogen material and nitrogen material are converted into described supercritical ammine fluid.

Use the present invention to obtain to be better than the benefit of prior art.Especially, the present invention can realize that the effective high-tension unit of cost is used for growing crystal such as GaN, AlN, InN, InGaN and AlInGaN etc.In a specific embodiment, method and apparatus of the present invention can move with simple relatively and the effective parts of its manufacturing cost.Depend on embodiment, apparatus and method of the present invention can be used conventional to those skilled in the art material and/or method manufacturing.According to a specific embodiment, apparatus and method of the present invention can realize under extreme pressure and the temperature condition with greater than 0.3 liter, greater than 1 liter, greater than 3 liters, greater than 10 liters, greater than 30 liters, greater than 100 liters with greater than 300 liters effective crystal growth of batch volumes cost and material processing.Depend on embodiment, can obtain in these benefits one or more.These and other benefit will be at whole specification sheets, more especially hereinafter be described.

The present invention obtains these and other benefit under the background of known process techniques.But further part and accompanying drawing in conjunction with specification sheets can further be understood character of the present invention and advantage.

Description of drawings

Fig. 1 a and 1b are the crystal growth skeleton construction according to embodiment of the present invention.

Fig. 2 a, 2b and 2c are the crystal growth seed crystal shelf structure according to embodiment of the present invention.

Fig. 3 a and 3b illustrate the sketch of the treatment process of crystal growing apparatus according to embodiments of the present invention.

Fig. 4 a, 4b and 4c illustrate the sketch of growing method according to embodiments of the present invention.

Fig. 5 is the schema sketch of explanation growing method according to an embodiment of the invention.

Fig. 6 a and 6b are the sketch that crystal growth recirculation operation according to embodiments of the present invention is described.

Embodiment

According to the present invention, provide the technology relevant with the processing of the material that is used for growing crystal.More specifically, the invention provides and a kind ofly obtain to contain gallium nitride crystalline method, but other can be arranged by ammonia alkali or propylhomoserin technology.In other embodiments, the invention provides a kind of device that is used for handling on a large scale element nitride crystal, but should be familiar with, also can handle other crystal and material.This crystalloid and material include but not limited to GaN, AlN, InN, InGaN, AlGaN and AlInGaN and are used to prepare other crystal and the material of bulk or patterned substrate.This class bulk or patterned substrate can be used for various application, comprise opto-electronic device, laser apparatus, photodiode, solar cell, water photoelectrolysis and devices such as hydrogen manufacturing, photodetector, unicircuit and transistor.

In the present invention, following definition is suitable for by one or more embodiment.This class definition is non-to be intended to restriction, and should help to read.Certainly, other variation, change and replacement scheme can be arranged.

Contain gallium nitride and refer to the gallium and the nitride of other XIII family element (according to IUPAC, 1989) randomly.It includes but not limited to binary compound GaN, ternary compound such as AlGaN, InGaN and AlInGaN, and wherein, the ratio of described other XIII family element and Ga can change in wide region.Certainly, other variation, change and replacement scheme can be arranged.

Autoclave refers to have the encloses container of reaction chamber, carries out in described reaction chamber according to ammonia alkali of the present invention or propylhomoserin method.As using routinely in this area, on ordinary meaning, airtight being interpreted as refers to seal and gastight.As using routinely in this area, on ordinary meaning, autoclave is interpreted as referring to that is to say indirect heating, makes the inner wall temperature of autoclave approximate the temperature with autoclave wall next-door neighbour's supercutical fluid.Certainly, other variation, change and replacement scheme can be arranged.

It is that about 100 degrees centigrade～about 800 degrees centigrade, pressure are the device that contains the gallium nitride growing environment of about 1 kilobar (kbar)～about 10kbar that high-tension unit refers to hold supercritical ammine and temperature.In one embodiment, high-tension unit comprises that as United States Patent (USP) 7,335 262 described autoclaves are incorporated this patent into this paper by quoting in full.In another embodiment, high-tension unit is as United States Patent (USP) 7,125,453 and U.S. Patent application 2006/0177362A1 and United States serial 12/133, inside heating high-pressure device described in 364 is incorporated these patents and patent application into this paper by quoting in full.Certainly, other variation, change and replacement scheme can be arranged.

In discussion subsequently, unit describe of the present invention is vertical.In another embodiment, in contrast, described device is horizontal, or the middle oblique angle orientation between vertical and horizontal, and can wave to promote the convection current of supercutical fluid in the high-tension unit.Method of the present invention can be used together with sealable container and high-tension unit.But the example of representational application apparatus sees and is set forth in United States Patent (USP) 7,101,433,7,125,453 and 7,160,388 and U.S. Patent application 61/073,687,12/133,365 and 12/133,364 in, incorporate all these into this paper by quoting in full.Also should be with reference to figure 5, it has listed the general step of implementing growing method according to an embodiment of the invention.As shown in the figure, Fig. 5 only is illustrative, should not limit the scope of claim herein inadequately.Those skilled in the art can expect other variation, change and replacement scheme.

The synoptic diagram that is used for seed crystal and raw-material framework has been shown among Fig. 1 a and the 1b.The appropriate structures that described framework is loaded into seed crystal and starting material before can be in placing high-tension unit to be used for crystal growth and so that the mode of subsequent operations load.Under crystal growth condition, described framework should keep favorable rigidity and to the environment of crystal growth unreactiveness, neither pollute the crystal of growth, and obvious corrosion does not take place yet.The structured material of described framework and parts thereof can comprise one or more kinds in copper, copper base alloy, gold, gold-base alloy, silver, silver-base alloy, palladium, platinum, iridium, ruthenium, rhodium, osmium, titanium, vanadium, chromium, iron, ferrous alloy, nickel, nickel-base alloy, zirconium, niobium, molybdenum, tantalum, tungsten, rhenium, silicon-dioxide, aluminum oxide, its combination etc.The ferrous alloy that can be used for forming described framework includes but not limited to stainless steel.The nickel-base alloy that can be used for forming described framework includes but not limited to Inconel(nickel alloys) (inconel), Hastelloy (hastelloy) etc.Equally, other variation, change and replacement scheme can be arranged.In some embodiments, the parts of described framework are by the alloy manufacturing that comprises at least two kinds of elements, to improve hardness and creep resistance.Described framework and parts thereof can comprise silk, Si Bu or net, paper tinsel, plate, sheet, square bar, circle bar, rectangular strip, pipe, screw rod and fastening piece.Described framework and parts thereof can fix and by fixing one of at least in fastening piece such as screw, bolt, screw rod, nut etc. by welding, electric-arc welding, resistance welding, brazing, clamping.

The frame that described framework can comprise baffle plate, starting material basket and hang the seed crystal plate is as parts and be connected at least two device in the above-mentioned parts.Being suitable in one group of embodiment of situation that crystal wherein to be grown has the solubleness that the rising with temperature increases shown in Fig. 1 a, basket is positioned at the baffle plate below, and the seed crystal chord position is in the baffle plate top.Have in another group embodiment of situation that solubleness that the rising with temperature reduces is retrograde solubility at the crystal wherein to be grown that is suitable for shown in Fig. 1 b, basket is positioned at the baffle plate top, and the seed crystal chord position is in the baffle plate below.Can be the zone that the crystal growth zone promptly contains the seed crystal frame the regional big volume that promptly contains basket than nutrition zone is provided.In a specific embodiment, the crystal growth zone is 1～5 with the volumetric ratio in nutrition zone.In another embodiment, this ratio is 1.25～3, or is 1.5～2.5.The overall diameter of framework and highly be chosen as close fitting in high-tension unit is to maximally utilise available volume and to optimize hydrokinetics.The diameter of framework can be 1 inch～2 inches, 2 inches～3 inches, 3 inches～4 inches, 4 inches～6 inches, 6 inches～8 inches, 8 inches～10 inches, 10 inches～12 inches, 12 inches～16 inches, 16 inches～24 inches or greater than 24 inches.The total height of framework and the ratio of its diameter can be 1～2,2～4,4～6,6～8,8～10,10～12,12～15,15～20 or greater than 20.

