WO2012090918A1 - 半導体結晶の製造方法、結晶製造装置および第13族窒化物半導体結晶 - Google Patents
半導体結晶の製造方法、結晶製造装置および第13族窒化物半導体結晶 Download PDFInfo
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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
- C30B29/38—Nitrides
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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
- 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
- C30B7/105—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 using ammonia as solvent, i.e. ammonothermal processes
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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
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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
- C30B29/406—Gallium nitride
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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
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
- Y10T117/10—Apparatus
- Y10T117/1024—Apparatus for crystallization from liquid or supercritical state
- Y10T117/1096—Apparatus for crystallization from liquid or supercritical state including pressurized crystallization means [e.g., hydrothermal]
Definitions
- the supercritical ammonia environment containing these mineralizers is an extremely severe corrosive environment.
- a pressure vessel can be manufactured using a material having a strength that can withstand this temperature and pressure (for example, Alloy 625, RENE41, which are Ni-based superalloys), but does not have a complete anticorrosive property against supercritical ammonia. .
- the acid mineralizer is highly corrosive to the alloy, it is necessary to establish an anticorrosion technique using a material having high corrosion resistance.
- JP 2006-193355 A JP-T-2006-514581
- a method for producing a semiconductor crystal by performing crystal growth in the presence of a supercritical and / or subcritical solvent in a reaction vessel comprising: a surface of the reaction vessel and a member used inside the reaction vessel; A method for producing a semiconductor crystal, wherein at least a part of the surface is coated with a platinum group-group 13 metal alloy film.
- One or more alloys wherein the platinum group-group 13 metal alloy coating is selected from the group consisting of Ga 3 Pt 5 , Ga 3 Pt 2 , GaPt, Ga 2 Pt, Ga 2 Pt, GaPt 2 and GaPt 3
- a crystal manufacturing apparatus in which a reaction vessel for crystal growth in a supercritical ammonia atmosphere is installed in a pressure-resistant vessel, the surface inside the reaction vessel and members used inside the reaction vessel A crystal manufacturing apparatus, wherein at least a part of the surface of the substrate is coated with a platinum group-group 13 metal alloy coating.
- the reaction vessel is a capsule made of a platinum group or an alloy containing a platinum group.
- the reaction vessel is a capsule made of an alloy containing a Pt—Ir alloy.
- the manufacturing method of the present invention it is possible to obtain a nitride crystal in which impurities that could not be removed conventionally are reduced.
- the platinum group-group 13 metal alloy coating is extremely stable under crystal growth conditions, the reaction vessel can be used a plurality of times, which is highly effective in improving productivity.
- the nitride crystal of the present invention is uniform and of high quality, it is useful as a semiconductor crystal for a light emitting device or an electronic device.
- a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the crystal growth step and / or the film formation step may be performed a plurality of times.
- a platinum group-group 13 metal alloy formed on at least a part of the surface inside the reaction vessel and the surface of the member used inside the reaction vessel even if the crystal growth step and / or the film formation step are performed a plurality of times Since the coating exists stably, it can be used over a long period of time without corroding the reaction vessel and / or member, and thus the productivity is greatly improved.
- the second aspect of the method for producing a semiconductor crystal of the present invention is a method for producing a semiconductor crystal by carrying out crystal growth in the presence of a supercritical and / or subcritical solvent in a reaction vessel, At least a part of the surface of the reaction vessel and the surface of the member used inside the reaction vessel is coated with a platinum group-group 13 metal alloy coating.
- Each process of the present invention includes a crystal production apparatus in which a reaction vessel for crystal growth is installed in the presence of a supercritical and / or subcritical solvent such as a supercritical ammonia atmosphere in at least a pressure resistant vessel. It is done using. At least a part of the surface inside the reaction vessel and the surface of the member used inside the reaction vessel is coated with a platinum group-group 13 metal alloy coating. Details of the platinum group-group 13 metal alloy coating will be described in detail in the section of the coating forming process.
- reaction vessel means a vessel for producing nitride crystals in a state where a solvent in a supercritical and / or subcritical state can directly contact its inner wall surface, Preferred examples include capsules installed in a pressure-resistant container.
- the reaction vessel can be selected from those that can withstand the high temperature and high pressure conditions when growing the nitride crystal.
- Examples of the reaction vessel include those described in JP-T-2003-511326 (International Publication No. 01/024921 pamphlet) and JP-T-2007-509507 (International Publication No. 2005/043638 pamphlet).
- a mechanism that adjusts the pressure applied to the reaction vessel and its contents from the outside may be provided, or an autoclave that does not have such a mechanism may be used.
