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WO2010060034A1 - Procédés de production d’un nutriment de gan pour la croissance ammonothermique - Google Patents

Procédés de production d’un nutriment de gan pour la croissance ammonothermique Download PDF

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Publication number
WO2010060034A1
WO2010060034A1 PCT/US2009/065513 US2009065513W WO2010060034A1 WO 2010060034 A1 WO2010060034 A1 WO 2010060034A1 US 2009065513 W US2009065513 W US 2009065513W WO 2010060034 A1 WO2010060034 A1 WO 2010060034A1
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Prior art keywords
gan
group iii
polycrystalline
growth
iii nitride
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Edward Letts
Tadao Hashimoto
Masanori Ikari
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SixPoint Materials Inc
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SixPoint Materials Inc
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0632—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/005—Growth of whiskers or needles
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • C30B29/406—Gallium nitride
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes

Definitions

  • the invention is related to a production method of polycrystalline GaN for use as a nutrient or source material in the ammonothermal method. Design of the reactor material to control impurities while producing high yields is discussed. 2. Description of the existing technology.
  • Gallium nitride (GaN) and its related group III alloys are the key material for various opto-electronic and electronic devices such as light emitting diodes (LEDs), laser diodes (LDs), microwave power transistors, and solar-blind photo detectors.
  • LEDs are widely used in cell phones, indicators, displays, and LDs are used in data storage disc drives.
  • the majority of these devices are grown epitaxially on heterogeneous substrates, such as sapphire and silicon carbide.
  • the heteroepitaxial growth of group III- nitride causes highly defected or even cracked films, which hinders the realization of high- end optical and electronic devices, such as high-brightness LEDs for general lighting or high-power microwave transistors.
  • Single crystalline group Ill-nitride wafers can be sliced from bulk group Ill-nitride crystal ingots and then utilized for high-end homoepitaxial growth of optical and electronic devices.
  • single crystalline GaN wafers are favorable because it is relatively easy to control the conductivity of the wafer and GaN wafers will provide the smallest lattice/thermal mismatch with device layers.
  • the GaN wafers needed for homogenous growth are currently expensive compared to heteroepitaxial substrates. It has been difficult to grow group Ill-nitride crystal ingots due to their high melting point and high nitrogen vapor pressure at high temperature.
  • ammonothermal method is a promising alternative growth method that has been used to achieve successful growth of real bulk GaN ingots (T. Hashimoto, et al., Jpn. J. Appl. Phys., 46, (2007), L889).
  • Ammonothermal growth has the potential for growing large GaN crystal ingots because its solvent, high-pressure ammonia, has advantages as a fluid medium including high transport speed and solubility of the source materials, such as GaN polycrystals or metallic Ga.
  • State-of-the-art ammonothermal method U.S. Patent No. 6,656,615; International Application Publication Nos. WO 2007/008198; and WO 2007/117689; and U.S. Application Publication No.
  • the parasitic GaN polycrystals in HVPE are in the suitable shape for ammonothermal nutrients; however, since HVPE are designed to minimize polycrystalline deposits and to improve epitaxial growth, the production yield of the GaN polycrystals is very low. Thus, using parasitic GaN polycrystals in HVPE as ammonothermal nutrient is not practical for mass production of bulk GaN. A method to produce large quantities of polycrystalline source material would improve the feasibility to scale the ammonothermal growth and facilitate large-scale production of high-end GaN ingots.
  • the present disclosure describes methods and reactor designs for growing polycrystalline group III nitride, such as polycrystalline gallium nitride (GaN).
  • polycrystalline group III nitride such as polycrystalline gallium nitride (GaN).
  • the polycrystalline group III nitride material is suitable for use in the formation of single-crystal group III nitride ingots.
  • the present disclosure provides a method of producing polycrystalline group III nitride.
  • the method comprises contacting a gaseous hydrogen halide with a group III element source material in a first heated region to produce a group III halide gas, contacting the group III halide gas with ammonia gas in a growth region, and producing a crystalline group III nitride, wherein greater than 80% of the total produced group III nitride is polycrystalline group III nitride.
  • the group III element may be gallium.
  • the present disclosure provides a method for recycling polycrystalline GaN source material used in a previous ammonothermal growth process.
  • the method comprises heating and maintaining the polycrystalline GaN source material at a temperature greater than 700 0 C, back etching a surface of the polycrystalline GaN source material to provide a back etched polycrystalline GaN, and depositing additional polycrystalline GaN on the surface of the back etched polycrystalline GaN by a hydride vapor phase growth process.
