Ultra-high purity mineralizers and improved methods for nitride crystal growth.

Abstract

To manufacture fluoride-containing mineralizers at a low cost without impurities in the bulk crystals.SOLUTION: The present invention provides a manifold comprising one or more transfer vessels, a source vessel containing a condensable mineralizer composition, and a receiving vessel. A metallic surface within the one or more transfer vessels is chilled. The metallic surface comprises a composition that does not form a reaction product when exposed to the condensable mineralizer composition. A quantity of the condensable mineralizer composition is transferred to the one or more transfer vessels via a vapor phase, causing condensation of the condensable mineralizer composition within the one or more transfer vessels. The quantity of the condensable mineralizer composition is measured within at least one transfer vessel. At least a portion of the condensable mineralizer composition is transferred to the receiving vessel, forming at least a portion of a group III metal nitride boule through an ammonothermal crystal growth process. The ammonothermal crystal growth process exposes a seed crystal to a temperature of at least about 400°C, thereby exposing the seed crystal to a mineralizer that is formed from the condensable mineralizer composition transferred from the receiving vessel.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates generally to the processing of materials for the growth of crystals useful in the formation of bulk or patterned substrates that can be used to form a variety of optoelectronic, integrated circuit, power devices, lasers, light emitting diodes, photovoltaic cells, and other related devices. [Background technology]

[0002] Gallium nitride containing crystalline materials serve as substrates for the fabrication of conventional optoelectronic devices such as blue light-emitting diodes and lasers. Such optoelectronic devices are typically fabricated on sapphire or silicon carbide substrates, which have a different composition than the nitride layer being deposited. In conventional metal-organic chemical vapor deposition (MOCVD) techniques, GaN deposition from ammonia and metal-organic compounds is carried out in the gas phase. While successful, the conventional growth rates achieved make it difficult to provide a bulk layer of GaN material. Furthermore, dislocation densities are high, which leads to poor performance of the optoelectronic device.

[0003] The growth of nitride crystals by ammonothermal synthesis has been proposed. Ammonothermal crystal growth methods are expected to be scalable, as described in non-patent literature 1-4. Ammonothermal methods generally require mineralizers, which chemically react with polycrystalline raw materials to form soluble intermediates that are transported in a supercritical fluid and recrystallized on the seed crystal. A continuing challenge with ammonothermally grown GaN crystals is the significant level of impurities, which can cause coloration of the crystals, e.g., yellow, green, gray, or brown. These residual impurities can cause light absorption in light-emitting diodes fabricated on these substrates, adversely affecting efficiency, reducing electrical conductivity, and / or generating stress within the crystal. One potential source of impurities is the mineralizer.

[0004] Numerous mineralizers have been proposed for the ammonothermal growth of crystalline Group III metal nitrides. These include alkali metals; alkali imides, imide amides, amides, nitrides, hydrides, or azides; alkaline earth metals, imides, imide amides, amides, nitrides, hydrides, or azides; ammonium halides, Group III metal halides, or reaction products of Group III metals with ammonia and hydrogen halides. Most of these mineralizers are highly hygroscopic and / or moisture-sensitive, making it quite difficult to reduce the level of oxygen impurities. Regarding the chemistry of ammonobasic mineralizers, Dwilinski et al. (Patent Document 1) proposed the use of azides, which are commercially available and, due to their relatively low hygroscopicity, are easier to purify than the corresponding amides or nitrides. However, azides have the disadvantage of being chemically unstable and can decompose under typical ammonothermal conditions to form excess nitrogen gas. Regarding ammonoacid chemistries, ammonium chloride and ammonium fluoride are commercially available with purity specifications of greater than 99.99% on a trace metals basis (i.e., oxygen and moisture impurity levels are not specified). Ammonoacid mineralizers, including fluoride-containing mineralizers, can offer certain advantages over ammonobasic mineralizers. Stepin et al. (Non-Patent Document 5) propose NH4Cl from HCl and NH3, and Naumova et al. (Non-Patent Document 6) propose the purification of NH4Cl by sublimation. However, to our knowledge, neither of these authors specify the oxygen impurity levels achievable by these methods.

[0005] Mikawa et al. (Patent Document 2) disclose the reaction of ultra-high purity hydrogen halide with ultra-high purity ammonia to form ultra-high purity ammonium halide, and the use of the ultra-high purity ammonium halide as a mineralizer for ammonothermal gallium nitride crystal growth. However, the method disclosed by Mikawa et al. is not well suited to the use of condensable hydrogen halides such as HF, which are useful in the synthesis of fluoride-containing mineralizers.

[0006] Alexander et al. (US Pat. No. 5,629,499) disclose the formation of ultra-high purity ammonium fluoride by a vapor phase transfer and intermediate condensation process. However, the method of Alexander et al. has certain limitations, and the present disclosure offers several improvements. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] U.S. Patent No. 7,364,619 [Patent Document 2] US Patent Application Publication No. 2011 / 0268645 [Patent Document 3] U.S. Patent No. 9,299,555 [Non-patent literature]

[0008] [Non-Patent Document 1] Dwilinski, et al, J. Crystal Growth 310, 3911 (2008) [Non-patent document 2] Ehrentraut, et al., J. Crystal Growth 305, 204 (2007) [Non-patent document 3] D'Evelyn, et al. J. Crystal Growth 300, 11 (2007) [Non-patent document 4] Wang, et al., Crystal Growth & Design 6, 1227 (2006) [Non-Patent Document 5] Stepin, et al., Poluch. Anal. Vestchestv. Osoboi Chist., 5th, 91-94 (1978) [Non-patent document 6] Naumova, et al., Zh. Prikh. Khim. 52, 249 (1979) Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, what is needed is a low-cost method for producing fluoride-containing mineralizers that are suitable for large-scale production of bulk gallium nitride crystals and that do not contribute to impurities in the bulk crystals. [Means for solving the problem]

[0010] The present disclosure provides techniques for processing materials for crystal growth. More specifically, the present disclosure provides mineralizers suitable for use as raw materials for crystal growth of Group III metal nitride crystals by ammonobasic or ammonoacidic techniques, although others may be used. In other embodiments, the present disclosure provides methods suitable for the synthesis of crystalline nitride materials, although it will be appreciated that other crystals and materials may also be processed. Such crystals and materials include, but are not limited to, GaN, AlN, InN, InGaN, AlGaN, and AlInGaN, as well as others for the fabrication of bulk or patterned substrates. Such bulk or patterned substrates can be used in a variety of applications, including optoelectronic devices, lasers, light-emitting diodes, solar cells, photoelectrochemical water splitting and hydrogen production, photodetectors, integrated circuits, and transistors, among others.

[0011] In a specific embodiment, the present disclosure provides a mineralizer composition. The mineralizer may include one or more fluorine-containing compositions, including hydrogen fluoride (HF), ammonium fluoride (NHF), ammonium fluoride acid (NHF), gallium fluoride (GaF) and its diamine complex (GaF·2NH), and ammonium hexafluoride gallate ((NH)GaF). In certain embodiments, the mineralizer includes a composition comprising two or more of fluorine (F), hydrogen (H), nitrogen (N), and gallium (Ga), or a reaction product of a metal with ammonia and hydrogen fluoride, or a reaction product of two or more of the foregoing compositions. The mineralizer may have a total oxygen content of less than about 100 parts per million (ppm) by weight in the mineralizer composition.

[0012] In another embodiment, a mineralizer composition is provided that includes at least one of fluorine and at least one of chlorine, bromine, and iodine.

[0013] The present disclosure further provides a method for forming a gallium nitride crystalline structure. The method includes feeding a purified mineralizer substantially free of trace impurities into an autoclave or capsule along with ammonia and a polycrystalline group-III metal nitride raw material, wherein the trace impurities are less than about 1000 ppm. The method includes treating the polycrystalline group-III metal nitride in supercritical ammonia at a temperature above 400°C and a pressure above 50 MPa to cause the formation of one or more crystalline structures having substantially transparent properties. In certain embodiments, the crystalline structures have high purity and are transparent. The crystalline structures can be processed to form one or more group-III metal nitride wafers. The group-III metal nitride wafers can be used as substrates for devices such as light-emitting diodes (LEDs), laser diodes, power diodes, and transistors.

[0014] Benefits over existing techniques are achieved using the present disclosure. In particular, the present disclosure enables cost-effective growth of GaN, AlN, InN, InGaN, and AlInGaN, as well as other crystals. In specific embodiments, the methods and resulting compositions of the present invention can be realized using relatively simple and cost-effective techniques and equipment. In specific embodiments, the resulting mineralizers are substantially pure and can serve as a starting point for high-purity crystals, etc. Depending on the embodiment, one or more of these benefits can be achieved. These and other benefits may be described in more detail throughout this specification and hereinafter.

[0015] The present disclosure achieves these benefits and others in the context of known process technology. However, a further understanding of the nature and advantages of the present disclosure may be realized by reference to the remainder of this specification and the accompanying drawings.

[0016] So that the above-mentioned features of the present disclosure can be understood in detail, a more particular description of the present disclosure, briefly summarized above, can be had by reference to several embodiments, some of which are illustrated in the accompanying drawings. It should be noted, however, that the accompanying drawings illustrate merely exemplary embodiments and therefore should not be considered limiting of the scope thereof, which may admit of other equally effective embodiments. [Brief explanation of the drawings]

[0017] [Figure 1] 1 is a schematic diagram of a system for delivery of a condensable mineralizer composition according to one embodiment of the present disclosure. [Figure 2] FIG. 1 is a schematic diagram of a transfer vessel for condensing and re-evaporating a condensable mineralizer composition according to one embodiment of the present disclosure. [Figure 3] Schematic diagram of a transfer vessel for purification by condensation, re-evaporation, and fractional distillation, according to one embodiment of the present disclosure. [Figure 4] 1 is a schematic diagram of a charging system for condensable mineralizer composition and ammonia according to one embodiment of the present disclosure. [Figure 5]Graph showing the equilibrium vapor pressure of ammonia as a function of temperature [Figure 6] Graph showing the equilibrium vapor pressure of hydrogen fluoride as a function of temperature [Figure 7] 1 is a schematic diagram of a charging system for condensable mineralizer composition and ammonia according to one embodiment of the present disclosure. [Figure 8] 1 is a schematic diagram of a filling system for a mineralizer composition according to one embodiment of the present disclosure. [Figure 9] 1 is a flow chart summarizing the synthesis of a composition according to one embodiment of the present disclosure. [Figure 10] 1 is a flow chart summarizing the use of a composition according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0018] To facilitate understanding, the same reference numerals have been used, whenever possible, to refer to identical elements that are common to the figures. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further description.