Baffle plate provides the high-tension unit that will wherein be inserted into framework to be divided into the device in two independent zones, and comprises one or more dish.Described two regional fluid communication with each other are because baffle plate has a plurality of through holes or opening.Therefore, a part of cross-sectional area of baffle plate is an opening.In a specific embodiment, the relative port area of baffle plate be about 0.5%～about 30%, but also can be other per-cent.In other embodiments, the relative port area of baffle plate is 2%～20% or 5%～15%.Baffle plate plays the effect that described at least a (or multiple) source material is limited to the specific region of chamber 108 or end and allows solvent and (under high pressure-temperature (HPHT) condition) supercutical fluid to move in whole high-tension unit by passing freely through the through hole in the baffle plate.Usually, this feature is particularly useful in using as crystal growth, therein, the described at least a material in a zone of the chamber that placement limited of supercutical fluid free baffle plate in future, nutrition materials conveyance are to another zone that crystal growth on the seed crystal wherein takes place.In a specific embodiment, the diameter of baffle plate equals the maximum diameter of whole framework.In other embodiments, the diameter of baffle plate is slightly less than the maximum diameter of whole framework, thereby is provided at can flow through its annular space of fluid under the crystal growth condition.The maximum diameter of the comparable whole framework of diameter of baffle plate is little 0.5 inch or littler.Opening in the baffle plate should be wide enough so that and not block easily.In a specific embodiment, the diameter of baffle plate split shed is 0.020 inch～0.5 inch.In another embodiment, the diameter of baffle plate split shed is 0.050 inch～0.25 inch.In a specific embodiment, it is 0.020 inch～0.5 inch dish that baffle plate comprises single thickness.In another embodiment, to comprise single thickness be 0.050 inch～0.25 inch dish to baffle plate.In some embodiments, baffle plate comprises two dishes, three dishes or more a plurality of dish.In some polydisc embodiments, one or more opening in the dish is positioned at top each other.In other polydisc embodiment, one or more opening in the dish is not positioned at top each other.Therefore effectively relatively port area in the polydisc baffle plate embodiment can be positioned between the product of relative port area of the relative port area (as the upper bound) of each dish and each dish.

The starting material basket provides easily, and device is used for shifting starting material (comprising source material and mineralizer), being used to allow zone and the interregional smooth fluid of crystal growth between the endogenous material granule of basket to be communicated with and to be used for taking the source material that does not consume away from reactor when growth process finishes to high-tension unit.In one embodiment, as schematically illustrated in the accompanying drawing, described basket comprises silk screen or silk cloth.The diameter of silk can be 0.001 inch～0.25 inch, 0.005 inch～0.125 inch or 0.010 inch～0.080 inch in net or the cloth.Silk screen or silk cloth can be contained in and comprise than in the framework of major diameter silk or be fixed in to comprise than the framework of major diameter silk and support so that improved mechanics to be provided.In another embodiment, described basket comprises paper tinsel or the plate with a plurality of through holes or opening.The size of silk screen, silk cloth or paper tinsel or plate split shed should make enough for a short time in crystal growing process in addition the starting material of signal portion be etched and/or consume by the crystal growth operation afterwards that the starting material particle can not pass through these openings.In a specific embodiment, the diameter of silk screen, silk cloth or paper tinsel or plate split shed is 0.005 inch～0.5 inch.In other embodiments, the diameter of described opening is 0.010 inch～0.125 inch, or is 0.025 inch～0.080 inch.In some embodiments, the intergranular zone of starting material and crystal growth interregional fluid are communicated with in the basket to improve by open tube that silk screen covered to have placed opening before loading starting material in described basket.The suitable configurations of this class open tube is at United States Patent (USP) 3,245, instruction arranged in 760, incorporates this patent into this paper by quoting in full.

In some embodiments, before seed crystal being placed on the seed crystal frame, source material is placed described basket, so that the minimizing possibility of latter's fragmentation.Source material can be supplied with by various forms.In some embodiments, source material comprises the piece or the grain of monocrystalline or polycrystalline material.In other embodiments, source material comprises the piece of agglomerating polycrystalline material.Under the gan situation, source material can be derived from hydride gas-phase epitaxy (HVPE) reactor and be deposited on wall or various lip-deep by product list-or many-brilliant GaN.In another specific embodiment, source material comprises by HVPE and is grown in list on the substrate-or plate of many-brilliant GaN.In another specific embodiment, source material is derived from agglomerating GaN powder, and as United States Patent (USP) 6,861,130 is disclosed, incorporates this patent into this paper by quoting in full.In another specific embodiment, source material is derived from the polycrystal GaN plate that comprises the cylindricality microstructure, and 2007/0142204A1 is disclosed as U.S. Patent application, incorporates this patent application into this paper by quoting in full.The concentration of the oxygen that source material can comprise is for being lower than 10 ¹⁹Cm ^-3, be lower than 10 ¹⁸Cm ^-3Or be lower than 10 ¹⁷Cm ^-3The concentration of the n-type doping agent (as Si or O) that source material can comprise, p-type doping agent (as Mg or Zn), counter doping agent (as Fe or Co) or magnetic-doped dose (as Fe, Ni, Co or Mn) is 10 ¹⁶Cm ^-3～10 ²¹Cm ^-3In a specific embodiment, the particle size distribution of source material is about 0.020 inch～about 5 inches.In another embodiment, the particle size distribution of source material is about 0.050 inch～about 0.5 inch.In a preferred embodiment, the total surface area of source material is at least three times of total surface area that place all seed crystal plates of seed crystal frame.

In some embodiments, source material comprises at elevated temperatures and will become melt metal such as gallium or indium.In some embodiments, mineralizer comprises at elevated temperatures and will become melt metal such as sodium, potassium or lithium.Directly contact if be placed as with the internal surface of autoclave or box, then described metal may form alloy and weaken the integrity of autoclave or box.Therefore, in some embodiments, in the starting material basket or at least one crucible placed by next-door neighbour's starting material basket and described crucible contains at least a metal.Described crucible should be chemically inert for the supercutical fluid environment of crystal growth and should be not and described at least a metal reaction or alloying.In a specific embodiment, crucible comprises molybdenum, tantalum, niobium, iridium, platinum, palladium, gold and silver or tungsten.In another specific embodiment, crucible comprises aluminum oxide, magnesium oxide, calcium oxide, zirconium white, yttrium oxide, aluminium nitride or gan.Crucible can comprise sintering or other polycrystalline material.

The seed crystal frame provides device easily to be used for the crystal that shifts seed crystal or plate, is used to allow the interregional smooth fluid of described seed crystal or plate and nutrition on the baffle plate opposite side to be communicated with and to be used for taking away from reactor growth when growth process finishes to high-tension unit.The seed crystal frame should be easy to loading and unloading, available crystal growth space is utilized effectively and makes broken and other yield losses of crystalline minimize.

In preferred embodiments, seed crystal or plate comprise gan.In other embodiments, seed crystal or plate can comprise aluminium nitride, sapphire, silicon carbide, MgAl ₂O ₄Spinel, zinc oxide etc.The seed crystal plate has at least one centimetre smallest lateral dimension.In some embodiments, the seed crystal plate has at least two centimetres maximum transverse size and at least one centimetre smallest lateral dimension.In other embodiments, the seed crystal plate has the smallest lateral dimension of at least three centimetres, at least four centimetres, at least five centimetres, at least six centimetres, at least eight centimetres or at least ten centimetres.In some embodiments, the seed crystal plate is the bulk-shaped monocrystal of gan.In some embodiments, the seed crystal plate is by the crystal preparation by hydride gas phase epitaxial growth.In other embodiments, the seed crystal plate is by the crystal preparation by ammonia thermal growth.In other embodiments, the seed crystal plate is by the crystal preparation by the solution growth in the fusing assistant.In a specific embodiment, the method preparation of seed crystal plate by disclosing in the U.S. Patent application 61/078,704 incorporated this patent application into this paper by reference.In some embodiments, the dislocation desity at the wide area surface place of seed crystal plate is lower than about 10 ⁶Cm ^-2In some embodiments, the dislocation desity at the wide area surface place of seed crystal plate is lower than about 10 ⁵Cm ^-2, be lower than about 10 ⁴Cm ^-2, be lower than about 10 ³Cm ^-2Or be lower than about 10 ²Cm ^-2In some embodiments, the halfwidth corresponding to the X-ray diffraction line of the crystallographic orientation of big area face is lower than 300 rads, is lower than 150 rads, is lower than 100 rads or be lower than 50 rads.