  • Still other embodiments of the present disclosure provide a reactor for growing polycrystalline GaN.
  • the reactor comprises a first heated region comprising a first gas inlet configured to introduce a nitrogen-containing gas, a second heated region comprising a second gas inlet configured to introduce a halide-containing gas, wherein the first heated region and the second heated region are configured to maintain separation of the gases in each region, and a growth region in gaseous contact with the first heated region and the second heated region and configured to allow growth of polycrystalline GaN.
  • Another embodiment of the present disclosure provides a method for forming single-crystal GaN.
  • the method comprises forming a polycrystalline GaN by a hydride vapor phase growth process, utilizing the polycrystalline GaN as the gallium source material in an ammonothermal crystal growth process, and forming single-crystal GaN by the ammonothermal crystal growth process.
  • FIG. 1 illustrates a schematic drawing of HVPG reactor according to one embodiment of the present disclosure.
  • FIG. 2 is an image of a growth region of the HVPG reactor according to one embodiment of the present disclosure.
  • Pyro lytic BN provides the deposition surface for the GaN growth. Recycled GaN and the new GaN growth are labeled.
  • the present disclosure provides methods for growing polycrystalline group III nitride material suitable for use as a group III nitride source material in formation of single- crystal group III nitride compositions, for example by an ammonothermal growth process.
  • the methods of the present disclosure also allow for recycling of poly crystalline group III nitride materials remaining after an ammonothermal growth process. Reactors designed for growing polycrystalline group III nitride material are also disclosed.
  • all numbers expressing quantities of ingredients, processing conditions and the like used in the specification and claims are to be understood as being modified in all instances by the term "about".
  • any numerical range recited herein is intended to include all sub-ranges subsumed therein.
  • a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of less than or equal to 10.
  • the present invention provides a method of producing poly crystalline GaN suitable for use as a nutrient or source material for the ammonothermal growth of group Ill-nitride wafers, primarily group Ill-nitride single crystalline wafers that include at least the element Ga with the possible addition of another group III elements B, Al, and In, such as Al x Gai_ x N or In x Gai_ x N (0 ⁇ x ⁇ l), or Al x In y Gai_ x _ y N (0 ⁇ x ⁇ l, 0 ⁇ y ⁇ l).
  • the group Ill-nitride wafers or ingots are grown by the ammonothermal method which utilizes high-pressure NH3 as a fluid medium, nutrient containing group III elements, and seed crystals that are group Ill-nitride single crystals.
  • the high-pressure NH3 provides high solubility of the nutrient and high transport speed of dissolved precursors.
  • the ammonothermal growth requires the steady supply of a nutrient, such as Ga metal or GaN.
  • a GaN source has the benefit of providing improved growth rate stability compared to Ga metal.
  • One particularly useful GaN source material is polycrystalline GaN.
  • HVPE Hydride Vapor Phase Epitaxy
  • the present disclosure provides a modification of the HVPE setup and a method in which the traditionally desired epitaxy is removed and the reactor design is instead optimized to produce a high yield of polycrystalline GaN.
  • the polycrystalline GaN may be then used as a source material for single-crystal growth, for example, by an ammonothermal growth process.
  • This new and non-obvious method will be denoted herein as Hydride Vapor Phase Growth (HVPG).
  • the reactor and method may also be suitable for the formation of other polycrystalline group III nitrides, such as aluminum nitride (AlN), indium nitride (InN) and mixed group III nitrides, such as Al x Gai_ x N or In x Gai_ x N (0 ⁇ x ⁇ l), or Al x In y Gai_ x _ y N (0 ⁇ x ⁇ l, 0 ⁇ y ⁇ l).
  • AlN aluminum nitride
  • InN indium nitride
  • mixed group III nitrides such as Al x Gai_ x N or In x Gai_ x N (0 ⁇ x ⁇ l), or Al x In y Gai_ x _ y N (0 ⁇ x ⁇ l, 0 ⁇ y ⁇ l.
  • one method of applying HVPG for the formation of a group III nitride such as gallium nitride; a group III halide gas, for example, a gallium halide gas such as gallium chloride gas enters a first region of the HVPG reactor.
  • a second nitrogen-containing gas, such as ammonia enters the reactor in a second region of the reactor.