[0019] The present disclosure provides techniques for processing materials for crystal growth. More specifically, the present disclosure provides high-purity mineralizers suitable for use as raw materials for crystal growth of Group III metal nitride crystals by the ammono-acid technique, although others may be used. In other embodiments, the present disclosure provides methods suitable for the synthesis of crystalline nitride materials, although it will be recognized that other crystals and materials may also be processed. Such crystals and materials include, but are not limited to, GaN, AlN, InN, BN, InGaN, AlGaN, AlInGaN, and BAlGaInN, as well as others for the fabrication of bulk or patterned substrates. Such bulk or patterned substrates can be used in a variety of applications, including optoelectronic devices, lasers, light-emitting diodes, solar cells, photoelectrochemical water splitting and hydrogen production, photodetectors, integrated circuits, and transistors, among others.

[0020] The present disclosure includes embodiments that may relate to compositions. The present disclosure includes embodiments that may relate to apparatus for making the compositions. The present disclosure includes embodiments that may relate to methods of making and / or using the compositions.

[0021] As used throughout the specification and claims, terms of approximation may be applied to modify any quantitative expression that may vary within acceptable limits without causing a change in the basic function to which it may relate. Thus, a value modified with a term such as "about" may not be limited to the exact value specified. In at least one example, the variation indicated by the term "about" may be determined with reference to the precision of the measuring device. Similarly, "free of" may be combined with a term that may contain an insignificant number or trace amounts of the modified term, but is still considered free unless otherwise specified.

[0022] In a specific embodiment, the present disclosure provides a mineralizer composition. The mineralizer comprises one or more fluorine-containing compositions, such as hydrogen fluoride (HF), ammonium fluoride (NH4F), ammonium fluoride acid (NH5F2), gallium fluoride (GaF3) and its diamine complex (GaF3·2NH3) or triamine complex (GaF3·3NH3), and ammonium hexafluoride gallate ((NH4)3GaF6). In certain embodiments, the mineralizer comprises or consists of a composition comprising two or more of fluorine (F), hydrogen (H), nitrogen (N), and gallium (Ga), or a reaction product of a metal with ammonia and hydrogen fluoride, or a reaction product of two or more of the above compositions. In certain embodiments, the condensable mineralizer composition comprises or consists of one or more of GaCl3, GaBr3, and GaI3. The mineralizer may have a total oxygen content in the mineralizer composition of less than about 10 parts per million (ppm) by weight, less than about 5 ppm, less than about 2 ppm, less than about 1 ppm, less than about 0.5 ppm, less than about 0.2 ppm, or less than about 0.1 ppm.

[0023] The inventors have discovered that commercially available point-of-use purifiers do not perform well with HF, and therefore, purification by distillation is highly desirable to avoid uncontrolled introduction of impurities into the gallium nitride bulk crystal growth process. The degree of purification by distillation processes is typically described in terms of theoretical plates, where one condensation / revaporization process corresponds to one theoretical plate. According to the process of the present disclosure, a portion of the condensable mineralizer composition purified by a distillation process of at least one theoretical plate, at least two theoretical plates, at least three theoretical plates, at least five theoretical plates, or at least ten theoretical plates is transferred from a mineralizer source to a receiving vessel.

[0024] Referring to FIG. 1, a manifold for delivery of a condensable mineralizer composition is provided. The manifold may include multiple valves; tubing; at least one vacuum pump; one or more traps in series with the at least one vacuum pump; a connection to a purge gas; a connection to an exhaust trap; one or more point-of-use purifiers; one or more transfer vessels into which the condensable mineralizer composition can be condensed; and one or more receiving vessels into which the condensable mineralizer can be delivered. The tubing and valves for the manifold may be constructed of stainless steel or a more corrosion-resistant alloy such as Hastelloy®, Monel®, or Inconel®. The tubing, valves, and other components may be connected by leak-proof fittings. The leak-proof fittings may be constructed of metal seals, knife-edge gasket metal seals, round-edge gasket metal seals, O-ring seals, ferrule seals, combinations thereof, or the like. The valve may include non-bonnet-type seals, such as bellows or diaphragm seals, and through seals constructed of polymers, such as Kel-F or polyimide. In certain embodiments, some components are made from or include polymeric materials, such as perfluoroalkoxyalkane (PFA Teflon®), poly(ethylene-co-tetrafluoroethylene) (ETFE), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene (ECTFE), THV (terpolymer of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride), and other fluoropolymers. For ease of discussion, but not for the purpose of limiting the scope of the present disclosure provided herein, various types of usable polymeric materials may be referred to herein as "plastic" materials. In certain embodiments, the manifold is enclosed in a ventilated enclosure for safety in the event of a leak. In certain embodiments, the pump contains a corrosion resistant fluid such as Krytox®.

[0025] At least one vacuum pump may comprise a conventional rotary oil pump. In other embodiments, the vacuum pump contains a corrosion-resistant fluid, such as Krytox®. In some embodiments, the vacuum pump may comprise or consist of a fluid-free pump, such as a diaphragm pump. In certain embodiments, a high-vacuum pump, such as a molecular drag pump or a turbomolecular pump, is provided. One or more of the pumps may be protected by one or more traps. The traps may be made of a transparent or translucent plastic, such as PFA (Teflon), and may contain a basic composition, such as pelletized NaOH, KOH, Ca(OH), CaCO, combinations thereof, or the like. In certain embodiments, the one or more traps are cooled during operation, for example, to cold water, ice, dry ice, or liquid nitrogen temperatures.

[0026] One or more bubbler traps or wet traps for venting to atmospheric pressure, at least two of which may be connected in series, may be made of transparent or translucent plastic, such as Nalgene, polypropylene, polyethylene, perfluoroalkoxy (PFA), "Teflon," etc. One or more of the bubbler traps may contain a basic aqueous solution including at least one of NaOH, KOH, Na2CO3, NaHCO3, etc.

[0027] The materials of construction of one or more transfer vessels or condensation vessels (e.g., "HF condensation vessel" in FIG. 1 ) or manifold components may include one or more of the following: transparent or translucent plastics such as perfluoroalkoxy (PFA) "Teflon," stainless steel, nickel, nickel alloys such as Hastelloy C-276 or Inconel 600, silver, silver alloys, Monel 400, or precious metals such as gold, platinum, palladium, rhodium, iridium, or ruthenium. In certain embodiments, one or more transfer vessels or manifold components include a coating such as silver, a precious metal, a polymer, or a plastic composition. The coating may be deposited within one or more transfer vessels or manifold components by one or more of electroless plating, electroplating, vapor deposition, or the like. In a preferred embodiment, the first transfer vessel includes metallic components within, on, or as an exterior portion of the vessel, thereby allowing condensation and associated heat exchange to occur efficiently on the metallic components. In a preferred embodiment, metal surfaces exposed to liquid mineralizer compositions, such as liquid HF, are fabricated from compositions that do not form reaction products upon exposure to the liquid-phase liquid mineralizer composition. In some instances, reaction products may include the formation of a "patina," a discolored film formed by chemical reaction between the metal and the liquid composition, which may fragment into particulate contaminants or cause significant corrosion during extended operation. "Significant corrosion" or a "significant amount of corrosion" may be defined as a loss of thickness of at least 5 micrometers, at least 25 micrometers, or at least 100 micrometers of a transfer vessel or manifold component over an extended period of operation, from about 3 months to about 10 years. The patina formed on the metal surface may comprise or consist of, for example, one or more of FeF3, FeF2, NiF2, CrF3, MoF4, and MoF5. The transfer container may have an inlet tube above the body of the container that has an inner diameter of less than about 10 millimeters, less than about 5 millimeters, less than about 3 millimeters, less than about 2 millimeters, or less than about 1 millimeter.The transfer container and / or the inlet tube thereover may be formed from an optically transparent, translucent, or at least partially opaque material and may include one or more markings or measurement lines that allow reading of the meniscus height of the fluid contained therein.

[0028] Preferably, the manifold is fabricated to avoid areas or features where liquid mineralizer composition may pool under the influence of gravity, and the manifold connection to the process vessel is the lowest gravity point of the assembly. Orienting the valve horizontally avoids any liquid pooling when closed. Referring again to FIG. 1 , the manifold includes horizontally or vertically oriented tubing members. In preferred embodiments, the manifold does not include any members or areas with a minimum height, as measured from a reference surface such as the floor, where accidentally formed liquid mineralizer may drip, collect, and form a pool. In preferred embodiments, this manifold layout avoids minimum heights for individual manifold members. In certain embodiments, one or more components of the manifold are enclosed within a heating jacket. In certain embodiments, most or all of the manifold components exposed to condensable mineralizer composition at pressures greater than about 200 Torr (26664.5 Pa) are enclosed within a heating jacket. In some embodiments, the temperature of one or more of the manifold components is maintained at a temperature that prevents condensation of all components of the condensable mineralizer material disposed therein. In certain embodiments, one or more of the manifold components is maintained at a temperature of from about 25° C. to about 150° C., or from about 30° C. to about 50° C. during operation when the condensable mineralizer composition is present.

[0029] 2 , first transfer container 200 may include outer enclosure 201 and lid 203 defining enclosed volume 205. Lid 203 may be removably attached to enclosure 201 by fasteners, e.g., with O-ring or gasket seals, or non-removably attached by, e.g., welding, brazing, or adhesives. First transfer container 200 may also include vapor inlet 207 having inlet valve 209 and vapor outlet 211 having outlet valve 213. In certain embodiments, first transfer container 200 includes internal heat exchange element 215 having fluid inlet 217 and fluid outlet 219. In preferred embodiments, internal heat exchange element 215 is made of or includes a metal that is chemically inert to condensable mineralizer compositions, such as anhydrous HF, does not significantly corrode under extended use, and / or does not readily form a patina upon exposure to fluorine-containing compositions. In certain embodiments, first transfer container 200 further includes an internal temperature sensor 221 and a fluid level sensor 223. In certain embodiments, internal temperature sensor 221 comprises at least one of a thermocouple, a thermistor, and a resistance temperature detector (RTD) and is interfaced to a control system (not shown). In certain embodiments, internal temperature sensor 221 is enclosed within a sheath that comprises or is made of a polymeric material (e.g., plastic) or metal that is chemically inert to the condensable mineralizer composition and does not form a patina. In certain embodiments, fluid level sensor 223 comprises or is made of at least one of a float-type sensor, an electrode-type sensor, a differential pressure transducer, a load cell, a magnetic level gauge, a capacitance transmitter, an ultrasonic level transmitter, a laser level transmitter, a guided pulse sensor, and a sensing guided pulse transducer. In certain embodiments, fluid level sensor 223 comprises a plastic-encapsulated probe that is at least partially immersed in the condensable mineralizer composition during operation. In certain embodiments, one or more connections to the first transfer container 200 are flexible, and the amount of the condensable mineralizer composition in the internal volume 205 is determined gravimetrically, i.e., by weight measurement, rather than by volumetric analysis.