Gan is hexagonal wurtzite structure crystal (spacer P6 ₃Mc; Point group 6mm), has unique vitellarium.Under one group of given growth conditions ,+c direction ,-c direction, m direction, a direction and other crystallographic direction on, growth is carried out with different speed.Usually, the direction of growth is tended to self and is grown to disappearance fast, so that the crystal that is produced is mainly stopped by the facet relevant with the slow direction of growth.Modal facet is a c-face (0001) and (000-1) under the hot growth conditions of ammonia, and m-face { 1-100}.Other face, for example { { 1-10-1}, occurrence frequency is less or have a less area for 11-20} and semi-polarity face for the a-face.Production efficiency is by using at seed crystal bigger on the dimension of growing more slowly or plate and carrying out main crystal growth and improve on the faster growing direction.In preferred embodiments, the big area face of seed crystal plate is stable under previously selected growth conditions, i.e. faceting not, this by select to have (0001), (000-1), { 1-100}, { 11-20} or { the seed crystal plate of 1-10-1} orientation promotes.

In addition, the impurity of different vitellariums absorbs the tendency difference.For example, as Frayssinet and colleague at Journal of Crystal Growth, volume 230, shown in the 442-447 page or leaf (2001), the concentration of the free carrier that point defect causes the block GaN crystalline+c of involuntary doping by particular technology growth and-remarkable different in the c vitellarium.Other author has reported similar result, general trend be [000-1] or-the c vitellarium than [0001] or+higher impurity concentration is introduced in the c vitellarium.The impurity absorption difference is undesirable, and reason has two at least.The first, the existence of concentration gradient will make the crystal production merchant constant product specification that more is hard to keep in the crystal.The second, the existence of concentration gradient will produce strain (usually, the impurity among the GaN will cause the increase slightly of lattice parameter) in the crystal, and this may cause bending, breaks, dislocation formation and other disadvantageous effect.Production efficiency (comprising yield, quality product and homogeneity of product) improves in a vitellarium by main crystal growth only is limited in.

In one or more embodiment, crystal growth is wished mainly to occur on the m face.For example, under one group of predetermined growth conditions, crystal growth may take place than faster on the m direction on a direction, on the m direction than+c or-faster on the c direction.Under such one group of predetermined growth conditions, the crystal of sporadic nucleation and growth will be hexagon flap shape, have big c facet and the long side that ends at the m face, and thickness is less than diameter.Also can rely on and improve crystalline quality, reduce the impurity introducing or rely on the introducing ability that improves doping agent or band gap change agent such as Al or In to make the growth on the m direction preferential conversely.Growth on the m direction also may be an ideal for the wafer that produces the m planar orientation.The seed crystal of m planar orientation or the opposing face of plate all will constitute the m face, so the use of this class seed crystal will produce the growth in the single crystalline growth district.

In one group of embodiment, seed crystal is fixed in the seed crystal frame as schematically illustrated among Fig. 2 a and the 2b.Each seed crystal can be selected or be cut into has approximately identical height, makes and can place a plurality of seed crystals adjacent to each other in a layer of seed crystal frame.Seed crystal can have rectangle big area face.Seed crystal can place up and down and locate between the seed crystal hack lever and by clip.Because seed crystal is thicker than the spacing between the opposite side of clip when clip is in free relaxed state, so clip can clamp seed crystal by spring force.In one group of alternate embodiment, the fastening piece that seed crystal is arranged by next-door neighbour's clip, seed crystal and seed crystal frame is fixed in clip, and described fastening piece for example is the screw rod of the certain-length of two ends band nut.In another group embodiment, clip is fixed in seed crystal earlier, is fixed in the seed crystal frame then.In some embodiments, clip has opening that at least one crystal can be by its growth so that the generation of strain and defective minimizes.In another group of embodiment, the end opposite that the seed crystal frame comprises seed crystal can slip into wherein recessed, groove, depression etc.Can be in the seed crystal frame seed crystal and recessed between place paillon foil with the taking-up after making things convenient for crystal growth.In preferred embodiments, each seed crystal is fixed in the seed crystal frame at least two positions, so that the minimizing possibility of seed crystal or crystal fracture before the crystal growth, in the process or afterwards, and makes seed crystal accurately remain on desired location place in the reactor.Adjacent seed crystal or plate can be by the crystal dividing plate separately.The crystal dividing plate can have in the hole of sliding on the seed crystal hack lever, can have open with the groove that slides on the seed crystal hack lever etc. on the side.

In some embodiments, hole or groove provide in seed crystal or plate, and seed crystal or plate are hung from the seed crystal frame by at least one rhizoid or paper tinsel band.In some embodiments, seed crystal is hung by at least two rhizoids or paper tinsel band.Hole in seed crystal or the plate or groove can by laser boring or cutting, by ultrasonic punching, by mechanical punching or milling, by grind, by sand milling, by electrical spark handle, by formation such as jet of water cuttings.

In one group of embodiment, crystal growth is wished mainly to occur on a face.Growth on a direction can be the approach that preparation semi-polarity substrate orientation provides usefulness.Also can rely on and improve crystalline quality, reduce the impurity introducing or rely on the introducing ability that improves doping agent or band gap change agent such as Al or In to make the growth on a direction preferential conversely.The seed crystal of a planar orientation or the opposing face of plate all will constitute a face, so the use of this class seed crystal will produce the growth in the single crystalline growth district.

Another the group embodiment in, crystal growth is wished mainly to occur on the c face, or+c direction ([0001] Ga-polar orientation) or-c direction ([000-1] N-polar orientation).For example, under one group of predetermined growth conditions ,+c or-the c direction on crystal growth may take place than faster on the m direction.Under such one group of predetermined growth conditions, the crystal of sporadic nucleation and growth will be hexagonal prism, prism or aciculiform shape, have little c facet and the long side that ends at the m face, and length is less than diameter.Also can rely on improve crystalline quality, reduce that impurity is introduced or rely on conversely improve the introducing ability that doping agent or band gap change agent such as Al or In and make+c or-growth on the c direction is preferential.+ c or-growth on the c direction also may be an ideal for the wafer that produces the c planar orientation.The seed crystal of c planar orientation or the opposing face of plate will constitute different faces, so the independent use of this class seed crystal will produce two growths in the different crystalline growth districts.Growth in the single crystalline growth district can be by back-to-back piling up the c planar orientation seed crystal or plate to similar face is obtained toward each other.For example, can make the seed crystal of two c planar orientations or plate-the c face is close to toward each other, make the seed crystal of two c planar orientations or plate+the c face towards outside and produce growth on the single crystallographic orientation.Conversely, can make the seed crystal of two c planar orientations or plate+the c face is close to toward each other, make the seed crystal of two c planar orientations or plate-the c face towards outside and produce growth on the single crystallographic orientation.Can being in direct contact with one another or can be separately with seed crystal by the crystal dividing plate to being placed as.If seed crystal or plate to growth together in growth process, then if desired, can behind this processing procedure, it be separated, maybe can allow it keep together and as seed (two) crystalline substance in the successive process.On it big area face all constitute+c or-the c planar orientation twin crystal on c surface is suitable for use as seed crystal, because the growth on the big area face will occur over just on the single crystallographic direction.May there be at least one orientation contact twin or the stacking fault substantially parallel in the described twin crystal with wide area surface.