  • the first region and the second region of the reactor are physically separated from one another by a wall or by a sufficient distance to allow the gases to migrate to the growth region without mixing to an appreciable extent or at all.
  • the group III halide gas may be formed by reacting a group III elemental material with a hydrogen halide gas.
  • gallium halide gas GaX 2 , where X is halide (i.e., F, Cl, Br, I) and z is an integer from 1-3
  • a gallium source material may be formed by reacting a gallium source material and a hydrogen halide gas, such as HF, HCl, HBr, or HI, in a first region of the reactor.
  • a hydrogen halide gas such as HF, HCl, HBr, or HI
  • suitable group III elemental material may be used as the source material.
  • suitable Ga source material may include, but is not limited to, elemental Ga in metallic, liquid, powder, pellet, granule, wire, or rod form may be used.
  • the hydrogen halide gas may be introduced into the first region of the reactor through an inlet, such as a nozzle.
  • the Ga source material, HCl, and the resultant GaCl may all be physically separated from the nitrogen-containing gas (i.e., the NH3 gas) until the GaCl enters a growth region of the reactor.
  • one embodiment of the methods of the present disclosure provides a method for producing polycrystalline group III nitride.
  • the method may comprise contacting a gaseous hydrogen halide with a group III element source material in a first heated region to produce group III halide gas, contacting the group III halide gas with a nitrogen containing gas, such as ammonia gas, in a growth region, and producing a crystalline group III nitride, wherein greater than 80% of the total produced group III nitride is polycrystalline group III nitride.
  • the group III element may be gallium.
  • the group III halide gas is therefore, GaX 2 , where X is a halide (F, Cl, Br, or I) and z is an integer from 1 to 3 and the group III nitride is GaN.
  • other group III elements such as aluminum or indium or mixtures of gallium with aluminum and/or indium may be used as the group III element source material.
  • suitable Ga source material may include various forms of metallic Ga, such as, for example, liquid Ga, Ga powder, Ga pellets, Ga granules, Ga wire, Ga rods or ingots, or mixtures of any thereof.
  • equivalent forms of metallic aluminum or indium may be utilized.
  • a gallium source material may be contacted with gaseous hydrogen chloride gas in a first heated region of the reactor.
  • the temperature of the first heated region may be at least 700 0 C, for example, at a temperature ranging from 700 0 C to 1200 0 C.
  • the gallium source material may be held within the first heated region of the reactor and the HCl gas may be introduced into the first heated region through a gas inlet such as a nozzle.
  • the gallium source material may then react with the HCl gas to produce a gallium chloride gas, such as GaCl 2 where z is an integer from 1-3.
  • the gallium chloride gas may then migrate or move from the first heated region to a growth region.
  • the growth region may be at a temperature of at least 700 0 C, for example at a temperature ranging from 700 0 C to 1300 0 C.
  • the gallium chloride gas may be contacted with ammonia gas to produce gallium nitride (GaN) vapor.
  • the gallium nitride vapor may then deposit or crystallize in the growth region to form crystalline GaN, wherein greater than 80% of the total produced GaN nay be polycrystalline GaN. In specific embodiments, greater than 90% of the total produced GaN may be polycrystalline GaN.
  • the method may comprise introducing a gallium halide gas, such as a gallium chloride gas into a first heated region and allowing the gallium halide gas to migrate to a growth region.
  • the first heated region may have a temperature of at least 700 0 C, for example at a temperature ranging from 700 0 C to 1200 0 C.
  • the gallium halide gas may then migrate to the growth region where it is contacted with ammonia gas to produce GaN vapor.
  • the GaN vapor may then deposit or crystallize in the growth region as polycrystalline GaN, such as described before.
  • the growth region may not have any material deposited in it prior to polycrystalline GaN growth.
  • the growth region may contain poly crystalline GaN prior to introducing gallium halide and nitrogen-containing gases.
  • the pre-existing poly crystalline GaN may nucleate additional growth of poly crystalline GaN and/or act as a template for additional growth.
  • the use of pre-existing polycrystalline GaN may increase yield of GaN in the reactor.
  • the pre-existing polycrystalline GaN may have had its surface etched prior to introducing it into the growth region, or the pre-existing polycrystalline GaN may be etched once placed in the growth region.
  • incorporation of impurities into the product polycrystalline group III nitride may increase due to increased growth rate.