[0030] When internal heat exchange member 215 is present, outer enclosure 201 can be made of plastic or metal, depending on the preferred design variation. In certain embodiments, heat exchange to or from the condensable mineralizer composition occurs through outer enclosure 201, which includes or consists of metal, instead of or in addition to internal heat exchange member 215. In certain embodiments, heat exchange through outer enclosure 201 is facilitated by an external heat exchange bath 225 containing bath fluid 226, the temperature of which can be changed by the heat exchange fluid entering fluid inlet 227, circulating through heat exchange loop 228 within bath fluid 226, and exiting through heat exchange fluid outlet 229. In certain embodiments, one or both of bath fluid 226 and heat exchange fluid include or consist of one or more of propylene glycol, ethylene glycol, alcohol, and water. The temperature of bath fluid 226 can be monitored by external temperature sensor 230. In certain embodiments, the external temperature sensor 230 comprises at least one of a thermocouple and a resistance temperature detector (RTD). In certain embodiments, an agitator (not shown) circulates the bath fluid 226. In certain embodiments, a fluid inlet 227 supplies fluid directly to the space between the outer heat exchange bath and the outer enclosure 201, rather than through the heat exchange loop 228.

[0031] A source of a condensable mineralizer composition, such as anhydrous HF, may be connected to the manifold. A source of a purge gas, such as argon (Ar) or nitrogen (N), may be connected to the manifold. Prior to use, the manifold may be verified to be gas-tight, such as by a helium leak test.

[0032] The manifold may further include one or more sensors. Suitable sensors may include one or more of: a pressure sensor, such as a vacuum gauge, Bourdon gauge, aneroid barometer, or capacitance manometer; a temperature sensor, such as a thermocouple or resistance temperature detector; and a gas composition sensor, such as a mass spectrometer or residual gas analyzer. The sensors may be located in or near the manifold and may communicate certain process parameters within the manifold to a controller, described below. In certain embodiments, some or all of the manifold may be maintained at an elevated temperature, for example, by a heating jacket, heating tape, or heating trace, to avoid condensation of condensable mineralizer compositions at preselected locations within the manifold. In certain embodiments, the elevated temperature may be selected within a range of 25 to 150°C, or within a range of 30 to 50°C.

[0033] In certain embodiments, the manifold is filled with a purge gas (e.g., argon or nitrogen) between uses. The pressure of the purge gas in the manifold before the filling operation begins can be from about 0.1 atmospheres to about 5 atmospheres. In alternative embodiments, the manifold is placed under vacuum between uses. The vacuum level in the manifold before the filling operation begins can be less than about 1 Torr (133.322 Pa), less than about 1 milliTorr (mTorr) (0.133322 Pa), or less than about 10 -5 It may be less than Torr (0.00133322 Pa).

[0034] The receiving vessel ("process vessel" in FIG. 1) may be attached to the manifold via a leak-proof connection. The receiving vessel may consist of a capsule suitable for ammonothermal crystal growth, such as those described in U.S. Patent Application Publication No. 2009 / 0301388 and U.S. Patent No. 10,029,955, and may include a fill tube terminated by a valve that is closed upon connection of the receiving vessel or capsule to the manifold. The receiving vessel may contain one or more Group III metal nitride seed crystals, polycrystalline Group III metal nitride nutrient, and one or more baffles. In certain embodiments, the receiving vessel or capsule is purged and / or evacuated prior to connection to the manifold. In certain embodiments, the receiving vessel or capsule is baked at a temperature of about 50° C. to about 800° C. prior to connection to the manifold, and the temperature is maintained at about 100° C. -2 Torr (1.33322 Pa) or less, or about 10 -4 The receiving vessel or capsule is evacuated to a pressure of less than 100 Torr (0.0133322 Pa). In certain embodiments, the receiving vessel or capsule is evacuated, purged, and / or baked prior to or while connected to the manifold. In certain embodiments, the manifold allows flow into fittings connected to valves on the receiving vessel during installation.

[0035] After connecting the receiving vessel or capsule to the manifold and closing the valve on the fill tube of the receiving vessel, the valve terminating the manifold connection to the receiving vessel can be opened, and at least a portion of the manifold and the space between the manifold and the receiving vessel can be evacuated. At least a portion of the manifold and the space between the manifold and the receiving vessel can be refilled with purge gas and re-evacuated. The refill / pumping sequence can be repeated, for example, at least about five times. During the refill portion of a cycle, the manifold pressure can be increased to a range of about 0.5 atmospheres to about 10 atmospheres, or about 1 atmosphere to about 5 atmospheres. During the pumping portion of a cycle, the manifold can be maintained at a pressure of less than 1 Torr (133.322 Pa), less than 0.1 Torr (13.3322 Pa), less than 10 atmospheres, or less than 10 atmospheres. -2 Torr (1.33322 Pa) or less, 10-3 Torr (0.133322 Pa) or less, 10 -4 Torr (0.0133322 Pa) or less, 10 -5 Torr (0.00133322 Pa) or less, 10 -6 Torr (0.000133322 Pa) or less, 10 -7 Torr (0.0000133322 Pa) or less, 10 -8 Torr (0.00000133322Pa) or less than 10 -9 The manifold, which includes at least one transfer vessel and a connection to a receiving vessel, may be evacuated to a pressure below 100 Torr. After the manifold, which includes at least one transfer vessel and a connection to a receiving vessel, has achieved a desired vacuum level or has been pumped a predetermined number of times, the valve to the vacuum pump may be closed.

[0036] At least a portion of first transfer container 200 can be cooled by flowing a cooling fluid, such as, for example: chilled water; a chilled mixture of water and ethylene glycol or propylene glycol; chilled alcohol, acetone, or methylene chloride; or liquid nitrogen, through internal heat exchange element 215 or external heat exchange element 228, thereby condensing the condensable mineralizer composition. Cooling can be achieved by: passing the chilled fluid through an ice bath, a dry ice bath; by a closed-cycle refrigerator; or by other means known in the art. In certain embodiments, outer enclosure 201 is cooled by immersion in a bath containing: water and ice; dry ice and one of alcohol, acetone, and methylene chloride; or liquid nitrogen, or using a closed-cycle refrigerator. One or more valves, including vapor inlet valve 209, between a source of condensable mineralizer composition, such as HF, and first transfer vessel 200 can be opened to allow vapor from the condensable mineralizer composition to flow from the source vessel into the cooled first transfer vessel 200 and condense within the first transfer vessel 200. The pressure of the vapor-phase condensable mineralizer composition can be from about 1 Torr (133.322 Pa) to about 10 atmospheres during the transfer operation. In certain embodiments, the duration of the vapor transfer process is selected by comparing the level of the meniscus of the condensed mineralizer composition within first transfer vessel 200 to a reference position of the first transfer vessel. In certain embodiments, the duration of the vapor transfer process to first transfer vessel 200 is selected to target a predetermined fluid level as measured by fluid level sensor 223. In certain embodiments, the vapor-phase transfer process is facilitated by heating a source vessel containing the condensable mineralizer composition, such as a cylinder of HF, and the tubing and valves connecting it to first transfer vessel 200 to a temperature of about 20°C to about 400°C, or about 25°C to about 100°C. In certain embodiments, the condensable mineralizer composition vapor passes through a point-of-use purifier, which may include a getter, before condensing in first transfer vessel 200. The vapor-phase transfer process can be facilitated by heating the point-of-use purifier to a temperature of about 30°C to about 400°C, or about 30°C to about 100°C.In certain embodiments, the first transfer vessel also contains a getter to further purify the condensable mineralizer composition before transfer to the receiving vessel, hi a specific embodiment, the getter comprises at least one of CoF, ZnF, ZrF, HfF, Hg, Cu, Ag, and Au.

[0037] After the desired amount of condensable mineralizer composition has been transferred in the vapor phase to first transfer vessel 200, one or more valves between the condensable mineralizer source vessel and first transfer vessel 200, including inlet valve 209, may be closed. First transfer vessel 200 and one or more of internal heat exchange element 215 and external heat exchange element 228, if present, may be warmed, for example, to room temperature, to vaporize at least a portion of the condensed mineralizer composition and prepare it for the subsequent transfer process.

[0038] In certain embodiments, it may be desirable to remove a portion of the condensable mineralizer composition from first transfer vessel 200 prior to transfer to the receiving vessel. For example, determining the amount of condensable mineralizer composition can be accomplished volumetrically using fluid level sensor 223 to compare the height of the meniscus of the condensable mineralizer composition to one or more markings on first transfer vessel 200 while the first transfer vessel is held at a predetermined temperature, e.g., room temperature, as measured by temperature sensor 221. One or more valves isolating first transfer vessel 200 from the liquid traps can be opened, and one or more valves to a purge gas source can be opened, allowing purge gas to flow over the condensable mineralizer composition in first transfer vessel 200, mix with vapor from the condensable mineralizer composition, and deliver it to the one or more liquid traps. During the purging operation, the pressure of the purge gas can be from about 1.1 atmospheres to about 5 atmospheres. Throttling the flow rate of the purge gas can maintain an acceptable rate of aeration and heat generation in the one or more liquid traps. In certain embodiments, one or more check valves prevent backflow of gas or vapor from the liquid trap into the manifold or from the manifold into the purge gas source line. The flow of purge gas can be terminated by closing one or more valves when the amount of condensable mineralizer composition in first transfer vessel 200 is reduced to a desired level. In certain embodiments, a portion of the condensable mineralizer composition in first transfer vessel 200 is removed by partial evacuation, for example, by opening one or more valves isolating first transfer vessel 200 from the vacuum pump for a controlled period of time. In certain embodiments, a dry trap, for example, pellets of at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, and calcium carbonate, protects the vacuum pump from the corrosive condensable mineralizer composition.