In another group embodiment, crystal growth wishes mainly to occur in semi-polarity { on the 1-10-1} face.Can rely on and improve crystalline quality, reduce the impurity introducing or rely on the introducing ability that improves doping agent or band gap change agent such as Al or In to make the growth on this semi-polarity direction preferential conversely.Perpendicular to { { for the wafer of 1-10-1}-orientation also may be ideal for producing in the growth of 1-10-1} face.{ seed crystal of 1-10-1}-orientation or the opposing face of plate will constitute different faces, so the independent use of this class seed crystal will produce two growths in the different crystalline growth districts.Growth in the single crystalline growth district can by back-to-back pile up the seed crystal of 1-10-1}-orientation or plate { face of 1-101}-orientation obtains toward each other to making.Can being in direct contact with one another or can be separately with seed crystal by the crystal dividing plate to being placed as.If seed crystal or plate to growth together in growth process, then if desired, can behind this processing procedure, it be separated, maybe can allow it keep together and as seed (two) crystalline substance in the successive process.On it big area face all constitute the 1-10-1} surface { 1-10-1}-orientation twin crystal is suitable for use as seed crystal, because the growth on the big area face will occur over just on the single crystallographic direction.May there be at least one orientation contact twin substantially parallel in the described twin crystal with wide area surface.

More generally, crystal growth may be wished mainly to occur on semi-polarity (the h k i l) face, i=-(h+k) wherein, l non-zero, and at least one non-zero among h and the k.Can rely on and improve crystalline quality, reduce the impurity introducing or rely on the introducing ability that improves doping agent or band gap change agent such as Al or In to make the growth on this semi-polarity direction preferential conversely.{ seed crystal of h k i l}-orientation or the opposing face of plate will constitute different faces, so the independent use of this class seed crystal will produce two growths in the different crystalline growth districts.Growth in the single crystalline growth district can by back-to-back pile up the seed crystal of h k i l}-orientation or plate to make the face of h k i l}-orientation toward each other thus two seed crystals or plate (face of h k i-l) towards outside the growth that produces on the single crystallographic orientation obtain.Can being in direct contact with one another or can be separately with seed crystal by the crystal dividing plate to being placed as.If seed crystal or plate to growth together in growth process, then if desired, can behind this processing procedure, it be separated, maybe can allow it keep together and as seed (two) crystalline substance in the successive process.The semi-polarity twin crystal that big area face all constitutes same semi-polarity orientation on it is suitable for use as seed crystal, because the growth on the big area face will occur over just on the single crystallographic direction.

In some embodiments, seed crystal or plate have rectangle or basic orthogonal shape.For m-face or a-face seed crystal plate, basic orthogonal shape may be suitable especially.In some embodiments, the corner of seed crystal or plate by sphering or chamfering so that broken minimizing possibility.The interior space of high-pressure crystal growing reactor is convenient to assemble and is convenient to effectively utilize to rectangular shape.In other embodiments, seed crystal or plate have hexagon or roughly hexagonal shape.When seed crystal that uses the c-planar orientation or plate, the hexagon shape may be convenient especially.In other embodiments, seed crystal or plate have circle, avette or circular or avette shape.

In some embodiments, the close-packed mode that those of non-rectangle seed crystal or plate particularly, seed crystal can non-rectangles is arranged, as shown in Fig. 2 c.The seed crystal frame can comprise honeycomb type to be arranged, the perforate of hexagon, circle, rectangle or other shape is arranged with the pattern of rule, rather than comprised the linear array of a plurality of layers the bar that is arranged to vertical stacking.Honeycomb structure can be formed by line discharge process, jet of water cutting, milling, punching etc. by thin slice.Perhaps, honeycomb structure can be by the crooked accurate horizontal bar manufacturing with vertical enhancing structure.

In some embodiments, particularly relate to and use autoclave as those of high-tension unit, framework also comprises one group of dish that piles up or baffle plate on the top of framework.Described dish that piles up or baffle plate will reduce in the crystal growing process transmission of heat by convection of upper end from the supercutical fluid to the autoclave, make the sealing of autoclave can be in than under the low temperature of the inner upper end of autoclave.In other embodiments, after framework being inserted in the high-tension unit, on frame roof, place one or more dish or baffle plate.

After framework loads seed crystal and starting material, framework is placed in the sealable container.Described sealable container can constitute and is designed for autoclave or the box that the high-tension unit with inside heating uses.Can add at least a mineralizer.Mineralizer can comprise hydride, acid amides, imide, amide-imide, nitride or the trinitride of basic metal (as Li, Na, K, Rb or Cs), alkaline-earth metal (as Mg, Ca, Sr or Ba) or basic metal or alkaline-earth metal.Mineralizer can comprise ammonium halide (as NH ₄F, NH ₄Cl, NH ₄Br or NH ₄I), gallium halide is (as GaF ₃, GaCl ₃, GaBr ₃, GaI ₃) maybe can pass through HF, HCl, HBr, HI, Ga and NH ₃In any compound of forming of the reaction of one or more kinds.Mineralizer can comprise other basic metal, alkaline-earth metal or ammonium salt, other halogenide, urea, sulphur or sulphide salt or phosphorus or phosphorated salt.Mineralizer can metal, loose powder, grain or at least a DB or ball provide.Mineralizer can be added in the starting material basket, can place crucible or can directly place high-tension unit or box.In a preferred embodiment, mineralizer (for example in glove box) under the situation that is not exposed to air is added in high-tension unit or the box.

Also can in reaction mixture, add getter.Getter reacts with the remaining or external oxygen or the moisture that exist preferential, thereby improves the GaN crystalline purity and the transparency that generates.Getter can comprise in alkaline-earth metal, Sc, Ti, V, Cr, Y, Zr, Nb, Hf, Ta, W, rare earth metal and nitride thereof, acid amides, imide, amide-imide or the halogenide one of at least.

In some embodiments, will place one of at least in the starting material basket or the crucible of next-door neighbour's starting material basket in mineralizer and the getter.

For starting material, mineralizer and/or getter, in some aspects, using metal precursor is easily.For example, metal can high purity obtain and need not further to synthesize usually from the market.But except that suitably being supported under the reaction conditions the complicacy with melt metal (as Ga, Na, K), the use of pure metal may produce undesirable gas such as hydrogen.For instance, under the ammonia thermal rection condition, below listed metal one or more will take place will plant following reaction:

Ga+NH ₃＝GaN+3/2H ₂

Na+NH ₃＝NaNH ₂+1/2H ₂

K+NH ₃＝KNH ₂+1/2H ₂

Mg+2NH ₃＝Mg(NH ₂) ₂+H ₂

3Mg+2NH ₃＝Mg ₃N ₂+3H ₂

Y+3NH ₃＝Y(NH ₂) ₃+3/2H ₂

Y+NH ₃＝YN+3/2H ₂

The existence of hydrogen can reduce and contains the gallium solubility of substances in the supercritical fluid solvent, in addition, the metal that constitutes autoclave wall is become fragile.

Using trinitride is easily as mineralizer, and this is because it often can high purity obtains from the market, can be further purified and water absorbability is significantly less than for example basic metal or acid amides or alkaline-earth nitride. At United States Patent (USP) 7,364, the use of trinitride mineralizer has been proposed in 619, incorporate this patent into this paper by quoting in full.But trinitride can decompose usually under reaction conditions, produces undesirable gas such as nitrogen:

3NaN ₃+2NH ₃＝3NaNH ₂+4N ₂

In a preferred embodiment, these two kinds of effects have been made up to repeal by implication.Metal (comprising starting material, mineralizer and getter) is added so that H with trinitride mineralizer precursor ₂And N ₂Generate with about 3: 1 ratio.Reaction vessel also comprises by H ₂And N ₂Catalysis forms NH ₃Device.In the reaction of metal and ammonia, reach the H that discharges in the decomposition of trinitride respectively ₂And N ₂Between form the reaction of ammonia again catalysis can carry out by autoclave wall or by extra catalyst.Extra catalyst can comprise powder, grain, paper tinsel, coating, bulk material or porous spherolite.Extra catalyst can comprise in iron, cobalt, nickel, titanium, molybdenum, tungsten, aluminium, potassium, caesium, calcium, magnesium, barium, zirconium, osmium, uranium or lanthanon, ruthenium, platinum, palladium or the rhodium one of at least.For example, add 1 mole of NaN ₃To produce 4/3 mole of N ₂The latter also can offset by adding 8/3 mole of Ga metal, and this will produce 8/3 * 3/2 mole=4 moles H ₂, promptly be three times in from NaN ₃N ₂Mole number.