  • oxygen concentration in single crystalline GaN is at the order of 10 17 atoms/cm 3 even though the reactor may be formed from an oxide containing material, such as quartz.
  • polycrystalline GaN grown in a conventional HVPE setup showed oxygen concentration as high as 10 18 atoms/cm . Without intending to be limited by any theory, it is believed that this may be because polycrystalline group III nitride has more defects and grain boundaries which may act as incorporation sites of oxygen.
  • the HVPG reactors in the present disclosure utilizes non-oxide containing or forming materials, such as e.g. pyrolytic BN components or components formed of other suitable materials not formed of oxides, from which oxygen might be extracted when in direct contact with the hydrogen halide gas, the group III halide gas, and the ammonia NH 3 in a heated region or growth region.
  • non-oxide containing or forming materials such as e.g. pyrolytic BN components or components formed of other suitable materials not formed of oxides, from which oxygen might be extracted when in direct contact with the hydrogen halide gas, the group III halide gas, and the ammonia NH 3 in a heated region or growth region.
  • impurities may be a larger concern for growth of polycrystalline GaN than for growth of single crystal GaN, since impurity incorporation is significantly greater for growth of polycrystalline material compared to single crystal epitaxial films grown by the traditional HVPE.
  • incorporation of oxygen in the polycrystalline GaN may result in impure polycrystalline GaN material that is less suited for use in other processes, such as ammonothermal growth processes.
  • the impurity and oxide concentration in GaN polycrystals from the HVPG process may be reduced by utilizing oxide-free materials in the growth environment for deposition of polycrystalline GaN.
  • all interior surfaces in the reactor such as the first heated region, the second heated region and the growth region, that are in direct contact with the gases may be formed of or coated with a non-oxide material.
  • a non-oxide material may be, e.g., boron nitride or pyrolytic boron nitride.
  • the non-oxide material may be pyrolytic boron nitride.
  • the entire reactor need not be formed of a material that lacks an oxide.
  • the growth region and optionally the first and/or second heated regions may be formed of a material that lacks an oxide, and the remainder of the HVPG reactor may be formed of conventional materials that may be one or more oxides (such as quartz).
  • surfaces in direct contact with the gases during the HVPG process such as surfaces in the first heated region and the growth region, may be coated with the non-oxide material.
  • Embodiments of the present methods provide for the production of polycrystalline group III nitride having an oxygen content quite low, such as less than about 1 x 10 19 atoms/cm 3 or less than 9 x 10 18 atoms/cm 3 .
  • the oxygen concentration in polycrystalline GaN may be about 8 x 10 18 atoms/cm 3 or lower, or in specific embodiments, at or beneath a detectable limit such as 3.0 x 10 16 atoms/cm 3 .
  • the oxygen content of polycrystalline GaN may be less than 1 x 10 17 atoms/cm 3 .
  • This polycrystalline GaN will have little or no single-crystal GaN associated with it.
  • the polycrystalline GaN also may not incorporate any other of the growth region materials into it and may be about or at or below the limit of detection that exists today for one or more elements that make up the growth region material.
  • polycrystalline GaN may be grown in a reactor formed from pyrolytic BN.
  • the polycrystalline GaN may have about or at or less than a detectable limit of boron.
  • a detection limit for B is 6.7 x 10 15 atoms/cm 3 , and the amount of boron in the polycrystalline GaN may be about this value, at this value, or below this value.
  • the methods and reactors of the present disclosure provide for the efficient production of polycrystalline group III nitride.
  • the methods described herein may produce the polycrystalline group III nitride, such as polycrystalline GaN, at growth rates of greater than 5 grams per hour (g/hr).
  • the methods and reactors described herein result in a production efficiency (conversion) where greater than 70% of the group III element source material is converted to polycrystalline group III nitride.
  • greater than 70% of gallium source material may be converted into polycrystalline GaN and in certain embodiments greater than 80% of the gallium source material may be converted into polycrystalline GaN.
  • producing the crystalline group III nitride may comprise crystallizing the crystalline group III nitride on a back etched surface of a polycrystalline group III base material.
  • the polycrystalline group III nitride base material may be recycled polycrystalline group III nitride material from an ammonothermal process.
  • the polycrystalline group III nitride base material may be pyrolytic boron nitride (BN).
  • the polycrystalline group III nitride base material may comprise pyrolytic boron nitride and recycled polycrystalline group III nitride (such as polycrystalline GaN) from an ammonothermal process.