[0039] In certain embodiments, some or all of the condensable mineralizer composition is then transferred from the first transfer vessel 200 to at least one of the second transfer vessel and the receiving vessel. In certain embodiments, this transfer operation is performed in the vapor phase by cooling at least one of the second transfer vessel and the receiving vessel, and optionally heating the first transfer vessel 200. In certain embodiments, the vapor phase transfer is performed with the condensable mineralizer composition in the manifold at a pressure of from about 50 Torr (6666.12 Pa) to about 2 atmospheres, or from about 200 Torr (26664.5 Pa) to about 1 atmosphere. In certain embodiments, this transfer operation is performed in the liquid phase, for example, by opening one or more valves to allow the (liquid) condensable mineralizer composition to flow into the second transfer vessel. In certain embodiments, the amount of condensable mineralizer composition delivered to the receiving vessel is measured by determining changes in the fluid level using fluid level sensor 223 or by comparing the position of the meniscus of the condensable mineralizer composition to one or more reference markings formed on or adjacent to a transparent or translucent portion of first transfer vessel 200. In certain embodiments, it may be desirable to remove a portion of the condensable mineralizer composition from the second transfer vessel prior to transfer to the receiving vessel. One or more valves isolating the second transfer vessel from the liquid trap may be opened, and one or more valves to a purge gas source may be opened, causing purge gas to flow over the condensable mineralizer composition in the second transfer vessel, mix with vapor from the condensable mineralizer composition, and pass to the one or more liquid traps. The flow of purge gas may be terminated by closing one or more valves when the amount of condensable mineralizer composition in the second transfer vessel has decreased to a desired level. In certain embodiments, the amount of condensable mineralizer composition in the second transfer vessel is determined by gravitational measurement. In certain embodiments, the second transfer container is attached to the manifold by a flexible connection, and the weight of the concentrate mineralizer composition is determined by weighing the second transfer container before and after transfer of the concentrate mineralizer composition.In other embodiments, the amount of condensable mineralizer composition is determined by disconnecting the second transfer vessel from the manifold (after multiple cycles of pumping and purging), weighing with and without the condensable mineralizer composition present, and reconnecting the second transfer vessel to the manifold (and performing multiple cycles of pumping and purging).

[0040] In certain embodiments, the amount of condensable mineralizer composition in first transfer vessel 200 is measured by level sensor 223. Level sensor 223 can communicate the measured height of condensable mineralizer composition in first transfer vessel 200 to a controller (not shown), which can convert the height signal to mineralizer volume and mass using internal temperature sensor 221 or external temperature sensor 230. The height to mineralizer mass conversion can be calibrated using water and an appropriate temperature-dependent HF density conversion. In configurations where the controller measures height and temperature in real time, the temperature may fluctuate during transfer of the condensable mineralizer composition, although this does not prevent accurate measurement of the (temperature-dependent) mineralizer mass. In some embodiments, the temperature can be stabilized before condensation or transfer by pausing for a period of, for example, about 1 second to about 1 minute. In embodiments where the level sensor has a dead zone or "dead zone" near the top and / or bottom of the level sensor, the amount of mineralizer initially condensed must take into account both the amount at the "bottoms" and the amount that will be transferred to the process vessel or capsule. When the desired amount of mineralizer is condensed into the first transfer vessel 200, the condensed amount can be re-measured and recorded as the starting volume before transfer to the receiving vessel. The level sensor equation can be written as follows:

[0041] [Table 1]

[0042] The transfer process of the condensable mineralizer composition may be repeated, for example, to a third, fourth, or more transfer vessels. In some embodiments, one or more of the additional transfer processes are carried out in the vapor phase and in the condensed state.

[0043] In certain embodiments, the effluent vapor from at least one of the first transfer vessel 200, the second transfer vessel, and the additional transfer vessel is further purified by fractional distillation. In certain embodiments, the pressure of the effluent vapor may be from about 50 Torr (6666.12 Pa) to about 2 atmospheres or from about 200 Torr (26664.5 Pa) to about 1 atmosphere during the fractional distillation process. In certain embodiments, as shown schematically in FIG. 3 , a distillation column 331 is positioned above or downstream from a transfer vessel, such as the first transfer vessel 200. The distillation column 331 may include an insulating sleeve 333. In certain embodiments, the insulating sleeve 333 provides structural support for an enclosure 335 of the distillation column 331, which may be thin and minimize axial heat exchange, allowing a temperature gradient to be established within the distillation column 331. Distillation column 331 may further include packing material 339 to facilitate multiple condensation and re-evaporation steps, whereby excess condensed portions of the condensable mineralizer composition drip back to the transfer vessel from where they vaporize. In other embodiments, distillation column 331 contains additional internal components, such as one or more of disks, trays, bubble caps, and sponges. In certain embodiments, one or more of the above components of distillation column 331 are made of or include a material that is inert to the condensable mineralizer composition, e.g., silver or another metal, or a plastic such as PFA "Teflon" or ETFE, that does not undergo significant corrosion or readily form a patina after extended use. The temperature of the region within distillation column 331 may be from about −20° C. to about 50° C., or from about 0° C. to about 35° C. during the vapor transfer process. In certain embodiments, the condensable mineralizer composition effluent vapor passes through mass flow controller 341 before or after passing through distillation column 331. In certain embodiments, integrating over time the output signal provided by mass flow controller 341, which is proportional to the flow rate of the vapor through the mass flow controller, provides a means for accurately measuring and determining the amount of condensable mineralizer composition transferred to the receiving vessel. In certain embodiments, the portion of mass flow controller 341 that is wetted by the process vapor is maintained at a temperature of from about 25°C to about 150°C or from about 30°C to about 50°C during the vapor transfer process.

[0044] In certain embodiments, as shown schematically in FIG. 8 , the condensable mineralizer composition is condensed in first transfer container 200 and then poured as a liquid into second transfer container 842 through connection 844 without first determining the amount of fluid in first transfer container 200 by volumetric or gravimetric measurement. In preferred embodiments, second transfer container 842 and connection 844 consist of or include a metal composition that does not undergo significant corrosion, for example, after extended use, or does not readily form a patina or scale upon reaction with the condensed mineralizer composition in its liquid phase. As noted above, in some embodiments, the metal composition is configured to not form reaction products upon exposure to the condensed mineralizer composition in its liquid phase. In certain examples, the metal composition is configured to not undergo corrosion corresponding to a thickness loss of more than 5 micrometers, more than 25 micrometers, or more than 100 micrometers upon use for a period of at least three months, or to not form a patina or scale upon reaction with the condensed mineralizer composition. By heating or maintaining second transfer vessel 842 at a temperature higher than that of first transfer vessel 200 and one or more downstream vessels during the fluid transfer operation, vapor can pass upward from second transfer vessel 842 into distillation column 331 through mass flow controller 341, and the amount of transferred mineralizer can be quantified by integrating the output of mass flow controller 341 over time. In this manner, continuous transfer of condensable mineralizer can be achieved while simultaneously achieving significant purification. In certain embodiments, first transfer vessel 200 is maintained at a temperature of about −20° C. to about 20° C. during the transfer operation, and second transfer vessel 842 is maintained at a temperature between 1° C. and 20° C. higher than first transfer vessel 200. In certain embodiments, first transfer vessel 200 consists of or includes a section of refrigerable tubing. In certain embodiments, second transfer vessel 842 consists of or includes the bottom of distillation column 331. In certain embodiments, the amount of mineralizer passed through distillation column 331 is determined gravimetrically, rather than using mass flow controller 341, for example, by condensing and weighing into final transfer vessel 345 (see FIG. 3) or a third transfer vessel (not shown).

[0045] In certain embodiments, the final transfer vessel upstream of the receiving vessel is configured for liquid-phase transfer of the condensable mineralizer composition to the receiving vessel. Referring again to FIG. 3 , in one specific embodiment, the outlet tube 343 of the final transfer vessel 345 extends generally to the bottom of the interior of the final transfer vessel 345. In certain embodiments, the final transfer vessel 345 can be cooled and heated by at least one of an internal heat exchange member and an external heat exchange bath, similar to the first transfer vessel 200 described above. In another specific embodiment, the final transfer vessel 345 is configured with a valve 347 at its lower end, which allows the condensable mineralizer composition to flow in liquid form into the receiving vessel 349 when the valve 347 is open. In certain embodiments, the final transfer vessel is heated to a temperature between about 2° C. and about 50° C., or between about 5° C. and about 25° C., higher than the temperature of the receiving vessel 349 during the liquid transfer operation. In this way, as is evident from the vapor pressure data shown in Figure 6 for the case of HF, the vapor pressure of the condensable mineralizer composition in the final transfer vessel 345 is significantly higher than the vapor pressure of the mineralizer in the receiving vessel 349 that is formed as soon as the liquid transfer process begins, and therefore the liquid transfer can continue by compressing the vapor in the receiving vessel 349 without having to vent the vapor from the receiving vessel 349, for example by venting.

[0046] Once the desired amount of concentrateable mineralizer composition is in the final transfer vessel (which in certain embodiments is first transfer vessel 200), the upstream valve is closed, one or more valves separating the final transfer vessel from the receiving vessel are opened, and the concentrateable mineralizer composition is transferred from the final transfer vessel to the receiving vessel. In certain embodiments, the transfer is facilitated by cooling the receiving vessel. In certain embodiments, the temperature of the receiving vessel is from about 77 Kelvin to about 320 Kelvin, or from about −80° C. to about 30° C. during the transfer operation. In certain embodiments, the transfer is facilitated by heating the final transfer vessel and the valve and one or more lines connecting the final transfer vessel to the receiving vessel, for example, to a temperature of from about 25° C. to about 150° C. or from about 30° C. to about 50° C. This transfer can be surprisingly rapid, requiring only about 60 minutes or less than about 20 minutes, due to the high thermal conductivity of the first transfer vessel and the receiving vessel, especially when these vessels comprise or consist essentially of silver. In certain embodiments, the vapor pressure of the condensable mineralizer composition in the final transfer vessel causes a majority liquid phase transfer of the condensable mineralizer composition from the final transfer vessel to the receiving vessel.

[0047] The amount of condensable mineralizer composition transferred to the receiving vessel may be from about 0.1 milliliters to about 100 liters, or from about 1 milliliter to about 10 liters. Transfer of amounts greater than about 10 milliliters is facilitated by heating one or more of the vessels and tubing during vapor phase transfer to maintain the vapor pressure of the condensable mineralizer composition above atmospheric pressure.