Close described sealable container and sealing then, except that with being connected of gas, liquid or vacuum manifold.In one embodiment, described sealable container comprises that as United States Patent (USP) 7,335 262 described autoclaves are incorporated this patent into this paper by quoting in full.In another embodiment, described sealable container comprises as United States Patent (USP) 7,125,453 metal tins of being discussed, the container of being discussed as U.S. Patent application 2007/0234946 or as name be called the U.S. Patent application 12/133 of " Improved capsule for high pressure processing and method of use for supercritical fluids ", 365 boxes of being discussed are incorporated all these patents and patent application into this paper by quoting in full.The internal diameter of autoclave or box can be 1 inch～2 inches, 2 inches～3 inches, 3 inches～4 inches, 4 inches～6 inches, 6 inches～8 inches, 8 inches～10 inches, 10 inches～12 inches, 12 inches～16 inches, 16 inches～24 inches or greater than 24 inches.Gap between the internal diameter of autoclave or box and the external diameter of framework can be 0.005 inch～1 inch or 0.010 inch～0.25 inch.The interior height of autoclave or box and the ratio of its internal diameter can be 1～2,2～4,4～6,6～8,8～10,10～12,12～15,15～20 or be higher than 20.

In some embodiments, autoclave or box are evacuated to remove air, moisture and other volatile contaminant.In some embodiments, high-tension unit or box are heated to about 25 degrees centigrade～about 500 degrees centigrade temperature in evacuation process.In some embodiments, autoclave or box heat with same heating unit used in the autoclaving process.In a specific embodiment, box is by also using the latter's heater heats in the pressure assembly that places inner heating.

In another group embodiment, the autoclave or the box that contain the framework of having filled are purged to remove air, moisture and other volatile contaminant, as shown in Fig. 3 a and 3b.Because the conduit by linking autoclave or box inside or the conduction of deep hole are limited, so the removing of air, moisture and other volatile contaminant that purging provides than the excellence of finding time.Connect autoclave or box and source of the gas by at least one filling tube or scavenging duct then,, preferably do not make the content of box be exposed to air according to a specific embodiment.Described source of the gas can comprise in nitrogen, argon gas, hydrogen, helium and the solvent vapour etc. one of at least.In one embodiment, source of the gas and/or venting port have connected first can or scavenging duct and second can or scavenging duct.In another embodiment, arranged in can or the outer scavenging duct interior scavenging duct and described in scavenging duct orientate the bottom that makes end next-door neighbour autoclave or box as.Interior scavenging duct and outer scavenging duct can be by one of at least manufacturings in copper, copper base alloy, gold, gold-base alloy, silver, silver-base alloy, palladium, platinum, iridium, ruthenium, rhodium, osmium, iron, ferrous alloy, nickel, nickel-base alloy, molybdenum and the combination thereof.The ferrous alloy of scavenging duct or outer scavenging duct includes but not limited to stainless steel in can be used to form.The nickel-base alloy of scavenging duct or outer scavenging duct includes but not limited to Inconel(nickel alloys), Hastelloy etc. in can be used to form.As shown, the internal diameter of comparable can of the external diameter of interior scavenging duct or outer scavenging duct is little at least 0.010 inch.According to a specific embodiment, scavenging duct and can or outer scavenging duct in can connecting by threeway or other suitable technique, make and leave near the bottom of autoclave or box by the sweep gas of interior scavenging duct introducing, length through autoclave or box, discharge by interior scavenging duct and outer can or the annular space in the outer scavenging duct of threeway then, thereby effectively removing of vapor phase contaminants is provided.Interface between threeway and interior scavenging duct can be slipper seal, and for example the classification of O-shape ring or Teflon sealing or O-shape ring vacuumizes group.The flow of sweep gas can be 0.05～10 standard Liter Per Minute.In the purge operations process, autoclave or box can be heated to for example 25 degrees centigrade～500 degrees centigrade temperature more effectively to remove water and other adsorbed contaminants.After cutting off gaseous purge stream, can allow solvent vapour for example vapor phase ammonia flow through autoclave or box to remove great majority or whole sweep gas.

In a specific embodiment, for example second filling tube or scavenging duct are connected with the source of liquid solvent with air flow inlet then.Autoclave or box and filling tube can be cooled, and perhaps liquid solvent delivery system and transfer line can be heated, make the former than the latter cold 1～50 degree centigrade.In autoclave or box, introduce liquid solvent with the flow of per minute 0.1～1000 gram then.The vapour pressure of ammonia is about 10 normal atmosphere under the room temperature.The temperature that depends on solvent source, therefore, the pressure of system can be higher than 7 normal atmosphere, is higher than 8 normal atmosphere, is higher than 9 normal atmosphere or is higher than 10 normal atmosphere in the solvent delivery process.In one embodiment, in the fill operations process, purge venting port and close, the solvent vapour of liquid top is forced to be condensed into liquid.In this embodiment, autoclave or box can be through initiatively cooling off to disperse the heat that condensation was discharged of solvent vapour.In another embodiment, purge venting port assembled vacuum breaker make when pressure during above predetermined threshold sweep gas or the solvent vapour of remnants can leave, but air or other gas can not flow back in the autoclave.The amount of solvent can use the liquid conveying system of the ability with accurate monitoring amount of liquid of carrying to determine in autoclave or the box.An example of the suitable device of the high purity liquid ammonia of conveying accurate measurement is iCon Dynamics, the InScale that LLC makes ^TMSystem.In some embodiments, the amount that is transported to the ammonia of autoclave or box is determined by the weight minimizing of at least one ammonia supply tube.If in the filling liquid process, allow the solvent gas discharging, be under the situation of described solvent then at ammonia, the amount of the solvent of discharging can be determined by the change that is captured in it in aqueous solution and measure pH, deduct the amount that this amount can be determined liquid in autoclave or the box from total amount of liquid of conveying.Be different from solvent under the situation of ammonia, can adopt similar method to determine the amount of the solvent of discharge.

In an alternate embodiment, solvent under high pressure is transported to autoclave or box with the steam form.For example second filling tube or scavenging duct are connected with the source of vapor phase solvent with air flow inlet then.Autoclave or box and filling tube can be cooled, and perhaps solvent delivery system and transfer line can be heated, make the former than the latter cold 1～50 degree centigrade.In autoclave or box, introduce vapor phase solvent with the flow of per minute 0.1～1000 gram then and be allowed to condition at autoclave or box in condensation.The pressure of solvent vapour should be higher than the equilibrium vapor pressure under the temperature of autoclave or box.The temperature that depends on autoclave or box and solvent delivery system, the pressure in the solvent delivery process can be higher than 7 normal atmosphere, are higher than 8 normal atmosphere, are higher than 9 normal atmosphere or are higher than 10 normal atmosphere.In one embodiment, in the fill operations process, purge venting port and close, the solvent vapour of liquid top is forced to be condensed into liquid.In this embodiment, autoclave or box can be through initiatively cooling off so that the heat that condensation was discharged of solvent vapour is distributed.In another embodiment, purge venting port assembled vacuum breaker make when pressure during above predetermined threshold sweep gas or the solvent vapour of remnants can leave, but air or other gas can not flow back in the autoclave.The amount of solvent can use the vapor delivery system of having assembled under meter to determine in autoclave or the box.In some embodiments, the amount that is transported to the ammonia of autoclave or box is determined by the weight minimizing of at least one ammonia supply tube.If in the filling liquid process, allow the solvent gas discharging, be under the situation of described solvent then at ammonia, the amount of the solvent of discharging can be determined by the change that is captured in it in aqueous solution and measure pH, deduct the amount that this amount can be determined liquid in the box from total amount of liquid of conveying.Be different from solvent under the situation of ammonia, can adopt similar method to determine the amount of the solvent of discharge.

Behind can autoclave or box, removable interior scavenging duct (if present).In some embodiments, interior scavenging duct after purge step but can step reach remove.The filling tube of the gate valve of sealing autoclave or box then.After the sealing, the inside of autoclave or box will be airfree substantially, and wherein contained described at least a material can be handled under the Pollution risk that reduces.Certainly, other variation, change and replacement scheme can be arranged.