  • polycrystalline GaN may be used as a template or nucleation material to grow polycrystalline GaN as discussed above.
  • polycrystalline GaN source material formed using HVPG growth as disclosed herein may be heated and maintained at a temperature above 700 0 C and back-etched using a hydrogen- containing gas such as NH 3 or HCl.
  • polycrystalline GaN having low oxygen content may be formed by placing previously- formed polycrystalline GaN into the growth region and forming new polycrystalline GaN on the pre-existing polycrystalline GaN. This is especially the case if the pre-existing polycrystalline GaN is etched prior to depositing new polycrystalline GaN in the growth region. Without intending to be limited by any theory, it is theorized that etching may help remove oxygen that may have been incorporated into the previously-grown GaN.
  • the pre-existing polycrystalline GaN may be etched using hydrogen gas or hydrogen containing gas or a combination of the two. In certain embodiments, the pre-existing polycrystalline GaN may be etched using an etching gas, such as, for example, HCl or NH 3 .
  • the pre-existing polycrystalline GaN may or may not have been formed by a method of this invention and may also include recycled polycrystalline GaN from an ammonothermal growth process.
  • the pre-existing polycrystalline GaN may be polycrystalline GaN remaining from a single crystal GaN growth process, such as an ammonothermal growth process.
  • Polycrystalline GaN may serve as a source material for an ammonothermal growth process.
  • the remaining polycrystalline GaN may be recycled in the various methods described herein.
  • the recycled or "old" polycrystalline GaN may be introduced into the HVPE process in the growth region to serve as a base material for new polycrystalline GaN growth.
  • the method of the present disclosure may further comprise submitting the polycrystalline group III nitride to an ammonothermal process to produce single-crystal group III nitride.
  • ammonothermal methods of growing single- crystal GaN may be found in the references incorporated by reference above.
  • Ammonothermal growth processes include solvothermal methods using high-pressure ammonia as a solvent for the growth of high purity and high quality single-crystal group III nitride ingots, suitable for use in various opto-electronic and electronic devices.
  • a gallium source material such as polycrystalline GaN is dissolved in supercritical ammonia a source dissolution region.
  • the GaN then flows to a crystal growth region, for example through a series of baffles, and crystallizes to form single crystal GaN.
  • the source dissolution region may be at a lower temperature than the crystal growth region.
  • the method comprises heating and maintaining the polycrystalline GaN source material at a temperature greater than 700 0 C, back etching a surface of the polycrystalline GaN source material to provide a back etched polycrystalline GaN, and depositing additional polycrystalline GaN on the surface of the back etched polycrystalline GaN by a hydride vapor phase growth (HVPG) process, such as any of the HVPG processes described herein.
  • HVPG hydride vapor phase growth
  • the polycrystalline GaN source material from the previous ammonothermal growth process may be back etched according to the process described herein (i.e., contacting the surface with a hydrogen containing gas, such as HCl or NH 3 ).
  • the polycrystalline GaN material that results from the recycling process has a low oxygen content and is suitable for use in a subsequent ammonothermal growth process to produce single crystal GaN ingots.
  • the resulting polycrystalline GaN may have oxygen contents such as those described for the HVPG processed herein, after the recycling process.
  • the low oxygen content may result from the back etching of the recycled polycrystalline source material to remove oxide material on the surface of the polycrystalline GaN source material.
  • the reactor may comprise a first heated region comprising a first gas inlet configured to introduce a nitrogen containing gas (such as ammonia gas), a second heated region comprising a second gas inlet configured to introduce a halide containing gas, and a growth region in gaseous contact with the first heated region and the second heated region and configured to allow growth of polycrystalline group III nitride (such as GaN).
  • the first heated region and the second heated region are configured to maintain separation of the gases in each region.
  • the first and second heated regions are configured so that the nitrogen containing gas and the halide containing gas have no substantial contact with each other until the gases enter the growth region.
  • the first heated region, the second heated region and the crystal growth region are each configured to be heated at temperatures ranging from 700 0 C to 1200 0 C for the first and second heated region and 700 0 C to 1300 0 C growth region.
  • the reactors may be designed so that the growth region, and in certain embodiments both the first heated region and the second heated region, have a surface configured to contact the gases, where the surface is formed from a material other than an oxide (i.e., a non-oxide material).