[0048] After the transfer of the condensable mineralizer composition to the receiving vessel is complete, the valve between the last transfer vessel and the receiving vessel may be closed, and the connection between the two valves may be opened. Any residual condensable mineralizer composition remaining in the manifold may be removed by passing a purge gas through the manifold, followed by a cycle of evacuation and refilling with purge gas while heating. The manifold may then be left charged with a predetermined pressure of purge gas or under vacuum. The receiving vessel may then be connected to a separate manifold for charging with ammonia.

[0049] This approach offers numerous advantages over prior art methods. Intentional vapor transfer and recondensation allows for accurate metering of the condensable mineralizer composition without the need to rely on mass flow controllers, which may have unknown calibration coefficients for the condensable mineralizer composition, and avoids unintended condensation and transfer line plugging, which can occur with simple vapor-phase transfer processes such as those described by Mikawa et al. Because the vapor pressures of the condensable mineralizer composition and potential impurities such as O and HO are significantly different, the distillation process itself provides further purification. Furthermore, getters can be added to the transfer vessel for purification without fear of contaminating downstream processes (as long as the getter and its reaction products with oxygen or other undesirable impurities are nonvolatile). Because commercial grades of condensable mineralizer compositions such as HF and GaCl typically contain impurities such as O, HO, and metals, at least a few parts per million up to 1% or more, additional purification is highly desirable.

[0050] By rigorously excluding air and moisture from the manifold, high purity mineralizers can be achieved and corrosion of the manifold's internal surfaces by condensable mineralizer compositions is avoided. Removal of substantial amounts of liquefied condensable mineralizer compositions by flowing purge gas into the liquid bubbler trap rather than by evacuation significantly extends the life of the dry trap and one or more vacuum pumps and avoids pump-down problems associated with the formation of condensable vapors in the pump oil. The use of basic compositions, such as alkali hydroxides, in the wet and dry traps protects one or more pumps from undesirable exposure to condensable mineralizer compositions and minimizes or avoids release of condensable mineralizer compositions into the ambient air.

[0051] In certain embodiments, it may be necessary to remove mineralizer from first transfer vessel 200 for maintenance and to optimize the purity of the mineralizer transfer process. For example, if the condensable mineralizer composition consists of or includes HF, the "bottoms" fraction left in first transfer vessel 200 after downstream vapor-phase transfer of a portion of the condensable mineralizer composition will be enriched in water relative to the transferred composition. Therefore, in preferred embodiments, this bottoms fraction is removed before another transfer operation begins. The remaining condensed mineralizer can be disposed of by a purging operation using an inert carrier gas transferred to an alkaline wet trap.

[0052] In certain embodiments, the purity of the transferred condensable mineralizer composition may be sampled prior to introduction into the receiving vessel 349. For example, referring again to FIG. 1 , a sampling vessel (not shown) may be connected to valve V5 of the manifold. The sampling vessel may be cooled to cause condensation of the condensable mineralizer composition within the sampling vessel, either before or after purification by one or more distillation processes or fractional distillation. In a specific embodiment, the concentration of residual water in the condensable mineralizer composition is quantified by measuring its conductivity, as described, for example, in N. Miki et al., J. Electrochem. Soc. 137, 787 (1990). In another specific embodiment, the concentration of residual water in the condensable mineralizer composition is quantified by one of Fourier transform infrared (FTIR) spectroscopy, mass spectroscopy, gas chromatography, conductivity measurement, or the like. In certain embodiments, the number of theoretical plates of purification is calculated by comparing the concentration of water in the purified mineralizer with the concentration of water in the steam received directly from the mineralizer source. If the purity of the purified condensable mineralizer composition is found to be unacceptable, in some embodiments, at least a portion of the condensable mineralizer composition may be vapor transferred (distilled) back to first transfer vessel 200 and another purification cycle may be performed. In some embodiments, the distillation purification system provides at least 2, at least 3, at least 5, or at least 10 theoretical stages of purification.

[0053] In certain embodiments, one or more additional mineralizer compositions including HCl, HBr, HI, Cl2, Br2, I2, GaCl3, GaBr3, and GaI3 may be added to the receiving vessel or capsule. In certain embodiments, the additional mineralizer compositions are transferred by vapor phase transport and condensed into at least one transfer vessel. In certain embodiments, the additional mineralizer compositions can be transferred directly into the receiving vessel or capsule by vapor phase transport, for example, using a mass flow controller to meter the amount of mineralizer composition transferred. In certain embodiments, the additional mineralizer compositions are transferred as a liquid.

[0054] In certain embodiments, following transfer of a predetermined, precisely metered amount of condensable mineralizer composition to a receiving vessel or capsule, the receiving vessel or capsule may be connected to a separate manifold for ammonia delivery, after which ammonia may be transferred to the capsule.

[0055] In certain embodiments, an integrated manifold 400 is used to add the condensable mineralizer composition and ammonia to the receiving vessel, as shown schematically in FIG. 4 . The integrated manifold 400 may include the condensable mineralizer manifold 350, previously described in detail, along with an ammonia manifold 450. The ammonia manifold 450 may include one or more of an ammonia source 452, a vacuum pump 454, a pressure gauge 456, a point-of-use purifier 458, and a mass flow controller 460. Because ammonia and HF readily react to form NHF at room temperature, it is important that the integrated manifold 400 include features that prevent HF and ammonia from being present in the same location at a given time, except for the receiving vessel 349. In certain embodiments, some or all of the unrefrigerated components of the condensable mineralizer manifold 350 may be maintained at an elevated temperature of about 25° C. to about 150° C., or about 30° C. to about 50° C., to prevent HF from condensing in undesirable locations. In certain embodiments, a purge gas, such as argon, is flowed through purge inlet 465 to flush out ammonia manifold 350, final transfer vessel 345, and any additional components in which condensable mineralizer composition may reside at some point in the process cycle before the ammonia enters. In certain embodiments, the purge gas can be flowed to a pressure of about 0.5 atmospheres to about 10 atmospheres, or 1 atmosphere to about 5 atmospheres. In certain embodiments, the purge gas can be flowed to a pressure of less than about 0.1 Torr (13.3322 Pa), less than about 10 -2 Torr (1.33322 Pa) or less, approximately 10 -3 Torr (0.133322 Pa) or less, approximately 10 -4 Torr (0.0133322 Pa) or less, or about 10 -5 The system is evacuated to a pressure of less than 100 Torr. In certain embodiments, at least two, at least three, or at least five pump / purge cycles are performed. In certain embodiments, at least one component in the condensable mineralizer manifold 350 and final transfer vessel 345 is heated and the pressure is monitored to ensure the absence of uncondensed mineralizer composition, such as liquid HF.

[0056] In certain embodiments, ammonia is transferred into the receiving vessel or capsule via a vapor-phase transfer process. For example, referring again to FIG. 4 , after removing the condensable mineralizer composition from the portion of condensable mineralizer manifold 350 that will be exposed to ammonia and from final transfer vessel 345, if present, the manifold can be vented through valve 347. The ammonia manifold 450 can be purged and evacuated. In certain embodiments, at least two, at least three, or at least five pump / purge cycles are performed. The receiving vessel 349 can be cooled, for example, to about dry ice temperature, which also reduces the vapor pressure of the condensable mineralizer already present in the receiving vessel 349 to a very low level. In certain embodiments, the temperature of the receiving vessel 349 is between about 77 Kelvin and about 320 Kelvin, or between about −80° C. and about 30° C., during the ammonia transfer process. One or more valves between the ammonia source 452 and valve 347 can be opened to charge the ammonia manifold with ammonia. Valve 347 can then be opened to allow the ammonia gas to flow through point-of-use purifier 458 , metered and controlled by mass flow controller 460 , and condensed as a liquid in receiving vessel 349 .

[0057] In certain alternative embodiments, ammonia is transferred into receiving vessel 349 via a liquid-phase transfer process. For example, referring again to FIG. 4 , after removing the condensable mineralizer composition from final transfer vessel 345, final transfer vessel 345 may be vented. In certain embodiments, final transfer vessel 345 is cooled, for example, to about dry ice temperature, and one or more valves between ammonia source 452 and final transfer vessel 345 are opened. Ammonia gas flows through point-of-use purifier 458, is metered and controlled by mass flow controller 460, and is condensed as a liquid in final transfer vessel 345. In certain embodiments, final transfer vessel 345 is cooled to a relatively high temperature, for example, from about −20° C. to about 15° C. Referring to FIG. 5 , which shows the vapor pressure of liquid ammonia as a function of temperature, liquid ammonia will condense in final transfer vessel 345 as long as the pressure of ammonia in the ammonia manifold is higher than the vapor pressure of ammonia at the temperature of final transfer vessel 345. For example, if the temperature of final transfer vessel 345 is −10° C. (this temperature can be achieved using a salt / water / ice bath), the pressure of ammonia in the ammonia manifold should be maintained above about 3 atmospheres; at 0° C., the pressure should be maintained above about 4.5 atmospheres; and at 10° C., the pressure should be maintained above about 6 atmospheres. The pressure of ammonia in ammonia source 452 can be maintained above about 10 atmospheres by maintaining the temperature of ammonia source 452 above about 25° C. Further details of possible ammonia charging processes are described in U.S. Pat. No. 8,021,481, which is incorporated herein by reference in its entirety. After the desired amount of ammonia has been added to final transfer vessel 345, final transfer vessel 345 may be heated to about 25° C., about 30° C., or higher, as needed, for example, by integrating the output of mass flow controller 458. If the receiving vessel 349 is at about room temperature, it can contain HF vapor at a pressure near 1 atmosphere, as shown in FIG. 6, which is a graph of HF vapor pressure as a function of temperature.As a result, when valve 347 is opened to receiving vessel 349, solid NHF begins to form immediately as ammonia begins to flow from final transfer vessel 345 to receiving vessel 349, and continues to form until the HF vapor and liquid in receiving vessel 349 are completely converted to NHF (and / or NH5F2). The initially formed NHF can be carried into receiving vessel 349 by flowing liquid ammonia, which is present at a pressure greater than 7 atmospheres or greater than 10 atmospheres, depending on the temperature of final transfer vessel 345. Any residual NHF in final transfer vessel 345 or in the tubing or valves between it and receiving vessel 349 can be transferred by heating it to a temperature between about 100°C and about 250°C. In certain embodiments, final transfer vessel 345 is heated to a temperature between about 2°C and about 50°C, or between about 5°C and about 25°C, higher than the temperature of receiving vessel 349 during the liquid transfer of ammonia. In this way, the vapor pressure of ammonia in the final transfer vessel 345 is significantly higher than the vapor pressure of ammonia in the receiving vessel 349 which forms as soon as liquid ammonia is present, and therefore the transfer of the liquid can continue by compressing the ammonia vapor in the receiving vessel 349 without having to vent the vapor from the receiving vessel 349, for example by venting.