In some embodiments, autoclave is heated to crystal growth condition then.In other embodiments, box is placed in autoclave, the inner pressure assembly that heats or other high-tension unit and is heated to crystal growth condition.In some embodiments, thermal cycling comprises that the pre-reaction section contains gallium complex etc. with formation mineralizer, polycrystalline gan, dissolved.In some embodiments, the atmosphere in the autoclave can change in processing procedure.For example, the excessive H that forms by the reaction of gallium metal and ammonia ₂Can release by gate valve maybe to allow it diffuse through the palladium film of heating.The excessive nitrogen that is decomposed to form by the trinitride mineralizer can be released by gate valve.Can add other ammonia and replenish solvent in the high-tension unit.

The suitable thermal cycling of crystal growth is at United States Patent (USP) 6,656, discussion arranged in 615 and 7,078,731, incorporates these patents into this paper by quoting in full.Described crystal is mainly perpendicular to the major diameter length of looking unfamiliar, but also growth can be arranged slightly in the horizontal.For the back-to-back c-face that piles up or { 1-10 ± 1} seed crystal may make an exception, and prevents that by the crystal dividing plate crystal growth from advancing each other.

After the preset time section is carried out in crystal growth, cooling autoclave or high-tension unit.Be lower than 100 degrees centigrade when autoclave or box are cooled to, be lower than 75 degrees centigrade, be lower than 50 degrees centigrade or when being lower than 35 degrees centigrade, open the valve of autoclave or ventilate, and remove ammonia to box.In one embodiment, allow vapor phase ammonia leave autoclave or box and the feasible chemistry capture of bubbling in acidic aqueous solution.In another embodiment, allow vapor phase ammonia form H with burning ammonia through flame ₂O and N ₂In a preferred embodiment, shown in Fig. 6 a and 6b, ammonia is captured and is used for recirculation and re-uses.

Referring to Fig. 6 a (being suitable for single-ended autoclave or box), ammonia can liquid or gas form remove.To remove ammonia with liquid form, interior scavenging duct (referring to Fig. 3 a, 3b) should be inserted again outer purge or filling tube in and the outlet of interior scavenging duct is connected to reception/purification pot.Make sweep gas exhaust joint (referring to Fig. 3 a and 3b) keep closing, open the valve of scavenging duct in leading to, with allow liquefied ammonia in autoclave, flow through in scavenging duct and entering in reception/purification pot, otherwise reception/purification pot cuts out.In ammonia jump operation process, but can make and compare, keep higher ammonia vapour pressure in the autoclave for example by cold water cooling reception/purification pot and/or heating high-pressure still or box and transfer line with the vapour pressure in the reception/purification pot.The temperature difference between autoclave or box and the reception/purification pot can remain on 1～50 degree centigrade.In another embodiment, ammonia removes with the steam form.The outlet of autoclave or box is connected to the condenser of reception/purification pot top and opens valve.Vapor phase ammonia enters condenser and be condensed into liquid under the pressure of about 100～250 pound per square inches in interchanger such as water-cooled coil pipe.Autoclave and transfer line can be heated to the temperature higher 1～50 degree centigrade than condenser.Remaining gas is N for example ₂And H ₂Can be by being discharged into scrubber and/or flame discharges.

Referring to Fig. 6 b (being suitable for both-end autoclave or box), ammonia can remove by liquid form.Filling tube on port on the autoclave bottom or the box bottom is linked to each other with reception/purification pot and open valve, liquefied ammonia is flow in reception/purification pot, otherwise reception/purification pot cuts out.In ammonia jump operation process, but can make and compare, keep higher ammonia vapour pressure in the autoclave for example by cold water cooling reception/purification pot and/or heating high-pressure still and transfer line with the vapour pressure in the reception/purification pot.The temperature difference between autoclave and the reception/purification pot can remain 1～50 degree centigrade.

For recirculation, can in reception/purification pot, arrange scavenging agent, for example the sodium metal.Sodium will react with oxygen and/or the water of remnants in the ammonia, thereby recovers very high purity.After one hour to 30 days time, ammonia can be transferred to transfer pot.In a preferred embodiment, described transfer is carried out via condenser by gas phase, makes scavenging agent stay in reception/purification pot.Liquefied ammonia can be transported to autoclave via dip-tube from transfer pot and be used for next crystal growth processing procedure.In an alternate embodiment, vapor phase ammonia can be transported to autoclave or box is used for next crystal growth processing procedure from transfer pot.

Cooling, remove ammonia and open autoclave or inner heating high-pressure device and box after, from autoclave or box, take out framework and take off the crystal of growth from the seed crystal frame.If desired, can by in suitable sour example hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid one of at least in the part of crystalline material that has been etched with the hypertrophy that removes clip.

Crystal is cut into previously selected orientation, as gathering among Fig. 4 a, 4b and the 4c.In one embodiment, seed crystal has the m-planar orientation, is cut into the wafer of m-planar orientation, as shown in Fig. 4 a.In another embodiment, seed crystal is+c or-c orientation (or being aforesaid twin crystal), be cut into the wafer of c-planar orientation, as shown in Fig. 4 b.In another embodiment, seed crystal is that { the 1-10-1} orientation is cut into the { wafer of 1-10 ± 1}-orientation.In another embodiment, seed crystal is the m-planar orientation, is cutting into slices with respect to the angle place of about 28 degree of big area m face with preparation { the semi-polarity wafer of 1-10 ± 1} orientation.In another embodiment, seed crystal is that { the 1-10-1} orientation is being cut into slices with respect to the angle place of about 18.8 degree of big area face with preparation { the semi-polarity wafer of 1-10 ± 2} orientation.In another embodiment, seed crystal is that { the 1-10-1} orientation is being cut into slices with respect to the angle place of about 29.9 degree of big area face with preparation { the semi-polarity wafer of 1-10 ± 3} orientation.In another embodiment, seed crystal is that { the 1-10-1} orientation is being cut into slices with respect to the angle place of about 26.2 degree of big area face with preparation { the semi-polarity wafer of 11-2 ± 2} orientation.In another embodiment, seed crystal is the c-planar orientation, is cutting into slices with respect to the angle place of about 32 degree of big area c face with preparation { the semi-polarity wafer of 1-10 ± 3} orientation.In another embodiment, seed crystal is the m-planar orientation, is cutting into slices with respect to the angle place of about 42.5 degree of big area m face with preparation { the semi-polarity wafer of 11-2 ± 2} orientation.In yet another embodiment, seed crystal is the c-planar orientation, is cutting into slices with respect to the angle place of about 43.2 degree of big area c face with preparation { the semi-polarity wafer of 1-10 ± 2} orientation.In yet another embodiment, seed crystal is the c-planar orientation, is cutting into slices with respect to the angle place of about 62.0 degree of big area c face with preparation { the semi-polarity wafer of 1-10 ± 1} orientation.In an embodiment again, seed crystal is the c-planar orientation, with respect to the angle place section of about 58.4 degree of big area c face with preparation { the semi-polarity wafer of 11-2 ± 2} orientation.In another embodiment, seed crystal is the c-planar orientation, is cutting into slices with preparation { the nonpolar wafer of 1-100} orientation with respect to the angle place of about 90.0 degree of big area c face.In another embodiment, seed crystal is the c-planar orientation, is cutting into slices with preparation { the nonpolar wafer of 11-20} orientation with respect to the angle place of about 90.0 degree of big area c face.

In other embodiments, seed crystal has crystallographic orientation and makes at least one big to be the face of faster growing.In a specific embodiment, seed crystal has the a-planar orientation.In other embodiments, seed crystal has the semi-polarity orientation.In specific embodiment, seed crystal be oriented to { 1-10 ± 1}, { 1-10 ± 2}, { 1-10 ± 3} or { 11-2 ± 2}.In some embodiments, the opposing face of the back-to-back seed crystal that makes that this is assembled together of putting together of two seed crystals has the crystallographic orientation that is equal to.Fast the use of growth orientation can realize totally throughput rate faster of high-quality crystal.In a specific embodiment, as shown in Fig. 4 c, seed crystal is the a-planar orientation.Originally grow fast on a direction along with crystalline upper limb and lower edge form the m-face and slow down.When the crystal growth end cycle, crystal is stopped by four big area m face facets, shown in the edge section among Fig. 4 c.From how much, m-face facet be initial a-face seed crystal plate length about 58%.Can be at a certain angle with this crystal cut to produce a plurality of m-faceted crystals.In other embodiments, at other angle place with this crystal cut to produce c-face wafer, a-face wafer or semi-polarity wafer.Described semi-polarity wafer can have { 1-10 ± 1} orientation, { 1-10 ± 2} orientation, { 1-10 ± 3} orientation, { 20-2 ± 1} orientation, { 11-2 ± 2} orientation, or more generally, (h k i l) orientation, wherein i=-(h+k), l non-zero, and at least one non-zero among h and the k.