  • a non-oxide material i.e., a non-oxide material
  • the reactor surfaces that may contact the gases may be formed from or coated with boron nitride or pyrolytic boron nitride. Surfaces formed from other non-oxide materials are also envisioned. As described herein, use of such non-oxide materials in the reactor design may result in reduced impurity incorporation, such as oxygen incorporation, in the resulting polycrystalline group III nitride.
  • the second heated region may comprise a second gas inlet configured to introduce GaCl 2 (where z is as described herein) as the halide-containing gas.
  • the second heated region may comprise a second gas inlet configured to introduce a hydrogen halide, such as HCl) as the halide-containing gas may be further configured to contain a gallium source material in contact with the hydrogen halide gas.
  • the second region may be configured to contain a tray made of a non-oxide material that contains a gallium source material and the second gas inlet configured to contact the hydrogen halide gas with the gallium source material in the tray.
  • the growth region may be configured to allow back etching of a pre-existing polycrystalline group III nitride material, such as BN and/or GaN.
  • the growth region may be configured to contain a tray made of a non-oxide material containing a pre-existing or recycled polycrystalline group III nitride material.
  • the growth region may be configured to allow introduction of a hydrogen containing back etching gas (as describe herein, such as HCl or NH 3 ) and allow contact and back etching of a surface of the re-existing or recycled polycrystalline group III nitride material.
  • Tube reactor 11 includes a heating mechanism 1 surrounded by an insulating material 2.
  • the first heated region 3 includes first gas inlet 4.
  • the second heated region 5 is formed from D-tube 6 inserted into the tube reactor and includes the second gas inlet 7 and a non-oxide tray 8 for containing the group III source material.
  • D-tube 6 prevents gaseous contact between the gas in the first heated region 3 and the gas in the second heated region 5.
  • the gases may then travel to growth region 9 having a liner 10 made from pyro lytic boron nitride (PBN).
  • PBN pyro lytic boron nitride
  • Fig. 2 One exemplary embodiment of the growth region of a reactor is illustrated in Fig. 2. Pyrolytic boron nitride liners 21 provide a deposition surface for GaN growth. Tray 22 contains recycled polycrystalline GaN material 23 and newly deposited GaN growth 24. Still other embodiments of the present disclosure include a polycrystalline group III nitride formed by a HVPG process such as described herein. One specific embodiment provides a polycrystalline GaN formed by any of the HVPG methods described herein. The polycrystalline GaN may be suitable for use in an ammonothermal growth process to form single crystal GaN ingots of high purity and high quality and suitable for use in various opto-electronic and electronic applications.
  • the methods may comprise forming polycrystalline GaN by a hydride vapor phase growth process such as any of the methods disclosed herein; utilizing the polycrystalline GaN as a nutrient or gallium source material in an ammonothermal growth process to grow single-crystal GaN; and forming single crystal GaN by the ammonothermal growth process.
  • Examples of ammonothermal methods of growing single-crystal GaN may be found in the references incorporated by reference above, and thus any method of forming single-crystal GaN as disclosed in those references may utilize polycrystalline GaN grown by any method disclosed herein. Also disclosed is single-crystal GaN made by this method.
  • the method of forming single crystal GaN may further comprise the step of recycling polycrystalline GaN source material remaining after completion of the ammonothermal growth process in a subsequent hydride vapor phase growth process.
  • the overall economic efficiency of the ammonothermal process for producing group III nitrides may be improved.
  • the methods and reactors disclosed herein may be used to form polycrystalline Al x Gai_ x N, In x Gai_ x N, and Al x In y Gai_ x _ y N (0 ⁇ x ⁇ l, 0 ⁇ y ⁇ l). Further, the polycrystalline material formed by methods disclosed herein may be used to make single-crystal Al x Gai_ x N, In x Gai_ x N, and Al x In y Gai_ x _ y N by any of the methods of forming these single-crystal materials, including those methods incorporated by reference herein.
  • FIG. 1 is a schematic drawing of the HVPG reactor.
  • 110.0 g of Ga source material was loaded into a pyrolytic BN tray or boat (FIG. 1, feature 8) which in turn was loaded into a D-tube (FIG. 1, feature 6) which allowed gas streams to be separated in the growth reactor.
  • Several pyrolytic BN parts or liners (Fig. 1, feature 10) were loaded in the growth region (FIG. 1, feature 9) of the reactor to act as the deposition surface.
  • the reactor was then sealed and connected to a gas/vacuum system, which could pump down the vessel as well as can supply NH3, HCl, and N2/H2 to the reactor.