[0058] In certain embodiments, as shown schematically in FIG. 7, separate condensable mineralizer manifolds 350 and ammonia manifolds 450 are used to add the condensable mineralizer composition and ammonia to the receiving vessel 349. Each manifold may have a separate connection to the receiving vessel 349. In certain embodiments, the mineralizer manifold 350 and the ammonia manifold 450 are connected to the same inlet of the receiving vessel 349, but sequentially so that at most one manifold is connected to the receiving vessel 349 at any given time, and repeated pump / purge cycles are performed before each disconnection operation and after each reconnection operation. In certain embodiments, the ammonia manifold 450 comprises an ammonia transfer vessel 745 interfaced to the receiving vessel 349 by outlet 743 and valve 747. The use of separate manifolds reduces the risk of accidental formation of NHF within the integrated manifold. In certain embodiments, the condensable mineralizer composition is transferred to receiving vessel 349 and then transferred into an ammonia receiving vessel or capsule via a vapor-phase transfer process. Ammonia manifold 450, including ammonia transfer vessel 745, if present, may be purged and evacuated. Receiving vessel 349 may be cooled, for example, to approximately dry ice temperature, which also reduces the vapor pressure of the condensable mineralizer already present in receiving vessel 349 to a very low level. One or more valves between ammonia source 452 and valve 747 may be opened to charge the ammonia manifold with ammonia. Valve 747 may then be opened to allow ammonia gas to flow through point-of-use purifier 458, metered and controlled by mass flow controller 460, and condensed as a liquid in receiving vessel 349.

[0059] In certain alternative embodiments, ammonia is transferred into receiving vessel 349 via a liquid-phase transfer process. For example, referring again to FIG. 7 , after transferring the condensable mineralizer composition into receiving vessel 349, ammonia transfer vessel 745 may be vented. In certain embodiments, ammonia transfer vessel 745 is cooled, for example, to about dry ice temperature, and one or more valves between ammonia source 452 and ammonia transfer vessel 745 are opened. Ammonia gas flows through point-of-use purifier 458, is metered and controlled by mass flow controller 460, and is condensed as a liquid in ammonia transfer vessel 745. In certain embodiments, ammonia transfer vessel 745 is cooled to a relatively high temperature, for example, from about −20° C. to about 15° C., and the ammonia transfer and condensation process is carried out under elevated pressure as described above. After the desired amount of ammonia has been added to ammonia transfer vessel 745, for example, by integrating the output of mass flow controller 458, ammonia transfer vessel 745 may be heated, as needed, to about 25° C., about 30° C., or higher. When receiving vessel 349 is at approximately room temperature, it can contain HF vapor at a pressure near 1 atmosphere, as shown in FIG. 6. As a result, when valve 747 is opened to receiving vessel 349 and ammonia begins to flow from ammonia transfer vessel 745 to receiving vessel 349, solid NHF begins to form immediately and continues to form until the HF vapor and liquid in receiving vessel 349 are completely converted to NHF (and / or NH5F2). Using a large throat valve, such as a ball valve, for valve 747, which can be fully opened instantaneously, and using a fill tube with an internal diameter greater than 1, 2, or 3 millimeters, can reduce or eliminate problems associated with clogging. The initially formed NHF can be carried into receiving vessel 349 by flowing liquid ammonia, which is present at a pressure greater than 7 atmospheres or greater than 10 atmospheres, depending on the temperature of ammonia transfer vessel 745. In certain embodiments, heating valve 747 and connection 743 to a temperature of about 25° C. to about 250° C. or about 30° C. to about 100° C. prevents NH 4 F from forming embolisms in the lines.Any residual NHF in the ammonia transfer vessel 745 or in the tubing or valves between it and the receiving vessel 349 can be transferred by heating to a temperature of about 100° C. to about 250° C. In certain embodiments, the average temperature of the ammonia transfer vessel 745 and final transfer vessel 345 is maintained at about 2° C. to about 50° C., or about 5° C. to about 25° C. higher than the average temperature of the receiving vessel 349 during the liquid-phase transfer from the ammonia transfer vessel 745 to the receiving vessel 349. The valve between the receiving vessel 349 and final transfer vessel 345 can be opened during the liquid-phase ammonia transfer operation, allowing vapor displaced from the receiving vessel 349 by the incoming liquid to migrate into the final transfer vessel 345, thus not preventing more liquid ammonia from entering the receiving vessel 349.

[0060] After the receiving vessel or capsule is removed from the manifold, it may be heated to room temperature. In certain embodiments, the fill tube connecting the body of the receiving vessel or capsule to the valve is welded shut.

[0061] In certain embodiments, the mineralizer formation process can occur spontaneously or after additional processing. For example, the formation of one or more of NHF and NHF can occur spontaneously upon direct addition of NH to a receiving vessel containing HF, either at low temperature or after heating. GaX (where X = F, Cl, Br, or I) can similarly form one or more complexes upon addition of NH. The rate of such formation reactions can be controlled by slowly adding gaseous NH to a receiving vessel containing HF, for example, at a rate of less than about 12 standard liters per minute (SLM), less than about 5 SLM, or less than about 1 SLM, until the formation of the reaction product is complete. The appropriate rate of slow NH addition can be confirmed by measuring the process pressure during the addition of NH. Depending on the ammonia flow rate, the temperature of the receiving vessel during NH3 addition, and the conductance of the connections between the manifold and the interior of the receiving vessel, the pressure in the manifold during ammonia addition may be from about 0.1 Torr (13.3322 Pa) to about 15 atmospheres. In preferred embodiments, during the continuous slow-fill process, the pressure during ammonia addition is stable and does not exhibit brief fluctuations or spikes having durations of from about 1 millisecond to about 10 seconds. In certain embodiments, for example, when the temperature of the receiving vessel is above about -25°C and the ammonia pressure during the fill operation is above about 1.5 atmospheres (see, e.g., Figure 5), the slow addition of NH3 can be carried out not as a continuous flow, but by multiple short pulses of ammonia having durations of from about 0.01 seconds to about 30 seconds, or from about 0.1 seconds to about 10 seconds, separated by pauses of from about 1 second to about 60 seconds, allowing the mineralizer-forming reaction to occur gradually in a controlled manner. Further mineralizer-forming reactions, such as the reaction of NH4F and NH3 with Group III metal nitrides to form one or more of GaF3·2NH3 and (NH4)3GaF6, can occur at elevated temperatures. To provide a range of ammonia fill rates around the completion of the mineralizer reaction, multiple mass flow controllers with the same or different mass flow ranges can be arranged in parallel, for example as shown in Figure 1, to significantly reduce fill times while maintaining good accuracy.Following formation of the mineralizer reaction product, ammonia may be added to the receiving vessel at a rate of from about 1 SLM to about 1000 SLM, from about 5 SLM to about 500 SLM, or from about 10 SLM to about 250 SLM.

[0062] A control system for a manifold may include: a controller; a processor in communication with the controller; and a wired or wireless communication system that allows the controller to communicate with sensors, valves, sources, monitoring and evaluation devices, etc. The controller includes a central processing unit (CPU), memory, and support circuits. The controller is used to control one or more of the process sequences disclosed herein. The CPU is a general-purpose computer processor configured for use in an industrial environment to control processing equipment and other associated devices. The memory described herein, which is generally non-volatile memory, may include random access memory, read-only memory, floppy or hard disk drives, or other suitable forms of digital storage, local or remote. The support circuits are conventionally coupled to the CPU and include cache, clock circuits, input / output subsystems, power supplies, etc., and combinations thereof. Software instructions (programs) and data may be coded and stored in memory to instruct the processor in the CPU. The software programs (or computer instructions) readable by the CPU in the controller determine which tasks can be performed by the components of the overall system disclosed herein. Preferably, a CPU-readable program in the controller includes code that, when executed by the processor (CPU), performs tasks associated with monitoring and executing one or more of the methods or method steps described herein. The program will include instructions used to control the various hardware and electronic components in the system to perform the various process tasks and various process sequences used to implement the processing methods described herein.

[0063] Sensors in the support circuitry located within the manifold can sense conditions within the manifold and / or transfer or receiving vessel, such as temperature, pressure, and / or gas concentration and composition, and can signal the information to a controller. Flow monitors can signal the controller with information regarding the flow rate through the corresponding inlet or outlet. The controller (via a processor) can respond to the received information and control devices according to the information and predetermined command parameters. For example, the controller can signal an energy source to provide thermal energy to a heating jacket for the manifold. The controller can signal one or more valves to open or close to predetermined flow levels during the course of mineralizer synthesis. The controller can be programmed to implement a method of synthesizing a purified mineralizer composition according to embodiments of the present disclosure.

[0064] The controller can be programmed to accept multiple parameters to achieve the desired control of pneumatic or solenoid valves during pre-programmed sequences for pumping, purging, HF distillation, HF transfer, HF bottoms dump, ammonia transfer, or capsule cutting, as well as multiple maintenance procedures. In addition to the pre-programmed sequences, a manual mode can be accessed for troubleshooting and non-routine maintenance and testing. In some configurations, mass flow controller (MFC) set points can be entered in manual mode outside of the pre-programmed sequences. Valve interlocks and alarms can be used to prevent the opening of certain valve combinations that are considered dangerous or destructive to the equipment.

[0065] Through the use of preprogrammed sequences stored in memory, text prompts unrelated to the valve sequence can be used to prompt the operator when to perform specific tasks, including heating and cooling the chiller, manifold, and / or capsule dewar; opening and closing gas cylinders; opening and closing manual valves; and performing various leak checks before performing a specific operation. In certain configurations, once the operator has performed a task, they can press "NEXT" to continue the preprogrammed sequence. Text prompts can also be used to inform the operator of the purpose of the current valve configuration and the conditions required for the process to transition to the next step. For example, this could take the form of "purging line, waiting for process pressure," accompanied by a timer display. Preprogrammed parameters for one, some, or all pump / purge sequences can include: the number of pump / purge cycles in a given sequence; the high pressure and purge time in the pump / purge cycle before transitioning to the pump step or next step in the sequence; and the low pressure target and pump time before transitioning to the purge step or next step in the sequence. In the loop, if an additional pump purge is required, the system can be checked using conditions such as passing a pressure buildup test. If not, the sequence can return to the pumping step. In certain embodiments, it is useful to combine pumping / purging steps with the transfer of condensable mineralizer and / or ammonia in these pre-programmed sequences to facilitate operation and ensure minimal contamination.