After the section, can be by method well known in the art with wafer grinding, polishing and chemical-mechanical polishing.

Described wafer can be used as substrate to manufacture photoelectron or electron device, for example in photodiode, laser diode, photodetector, avalanche photodide, transistor, rectifier and the thyristor one of at least; Transistor, rectifier, Schottky rectifier, thyristor, the p-i-n diode, the metal-semiconductor-metal diode, High Electron Mobility Transistor, metal-semiconductor field effect transistor, MOS (metal-oxide-semiconductor) memory, power metal oxide semiconductor field-effect transistor, the power metal insulator semiconductor field effect transistor, bipolar junction transistor, the metal insulator field-effect transistor, heterojunction bipolar transistor, the power insulated gate bipolar transistor, power vertical junction field-effect transistor, cascaded switch, interior sub-band projector, the quantum well infrared light detector, the quantum dot infrared light detector, solar cell and be used for diode a kind of of water photoelectrolysis and hydrogen manufacturing.

In a specific embodiment, any in the above-mentioned steps sequence provides the method according to one embodiment of the invention.In a specific embodiment, the gained crystalline material that the invention provides a kind of method and provide by pressure assembly with basket structure.Also can provide wherein increases step, removes other replacement scheme that one or more step or one or more step provide with different orders and do not depart from the scope of claim herein.

Though above completely described specific embodiment, can use various changes, alternative constructions and Equivalent.Therefore, top description and explanation should not be considered as limiting the scope of the invention, and scope of the present invention is limited by subsidiary claims.

Claims (50)

1. a growth contains gallium nitride crystalline method, and described method comprises:

Provide and contain the gallium source material;

Mineralizer is provided;

At least two seed crystal plates are provided, comprise the first seed crystal plate and the second seed crystal plate;

Support described first seed crystal plate and the described second seed crystal plate in the first location and the second position of seed crystal frame, described first seed crystal plate and the described second seed crystal plate have the crystallographic orientation that is equal to substantially in five degree, and described first seed crystal plate and the described second seed crystal plate all have length;

Described source material, mineralizer and seed crystal plate are placed sealable container;

In described sealable container, introduce nitrogen-containing solvent; With

Pack processing is contained in described source material, mineralizer and seed crystal plate in the described sealable container in supercutical fluid under certain temperature and pressure.

2. the process of claim 1 wherein that described first seed crystal plate and the described second seed crystal plate all comprise first side and second side, described first side and described second side have the crystallographic orientation that is equal to substantially in five degree; Wherein said first seed crystal plate and the described second seed crystal plate all have at least 1 centimetre length; And wherein said temperature is higher than about 400 degrees centigrade, pressure and is higher than about 2 kilobars.

3. the process of claim 1 wherein that described first seed crystal plate or the described second seed crystal plate are characterised in that to have at least two centimetres maximum transverse size and at least one centimetre smallest lateral dimension; Wherein said sealable container is autoclave or box.

4. the method for claim 1 also comprises at least 1 millimeter of the thickness increase that makes at least one described seed crystal plate.

5. the method for claim 4, wherein the thickness increase of at least one described seed crystal plate is at least 2 millimeters.

6. the process of claim 1 wherein that at least one surface of at least one described seed crystal plate has { the crystallographic orientation in five degree of 1-100}m-face.

7. the method for claim 6, wherein said seed crystal plate has basic orthogonal shape.

8. the process of claim 1 wherein that at least one surface of at least one described seed crystal plate has { the crystallographic orientation in five degree of 1-10 ± 1} semi-polarity face.

9. the method for claim 8, wherein said seed crystal plate has basic orthogonal shape.

10. the process of claim 1 wherein that the wide area surface of described seed crystal plate has the interior crystallographic orientation of five degree of (0001) Ga-polarity c-face.

11. the process of claim 1 wherein that the wide area surface of described seed crystal plate has the interior crystallographic orientation of five degree of (000-1) N-polarity c-face.

12. the method for claim 1, also comprise the crystal bar section that will derive from described first seed crystal plate or the described second seed crystal plate with in preparation m-face, a-face, c-face or the semi-polarity substrate one of at least.

13. a growth contains gallium nitride crystalline method, comprising:

Provide and contain the gallium source material;

Mineralizer is provided;

At least the first seed crystal plate and the second seed crystal plate are provided, the described first seed crystal plate has first side that first crystallographic orientation is arranged and second side that second crystallographic orientation is arranged, the described second seed crystal plate has first side that first crystallographic orientation is arranged and second side that second crystallographic orientation is arranged, and second side of second side of the described first seed crystal plate and the described second seed crystal plate has being equal to crystallographic orientation and having at least 1 centimetre smallest lateral dimension in five degree;

Support first side that described first seed crystal plate and the described second seed crystal plate make described first seed crystal and separate predetermined gap towards first side of described second seed crystal and between first side of first side of described first seed crystal and described second seed crystal;

Described source material, mineralizer and described seed crystal plate are placed sealable container;

In described sealable container, introduce nitrogen-containing solvent; With

Be contained in described source material, mineralizer and seed crystal plate in the described sealable container being higher than about 400 degrees centigrade temperature and being higher than under the pressure of about 2 kilobars in supercutical fluid pack processing.

14. the method for claim 13, wherein described first side separately or described second side of the first seed crystal plate or the second seed crystal plate have at least two centimetres maximum transverse size and at least one centimetre smallest lateral dimension.

15. the method for claim 13, also comprise first thickness that makes the described first seed crystal plate and the second seed crystal plate second thickness each increase at least 1 millimeter.

16. the method for claim 13, also comprise first thickness that makes the described first seed crystal plate and the second seed crystal plate second thickness each increase at least 2 millimeters.

17. the method for claim 13, wherein each described second side outward has the interior crystallographic orientation of five degree of (0001) Ga-polarity c-face.

18. the method for claim 13, wherein each described second side outward has the interior crystallographic orientation of five degree of (000-1) N-polarity c-face.

19. the method for claim 13, wherein each described second side outward has the interior crystallographic orientation of five degree of (1-10-1) semi-polarity face.

20. the method for claim 13, also comprise the crystal bar section that will derive from described first seed crystal plate or the described second seed crystal plate with in preparation m-face, a-face, c-face or the semi-polarity substrate one of at least.

21. a method of using one or more seed crystal frame growth crystalline to contain gallium nitride, described method comprises:

The high-tension unit that comprises sealable container is provided, and described sealable container has: the seed crystal rack device, in a district contain gallium material, another the district in described seed crystal rack device at least one seed crystal;

In a described at least district and described another district, introduce the solvent that can form supercutical fluid;

In described supercutical fluid, handle described one or more part of gallium material that contains to be provided at the supercritical solution that contains the gallium material at least that comprises under first temperature; With

Containing the gallium nitride material by described supercritical solution growth crystalline under second temperature on described seed crystal, described second temperature is characterised in that and makes the described gallium material that contains form described crystalline contain the gallium nitride material on described seed crystal.

22. the method for claim 21, wherein said seed crystal frame comprise in copper, copper base alloy, gold, gold-base alloy, silver, silver-base alloy, palladium, platinum, iridium, ruthenium, rhodium, osmium, titanium, vanadium, chromium, iron, ferrous alloy, nickel, nickel-base alloy, zirconium, niobium, molybdenum, tantalum, tungsten, rhenium, silicon-dioxide, aluminum oxide and the combination thereof etc. one of at least.

23. the internal diameter of the described sealable container in the method for claim 21, wherein said high-tension unit is greater than 75mm.