  • the reactor was evacuated and refilled 3 times to remove any oxygen.
  • the reactor was heated to 1100 0 C as measured by thermocouples at the growth region while it was purged with a N2/H2 mixture.
  • NH3 and HCl gas flows were added to the reactor (FIG 1, features 4 and 7, respectively).
  • the HCl gas flowed through the lower nozzle 7 and into in the D-tube 6 where the gas could react with Ga in the Ga tray or boat 8 to form GaCl which was then transported to the growth environment or region 9, and NH 3 gas flowed through the upper gas nozzle 4 such that the GaCl and NH3 gases contacted one another in growth region 9.
  • the growth was stopped and the reactor opened upon cooling.
  • Polycrystalline GaN growth and Ga metal consumption were measured as 108.2 g and 107.3 g, respectively.
  • the molar weight of Ga and GaN is 69.72 g/mol and 83.73 g/mol , respectively. If all consumed Ga is turned into GaN, the theoretical GaN weight is estimated to be 128.9 g. Therefore, Ga to GaN conversion efficiency was approximately 84% in this example.
  • a tube furnace with an inner diameter of 2" was used for the HVPG growth.
  • 110.0 g of Ga source material was loaded into a pyrolytic BN tray 8 of Fig. 1 which in turn was loaded into a D-tube 6 which allowed gas streams to be separated in the growth reactor.
  • Several pyrolytic BN parts were loaded in the growth region of the reactor to act as the deposition surface.
  • 30.0 g of old GaN source material 23 remaining from a series of ammonothermal experiments (“old GaN polycrystalline growth" was also loaded onto a pyrolytic BN tray and placed in the growth region 9 of Fig. 1.
  • the source material had been rinsed with DI water and baked after unloading from the ammonothermal autoclave.
  • the reactor was then sealed and connected to a gas/vacuum system, which could pump down the vessel as well as can supply NH 3 , HCl, N2/H2 to the reactor.
  • the reactor was evacuated and refilled 3 times to remove any oxygen.
  • the reactor was heated to 1100 0 C as measured by thermocouples at the growth region while purged with a N2/H2 mixture.
  • NH3 and HCl gas flows were added to the reactor.
  • the HCl gas flowed into the D-tube where it can react with the Ga to form GaCl which was transported to the growth environment 9. After 7 hours the growth was stopped and the reactor opened upon cooling down.
  • the polycrystalline GaN growth and Ga metal consumption were measured as 108.1 g and 103.4 g respectively.
  • Ga to GaN conversion efficiency was calculated to be approximately 87%, which showed slight increase from Example 1. This is likely due to the increase in possible growth surface area provided by the old GaN 23.
  • An image of the old and new polycrystalline growth (23 and 24, respectively) is shown in FIG. 2.
  • the present invention disclosed new production methods of polycrystalline GaN for use in the ammonothermal growth of group III -nitride material. Quantities over 100 g of polycrystalline GaN with low impurity concentration can be consistently produced in times of 7 hours. Additionally any remaining GaN source material from previous ammonothermal growth can be recycled providing additional future source material. These methods improve production rates to produce polycrystalline GaN optimized for use in the ammonothermal growth of Ill-nitride material. The following describes some alternative embodiments for accomplishing the present invention.
  • the present invention does not have any limitations on the size of the reactor or the amount recycled or grown, so long as the same benefits can be obtained.

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Abstract

La présente invention concerne des procédés de production de grandes quantités de GaN polycristallin pour utiliser dans la croissance ammonothermique de matériaux en nitrure du groupe III. Des vitesses de production élevées de GaN peuvent être produites dans un système de croissance en phase vapeur d’hydrure. Un inconvénient de la croissance polycristalline améliorée est l’augmentation de l’incorporation d’impuretés, comme l’oxygène. L’invention concerne une nouvelle conception de réacteur utilisant un matériau non oxyde qui réduit les concentrations d’impuretés. L’invention concerne aussi la purification du matériau source restant après une croissance ammonothermique. Les procédés décrits produisent de quantités suffisantes de matériau source de GaN polycristallin pour la croissance ammonothermique de matériau en nitrure du groupe III.
PCT/US2009/065513 2008-11-24 2009-11-23 Procédés de production d’un nutriment de gan pour la croissance ammonothermique Ceased WO2010060034A1 (fr)

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