[0066] Warnings and alarms sent from the controller can be configured to notify operators of process conditions that are out of specification or when the process needs attention. These can take the form of high / low and low / low pressure and flow rate alarms, or pre-programmed steps that exceed a certain time. Additionally, the warning and alarm system can track mineralizer and ammonia usage to provide notification when maintenance is required. For setpoints that change from run to run (including mineralizer and ammonia amounts), pre-programmed process setpoints can be prompted to change at the start of a sequence.

[0067] By practicing the methods described herein, the ultra-high purity mineralizer desirably has a total oxygen concentration, including adsorbed moisture, hydrates, and chemically bonded oxides, of less than about 100 parts per million by weight. In certain embodiments, the oxygen concentration in the purified mineralizer is less than about 10 parts per million, less than about 5 parts per million, less than about 2 parts per million, less than about 1 parts per million, less than about 0.3 parts per million, or less than about 0.1 parts per million. The ultra-high purity mineralizer may also have a purity of greater than 99%, greater than 99.9%, greater than 99.99%, greater than 99.999%, or greater than 99.9999% on a trace metals basis. The ultra-high purity mineralizer may also have a total concentration of other light group elements, such as boron, carbon, silicon, phosphorus, and sulfur, of less than 10 parts per million, less than 1 parts per million, or less than 0.1 parts per million.

[0068] A simplified flowchart 900 for the synthesis of ultra-high purity mineralizer is shown in FIG. 9, which may be implemented using one or more programs executed by a processor of a controller. This diagram is merely an example and is not intended to limit the scope of the disclosure provided herein. Those skilled in the art will recognize other modifications, variations, and alternatives. In step 902, a receiving vessel is connected to a condensable mineralizer transfer manifold using a leak-proof seal. In step 904, the tubing and / or the space encompassed by the new connection are evacuated and purged, with further evacuation and purging of additional portions of the manifold. In step 906, the first transfer vessel is cooled. In step 908, a quantity of condensable mineralizer composition is transferred in the vapor phase from the source vessel to the first transfer vessel. In step 910, optionally, at least a portion of the condensable mineralizer composition is transferred to one or more additional transfer vessels. In step 912, the amount of condensable mineralizer composition in at least one transfer vessel is measured and adjusted to a predetermined level, if necessary. In step 914, the condensable mineralizer composition from the last transfer vessel is transferred to a receiving vessel. In certain embodiments, the pressure in the manifold is maintained below a pressure of about 1 to about 3 atmospheres.

[0069] Surprisingly, the method described herein provides a reliable and accurate means for delivering ultra-high purity mineralizer to a receiving vessel for ammonothermal crystal growth. It is common in the semiconductor industry to utilize vacuum systems and gas manifolds constructed entirely of metal, e.g., entirely of stainless steel, and to control gas flow rates using only mass flow controllers. For example, the mineralizer synthesis method described by Mikawa et al. generally follows these procedures. In contrast, the method of the present invention can utilize plastic and metal compositions and volumetric measurement methods that are generally considered insufficiently accurate for semiconductor-grade work. For example, the use of both metal and plastic components in a vacuum system or gas manifold implies the need for metal-to-plastic seals, which are generally considered unreliable and prone to leaks. The inventors surprisingly discovered that the metal-to-plastic seals of the manifolds of the present invention can operate reliably, albeit with periodic preventative maintenance, thereby enabling simple volumetric measurement methods to measure mineralizer volume with accuracy better than 5%, better than 2%, or better than 1%. As mentioned above, these volumetric measurement methods avoid potential calibration issues with mass flow controllers. Additionally, these methods avoid clogging problems that are common, especially when using low conductance components such as point-of-use purifiers to process condensable vapors.

[0070] In some embodiments, the mineralizer is used as a raw material for ammonothermal growth of at least one single crystal of a Group III metal nitride. A capsule containing ultra-high purity mineralizer and ammonia is placed in an autoclave or an internally heated high-pressure apparatus, such as those described in U.S. Pat. No. 8,021,481 and U.S. Patent Application Publication Nos. 2010 / 0031875 and 13 / 472356. When used in an autoclave, the space between the capsule and the inner diameter of the autoclave is filled with ammonia to a volume percentage similar to that inside the capsule, thereby creating a pressure outside the capsule similar to that inside the autoclave when heated, thereby minimizing capsule deformation (a so-called pressure balancing method known in the art). After all raw materials are added to the autoclave or high-pressure apparatus, the autoclave or high-pressure apparatus is sealed.

[0071] The polycrystalline group-III metal nitride is then treated in supercritical ammonia at a temperature greater than about 400° C. and a pressure of about 50 megapascals (MPa), during which at least a portion of the polycrystalline group-III metal nitride is etched away and recrystallized into at least one group-III metal nitride crystal having a wurtzite structure. In some embodiments, the polycrystalline group-III metal nitride is treated in supercritical ammonia at a temperature greater than about 500° C., greater than about 550° C., greater than about 600° C., greater than about 650° C., greater than about 700° C., or about 750° C. In some embodiments, the polycrystalline group-III metal nitride is treated in supercritical ammonia at a pressure greater than about 100 MPa, greater than about 200 MPa, greater than about 300 MPa, greater than about 400 MPa, greater than about 500 MPa, or greater than about 600 MPa.

[0072] After crystal growth is performed for a predetermined period of time, the autoclave or high-pressure apparatus is cooled. After the autoclave or capsule has cooled to less than about 100°C, less than about 75°C, less than about 50°C, or less than about 35°C, the valve to the autoclave is opened and / or the capsule is vented to remove the ammonia. In certain embodiments, the gas-phase ammonia is allowed to flow from the autoclave or capsule and is chemically captured by passing it through an acidic aqueous solution. In certain embodiments, the gas-phase ammonia is combusted by passing it through a flame to form HO and N. In certain embodiments, the ammonia is recovered for purification and reuse.

[0073] After cooling, removing the ammonia, and opening the autoclave or internally heated high pressure apparatus and capsule, the grown crystals, or boule, are removed from the capsule or autoclave.

[0074] One or more wafers can be prepared from the as-grown boule using a single or multi-wire saw, an ID saw, an OD saw, or the like. Wafers can be prepared with a predetermined miscut angle by precisely orienting the boule using an X-ray goniometer before cutting. After slicing, the crystalline wafers can be lapped, polished, and chemically mechanically polished using methods known in the art. In some embodiments, the dislocation density across the large area surface of the wafer is less than about 10 7 cm -2 Less than, about 10 6 cm -2 Less than, about 10 5 cm -2 Less than, about 10 4 cm -2 Less than, about 10 3 cm -2 Less than or about 10 2 cm -2 In some embodiments, the full width at half maximum of the X-ray diffraction lines corresponding to the crystallographic orientation of the large area surface is less than 300 arc seconds, less than 150 arc seconds, less than 100 arc seconds, less than 50 arc seconds, less than 40 arc seconds, less than 30 arc seconds, or less than 20 arc seconds.

[0075] FIG. 10 shows a block diagram of a system for the growth of Group III metal nitride crystals using the ultra-high purity mineralizers disclosed herein.

[0076] As shown, the method of system 1000 begins in step 1002 with loading a capsule filled with a predetermined amount of ultra-high purity mineralizer and ammonia into a high-pressure apparatus, such as an autoclave or internally heated high-pressure reactor. In step 1004, the capsule is heated to a temperature greater than about 400°C to generate an internal pressure greater than about 50 MPa. In step 1006, the capsule is cooled in the high-pressure reactor. In step 1008, the ammonia is removed from the capsule. In step 1010, at least one group III metal nitride boule is removed from the capsule. In step 1012, at least one group III metal nitride wafer is prepared from the at least one group III metal nitride boule. In step 1014, a group III metal nitride wafer is prepared from the at least one group III metal nitride boule, e.g., In. x Al y Ga 1-x-y A semiconductor structure including an N active layer, where 0≦x, y, x+y≦1, is formed on the III-metal nitride wafer. Step 1016 fabricates a device including the semiconductor structure, such as at least one of a light emitting diode, a laser diode, a diode, a photodiode, a sensor, and a transistor.

[0077] The Group III metal nitride crystal wafer can be used as a substrate for the fabrication of semiconductor structures and further optoelectronic and electronic devices such as at least one of: light emitting diodes, laser diodes, photodetectors, avalanche photodiodes, transistors, rectifiers, and thyristors; transistors, rectifiers, Schottky rectifiers, thyristors, PIN diodes, metal semiconductor metal diodes, high electron mobility transistors, metal semiconductor field effect transistors, metal oxide field effect transistors, power metal oxide semiconductor field effect transistors, power metal insulator semiconductor field effect transistors, bipolar junction transistors, metal insulator field effect transistors, heterojunction bipolar transistors, power insulated gate bipolar transistors, power vertical junction field effect transistors, cascade switches, intra-subband emitters, quantum well infrared photodetectors, quantum dot infrared photodetectors, solar cells, and diodes for photoelectrochemical water splitting and hydrogen production devices.

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

[0079] Further embodiments support the methods of making and using the ultra-pure mineralizers disclosed herein. Any of the following embodiments can be implemented in various variations.

[0080] While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the present disclosure may be devised without departing from the basic scope thereof. Preferred embodiments of the present invention will now be described in detail.

[0081] Embodiment 1 1. A method for growing Group III metal nitride crystals, comprising: The method comprises: providing a manifold comprising one or more transfer vessels, a source vessel containing a condensable mineralizer composition, and a receiving vessel; cooling a metal surface within the one or more transfer vessels, the metal surface being comprised of a composition that does not form reaction products when exposed to the condensable mineralizer composition in a liquid phase; transferring a quantity of the condensable mineralizer composition in a vapor phase to the one or more transfer vessels and causing condensation of the condensable mineralizer composition within the at least one transfer vessel; measuring the amount of the concentrate mineralizer composition in at least one of the one or more transfer vessels; transferring at least a portion of the condensable mineralizer composition to the receiving vessel; and forming at least a portion of a group III metal nitride boule by an ammonothermal crystal growth process, said ammonothermal crystal growth process comprising: exposing the seed crystal to a temperature of at least about 400°C; and exposing the seed crystals to mineralizer formed from the condensed mineralizer composition transferred from the receiving vessel. Including steps A method comprising:

[0082] Embodiment 2 the transferred amount of the condensable mineralizer composition in the one or more transfer vessels is determined by volumetric measurement; 10. The method of embodiment 1, further comprising measuring the temperature of the condensable mineralizer composition.