24. the crystalline of growing contains the method for gallium nitride, described method comprises:

The high-tension unit that comprises sealable container is provided, and described sealable container has: in a district contain gallium material, another the district at least one seed crystal;

In a described at least district and described another district, introduce the solvent that can form supercutical fluid;

Pressure in a described district and described another district is remained on or be higher than about seven (7) individual normal atmosphere;

In described supercutical fluid, handle described one or more part of gallium material that contains to be provided at the supercritical solution that contains the gallium material at least that comprises under first temperature; With

Containing the gallium nitride material by described supercritical solution growth crystalline under second temperature on described seed crystal, described second temperature is characterised in that and makes the described gallium material that contains form described crystalline contain the gallium nitride material on described seed crystal.

25. the method for claim 24, being introduced in when described solvent is liquid form substantially of wherein said solvent carried out.

26. the method for claim 24 also is included in and introduces the described sealable container of the preceding purging of described solvent.

27. the method for claim 24, the internal diameter of wherein said sealable container is greater than 75mm.

28. the crystalline of growing contains the method for gallium nitride, described method comprises:

Autoclave is provided, and described autoclave comprises in a district and contains gallium material and comprise at least one seed crystal in another district;

In a described at least district and described another district, introduce first solvent that can form supercutical fluid;

Pressure in a described district and described another district is remained on or be higher than about seven (7) individual normal atmosphere;

In described supercutical fluid, handle described one or more part of gallium material that contains to be provided at the supercritical solution that contains the gallium material at least that comprises under first temperature;

Containing the gallium nitride material by described supercritical solution growth crystalline under second temperature on described seed crystal, described second temperature is characterised in that and makes the described gallium material that contains form described crystalline contain the gallium nitride material on described seed crystal;

Remove heat energy to form second solvent from described autoclave by described supercritical solution; With

Remove described second solvent by outlet from described autoclave.

29. the method for claim 28 also comprises described second solvent is transferred to scavenging process from described outlet.

30. the method for claim 28 also comprises described second solvent is transferred to scavenging process with described second solvent of recirculation from described outlet.

31. the method for claim 28 also comprises described second solvent is transferred to scavenging process with described second solvent of recirculation from described outlet; In described scavenging process, purify described second solvent to form the 3rd solvent; With described the 3rd solvent is transferred to described autoclave.

32. the method for claim 31, wherein said the 3rd solvent and described first solvent are basic identical.

33. the method for claim 28, wherein said second solvent comprise hydrogen material, nitrogen material, one or more kind trace metal and dissolved mineralizers.

34. the method for claim 28, wherein said first solvent are NH substantially ₃

35. the crystalline of growing contains the method for gallium nitride, described method comprises:

Autoclave is provided, described autoclave comprises in the basket structure in a district and contains gallium material, in another district, comprise at least one seed crystal, and comprising the solvent that can form supercutical fluid, described basket structure construction is transferred to described another district for one or more solid part that prevents described raw material substantially from a described district;

In described supercutical fluid, handle described one or more part of gallium material that contains to be provided at the supercritical solution that contains the gallium material at least that comprises under first temperature;

Flow through from the described district part of described basket of one or more part that comprises the described supercritical solution that contains the gallium material is entered described another district; With

Containing the gallium nitride material by described supercritical solution growth crystalline under second temperature on described seed crystal, described second temperature is characterised in that and makes the described gallium material that contains form described crystalline contain the gallium nitride material on described seed crystal.

36. the method for claim 35 also comprises at least one crucible, in this crucible, in a described district, place in gallium metal and the basic metal one of at least; And wherein said basket structure comprises one or more supporting structure, and described supporting structure is made by the material that one or more kinds are selected from copper, copper base alloy, gold, gold-base alloy, silver, silver-base alloy, palladium, platinum, iridium, ruthenium, rhodium, osmium, titanium, vanadium, chromium, iron, ferrous alloy, nickel, nickel-base alloy, zirconium, niobium, molybdenum, tantalum, tungsten, rhenium, silicon-dioxide, aluminum oxide and combination thereof.

37. the method for claim 36, wherein said crucible comprise in molybdenum, tantalum, niobium, iridium, platinum, palladium, gold and silver, tungsten, aluminum oxide, magnesium oxide, calcium oxide, zirconium white, yttrium oxide, aluminium nitride or the gan one of at least.

38. the method for claim 37, the internal diameter of wherein said autoclave is greater than 75mm.

39. the method for claim 36 wherein saidly contains gallium material to comprise concentration is 10 ¹⁶Cm ^-3～10 ²¹Cm ^-3At least a doping agent.

40. the method for claim 39, wherein said doping agent comprise among Si, O, Mg, Zn, Fe, Ni, Co or the Mn one of at least.

41. the method for claim 36, also comprise framework, wherein said belfry is to shift described basket structure, baffle plate and seed crystal frame in beginning crystal growth forward direction described autoclave, and is configured to when the crystal growth processing procedure finishes the crystal of described basket structure, described baffle plate and growth is migrated out described autoclave.

42. the method for claim 36 wherein saidly contains gallium material to comprise particle size distribution is 0.020 inch～5 inches gan.

43. the method for claim 36, also be included in a described district and/or described another district one or both of vicinity in introduce getter material and/or structure.

44. the method for claim 43, wherein said getter comprise in alkaline-earth metal, Sc, Ti, V, Cr, Y, Zr, Nb, Hf, Ta, W, rare earth metal and nitride thereof, acid amides, imide, amide-imide or the halogenide one of at least.

45. the crystalline of growing contains the method for gallium nitride, described method comprises:

High-tension unit is provided, described high-tension unit comprises in a district and contains gallium material, in another district, comprise at least one seed crystal, and comprising trinitride mineralizer and at least a metal, described trinitride mineralizer and described metal provide with predetermined ratio and make and decomposed the nitrogen that generates and be about 1: 3 by the ratio of the hydrogen of the reaction generation of described metal and supercutical fluid by described trinitride mineralizer;

In described supercutical fluid, handle described one or more part that contains gallium material and comprise the supercritical solution that contains the gallium material at least under first temperature to be provided at; With

Containing the gallium nitride material by described supercritical solution growth crystalline under second temperature on described seed crystal, described second temperature is characterised in that and makes the described gallium material that contains form described crystalline contain the gallium nitride material on described seed crystal.

46. the method for claim 45, also being included in the vicinity at least one district of described high-tension unit or described another district provides catalyzer so that described nitrogen and hydrogen are converted into ammonia.

47. the method for claim 46, wherein said catalyzer comprise in iron, cobalt, nickel, titanium, molybdenum, tungsten, aluminium, potassium, caesium, calcium, magnesium, barium, zirconium, osmium, uranium or lanthanon, ruthenium, platinum, palladium or the rhodium one of at least.

48. the crystalline of growing contains the method for gallium nitride, described method comprises:

High-tension unit is provided, described high-tension unit comprises in a district and contains gallium material, in another district, comprise at least one seed crystal, and in a described district and/or described another district one or both of vicinity in comprise trinitride mineralizer, at least a metal and catalyzer, described trinitride mineralizer and described metal provide with predetermined ratio and make and decomposed the nitrogen that generates and be about 1: 3 and Geng Gao by the ratio of the hydrogen material of the reaction generation of described at least metal and supercritical ammine by described trinitride mineralizer;

In described supercritical ammine, handle described one or more part that contains gallium material and comprise the supercritical ammine solution that contains the gallium material at least under first temperature to be provided at;

Containing the gallium nitride material by described supercritical ammine solution growth crystalline under second temperature on described seed crystal, described second temperature is characterised in that and makes the described gallium material that contains form described crystalline contain the gallium nitride material on described seed crystal;

At least generate described hydrogen material by the reaction between described metal and described supercritical ammine fluid; With

At least with the described hydrogen material of described catalyst treatment so that described hydrogen material and nitrogen material are converted into described supercritical ammine fluid.

49. the method for claim 48, wherein said about 1: 3 ratio can be about 0.8: 3～1: 3.8.

50. the method for claim 48, wherein said catalyzer comprise in iron, cobalt, nickel, titanium, molybdenum, tungsten, aluminium, potassium, caesium, calcium, magnesium, barium, zirconium, osmium, uranium or lanthanon, ruthenium, platinum, palladium or the rhodium one of at least.

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