[0083] Embodiment 3 the fluid level of the condensable mineralizer composition is measured by a fluid level sensor; 3. The method of embodiment 2, wherein the fluid level sensor comprises at least one of an ultrasonic level transmitter, a laser level transmitter, a guided pulse sensor, and a sensing guided pulse transducer.

[0084] Embodiment 4 10. The method of embodiment 1, wherein the transferred amount of the concentrated mineralizer composition in the one or more transfer vessels is determined by gravitational measurement.

[0085] Embodiment 5 2. The method of embodiment 1, wherein the metal surface is comprised of silver.

[0086] Embodiment 6 2. The method of claim 1, wherein not forming reaction products when exposed to the condensable mineralizer composition in a liquid phase comprises not producing corrosion products corresponding to a thickness loss of more than 100 micrometers after use for a period of at least three months.

[0087] Embodiment 7 2. The method of embodiment 1, wherein the condensable mineralizer composition comprises HF, which subsequently reacts with NH to form at least one of NHF and NHF.

[0088] Embodiment 8 10. The method of embodiment 1, further comprising transferring a second mineralizer composition comprising at least one of chlorine, bromine, and iodine to the receiving vessel.

[0089] Embodiment 9 2. The method of embodiment 1, further comprising passing the condensable mineralizer composition to a distillation column and subjecting the condensable mineralizer composition to a fractional purification process.

[0090] Embodiment 10 10. The method of embodiment 1, further comprising passing the condensable mineralizer composition through a mass flow controller.

[0091] Embodiment 11 11. The method of embodiment 10, wherein the condensable mineralizer composition in the receiving vessel has a total oxygen content of less than about 1 parts per million (ppm) by weight.

[0092] Embodiment 12 10. The method of embodiment 1, further comprising characterizing the condensable mineralizer composition by at least one method selected from electrical conductivity measurements, Fourier transform infrared spectroscopy, mass spectroscopy, and gas chromatography.

[0093] Embodiment 13 2. The method of embodiment 1, wherein a purification of at least 5 theoretical plates is achieved for the mineralizer composition received directly from the source vessel.

[0094] Embodiment 14 using an integrated manifold to transfer controlled amounts of the condensable mineralizer composition and ammonia to the receiving vessel through a single outlet; forming at least a portion of the group III metal nitride boule further comprises exposing at least a portion of the integral manifold to the condensable mineralizer composition, followed by exposing the at least a portion of the integral manifold to ammonia; The formation of reaction products between the condensable mineralizer composition and ammonia in the integrated manifold comprises: maintaining the temperature of the integral manifold at a temperature greater than about 30°C; and performing one or more pumping / purging cycles within the integrated manifold between exposing the at least a portion of the integrated manifold to the condensable mineralizer composition and exposing the at least a portion of the integrated manifold to ammonia. 2. The method of embodiment 1, wherein the method is prevented by at least one of:

[0095] Embodiment 15 2. The method of embodiment 1, further comprising transferring a controlled amount of ammonia to the receiving vessel, wherein a flow rate of the ammonia stream is controlled using at least one mass flow controller and comprises a first flow rate and a second flow rate, the second flow rate being greater than the first flow rate.

[0096] Embodiment 16 16. The method of embodiment 15, wherein the first flow rate is less than about 12 standard liters per minute and does not produce measurable short-term pressure fluctuations having a duration of between 1 millisecond and 10 seconds.

[0097] Embodiment 17 10. The method of embodiment 1, wherein at least one transfer operation is carried out at a vapor pressure of the condensable mineralizer composition greater than 1 atmosphere.

[0098] Embodiment 18 10. The method of embodiment 1, wherein the step of transferring the condensable mineralizer composition to the receiving vessel is carried out primarily in the liquid phase.

[0099] Embodiment 19 2. The method of embodiment 1, wherein the step of transferring ammonia to the receiving vessel is carried out primarily in the liquid phase.

[0100] Embodiment 20 2. The method of embodiment 1, further comprising forming at least one group III metal nitride wafer from the ammonothermally grown group III metal nitride boule.

[0101] Embodiment 21 1. A method for growing Group III metal nitride crystals, comprising: The method comprises: providing a manifold comprising at least one transfer vessel, a source vessel containing a condensable mineralizer composition, and a receiving vessel; cooling a metal surface in said at least one transfer container, said metal surface being comprised of a composition that does not undergo corrosion corresponding to a thickness loss of more than 100 micrometers upon reaction with said condensable mineralizer composition after use for a period of at least three months; transferring a quantity of the condensable mineralizer composition in a vapor phase to the at least one transfer vessel and causing condensation of the condensable mineralizer composition within the at least one transfer vessel; passing the condensable mineralizer composition through a distillation column to subject the condensable mineralizer composition to a fractional distillation purification process; passing the condensable mineralizer composition through a mass flow controller; transferring at least a portion of the condensable mineralizer composition to the receiving vessel and quantifying the amount of the condensable mineralizer composition transferred using the mass flow controller; and forming at least a portion of a group III metal nitride boule by an ammonothermal crystal growth process, said ammonothermal crystal growth process comprising: exposing the seed crystal to a temperature of at least about 400°C; and exposing the seed crystals to mineralizer formed from the condensed mineralizer composition transferred from the receiving vessel. Including steps A method comprising: [Explanation of symbols]

[0102] 200 First transfer container 201 Outer Enclosure 203 Lid 205 Closed volume, internal volume 207 Steam inlet 209 Inlet Valve 211 Steam outlet 213 Outlet Valve 215 Internal heat exchanger 217, 227 Fluid inlet 219 Fluid Outlet 221 Internal temperature sensor 223 Fluid level sensor, liquid level sensor 225 Outer heat exchange bath 226 Bath Fluid 228 Heat exchange loop, external heat exchange element 229 Heat exchange fluid outlet 230 External Temperature Sensor 331 Distillation Tower 333 Insulation Sleeve 335 Enclosure 339 Filling materials 341, 460 Mass Flow Controller 343 Outlet Tube 345 Last Transport Container 347, 747 valve 349 Receiving container 400 Integrated Manifold 450 Ammonia Manifold 452 Ammonia Source 454 Vacuum Pump 456 Pressure Gauge 458 Position-based purifier 465 Purge Inlet 743 Outlet 745 Ammonia transport vessel 842 Second transport container 844 connections 1000 systems

Claims

1. A method for producing a manifold comprising: providing at least two transfer vessels, a first source vessel containing a condensable mineralizer composition including HF, a second source vessel containing ammonia, and a receiving vessel; evacuating the receiving vessel; transferring a first amount of the condensable mineralizer composition in a vapor phase to a first transfer vessel and causing condensation of the condensable mineralizer composition within the first transfer vessel; measuring the first amount of the concentrated mineralizer composition in the first transfer container; transferring the measured second amount of the condensable mineralizer composition from the first transfer vessel to the receiving vessel; transferring a first quantity of ammonia to a second transfer vessel; and transferring a second quantity of ammonia from the second transfer vessel to the receiving vessel in the liquid phase through a fill tube, the fill tube having an inner diameter greater than 1 millimeter; A method for producing a Group III metal nitride crystal, comprising:

2. The manufacturing method described in claim 1, further comprising a step of forming at least a portion of a Group III metal nitride boule by an ammonothermal crystal growth process, exposing a seed crystal to a mineralizer formed from the second amount of condensable mineralizer composition and the second amount of ammonia transferred to the receiving vessel.

3. The method of claim 1 or 2, wherein the filling tube has an inner diameter of greater than 2 millimeters.

4. The method of claim 1 , wherein the first transfer container and the fill tube comprise at least one of silver, a silver alloy, Monel 400, gold, platinum, palladium, rhodium, iridium, or ruthenium.

5. 10. The process of claim 1, wherein the second amount of condensable mineralizer composition is in a liquid phase when transferred from the first transfer vessel to the receiving vessel.

6. 10. The process of claim 1, wherein the second quantity of ammonia is transferred in liquid phase from the second transfer vessel to the receiving vessel through a large throat valve comprising a ball valve.

7. 10. The process of claim 1, wherein liquid ammonia has a pressure greater than 7 atmospheres during transfer of the second quantity of ammonia from the second transfer vessel to the receiving vessel.

8. 10. The process of claim 1, wherein valves and connections between the second transfer vessel and the receiving vessel are heated to a temperature of from 25° C. to 250° C. during transfer of the second amount of ammonia from the second transfer vessel to the receiving vessel.

9. 9. The process of claim 8, wherein the valve and the connection between the second transfer vessel and the receiving vessel are heated to a temperature of from 30° C. to 100° C. during the transfer of the second amount of ammonia from the second transfer vessel to the receiving vessel.

10. 2. The method of claim 1, wherein condensing the condensable mineralizer composition in the first transfer vessel is achieved by cooling a metal member in the first transfer vessel, the metal member comprising at least one of silver, a silver alloy, Monel 400, gold, platinum, palladium, rhodium, iridium, or ruthenium, and having a metal surface configured to condense and cool the condensable mineralizer composition in a liquid phase.

11. the transferred amount of the condensable mineralizer composition in the first transfer vessel is determined by volumetric measurement; The method of claim 1 further comprising measuring the temperature of the condensable mineralizer composition.

12. 10. The manufacturing method of claim 1, wherein the fluid level of the condensable mineralizer composition is measured by a fluid level sensor, the fluid level sensor comprising at least one of an ultrasonic level transmitter, a laser level transmitter, a guided pulse sensor, and a sensing guided pulse transducer.

13. 10. The method of claim 1, further comprising transferring a second mineralizer composition comprising at least one of chlorine, bromine, and iodine to the receiving vessel.

14. 10. The method of claim 1, further comprising passing the condensable mineralizer composition through a distillation column to subject the condensable mineralizer composition to a fractional purification process.

15. 11. The process of claim 10, wherein a refinement of at least 5 theoretical plates is achieved for the mineralizer composition received directly from the source vessel.

16. 10. The method of claim 1, wherein the first transfer vessel is heated to a temperature 2°C to 50°C higher than the temperature of the receiving vessel during transfer of the condensable mineralizer composition.

17. 10. The process of claim 1, wherein the second transfer vessel is heated to a temperature between 2°C and 50°C higher than the temperature of the receiving vessel during the liquid phase transfer of the second amount of ammonia.

18. The method of claim 2 further comprising forming at least one group III metal nitride wafer from the ammonothermally grown group III metal nitride boule.

Images