- the pressure-resistant vessel used in the present invention is selected from those that can withstand high-temperature and high-pressure conditions when growing nitride crystals by the ammonothermal method.
- a material composed of a material having a high temperature strength and a high corrosion resistance is preferable.
- a Ni-based alloy having excellent corrosion resistance against solvents such as ammonia, Stellite (registered trademark of Deloro Stellite Company, Inc.)
- Those composed of a Co-based alloy such as More preferably, it is a Ni-based alloy.
- a method of directly lining or coating the inner surface with a material having further excellent corrosion resistance, or a capsule made of a material having further excellent corrosion resistance is used. It is preferable to form the reaction vessel by a method of placing it inside.
- Examples of the material constituting the reaction vessel include a platinum group and a noble metal. Specifically, ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt). , Gold (Au), silver (Ag). These materials may be used alone or as an alloy combining a plurality of these materials. Moreover, as long as the effect of this invention is not impaired, the other metal may be included as a material which comprises reaction container. Among these, it is preferable to use a platinum group or an alloy containing a platinum group having excellent corrosion resistance, more preferably an alloy containing Pt or Pt, and still more preferably a Pt or Pt—Ir alloy.
- the manner of constituting the reaction vessel is not particularly limited, but in the method of directly lining or coating the inner surface of the pressure resistant vessel, it is difficult to line or coat all surfaces that can come into contact with the ammonia solvent inside the reaction vessel. Therefore, a method in which capsules made of a material having excellent corrosion resistance are arranged in a pressure resistant container is a more preferable embodiment.
- the shape of the reaction vessel can be any shape including a cylindrical shape. Further, the reaction vessel may be used standing upright, horizontally or diagonally.
- FIGS. 1 and 2 are schematic views of a crystal manufacturing apparatus that can be used in the present invention.
- the crystal manufacturing apparatus shown in FIG. 1 performs crystal growth in a reaction vessel provided with a lining 3 on the inner surface of an autoclave 1 that is a pressure-resistant vessel.
- crystal growth is performed in a capsule 20 loaded as a reaction vessel (inner cylinder) in the autoclave 1.
- the interior of the lining 3 and the capsule 20 are composed of a raw material dissolution region 9 for dissolving the raw material and a crystal growth region 6 for growing crystals.
- a solvent and a mineralizer can be placed in the raw material dissolution region 9 together with the raw material 8, and the seed crystal 7 can be installed in the crystal growth region 6 by suspending it with a wire.
- a partition baffle plate 5 is installed in two regions.
- the baffle plate 5 has a hole area ratio of preferably 2% or more, more preferably 3% or more, more preferably 60% or less, and even more preferably 40% or less.
- the material of the surface of the baffle plate is preferably the same as the material of the capsule 20 that is a reaction vessel.
- the surface of the baffle plate should be Ni, Ta, Ti, Nb, Pd, Pt, Au, Ir, or an alloy thereof, pBN. Pd, Pt, Au, Ir, or an alloy thereof, or pBN is more preferable, and Pt or an alloy thereof is particularly preferable.
- the gap between the inner wall 2 of the autoclave 1 and the capsule 20 can be filled with the second solvent.
- ammonia can be filled as the second solvent while filling the nitrogen gas from the nitrogen cylinder 13 through the valve 10 or confirming the flow rate from the ammonia cylinder 12 with the mass flow meter 14.
- the vacuum pump 11 can perform necessary pressure reduction. Note that a valve, a mass flow meter, and a conduit are not necessarily installed in the crystal manufacturing apparatus used when the nitride crystal manufacturing method of the present invention is carried out.
- the material for the lining 3 in FIG. 1 is at least one metal or element of Pt, Ir, Ag, Pd, Rh, Cu, Au, and C, or an alloy or compound containing at least one metal.
- it is an alloy or a compound containing at least one or more kinds of metals or elements of Pt, Ag, Cu and C, or at least one kind of metals because it is easy to line.
- Pt simple substance, Pt—Ir alloy, Ag simple substance, Cu simple substance, graphite and the like can be mentioned.
- the production method of the present invention is generally performed in a state where members are installed inside the reaction vessel.
- the “member” as used herein means a member that is installed in a container when producing a nitride crystal by the ammonothermal method and can be separated from the reaction container.
- a growth frame for holding the seed crystal, a baffle plate for controlling the convection of the solution, a raw material basket, a wire for hanging the seed crystal, and the like can be used.
- the surfaces of these members are also preferably covered with the material having excellent corrosion resistance as described above.
- the crystal growth step is a step of performing crystal growth in the presence of a supercritical and / or subcritical solvent in a reaction vessel.
- conditions for crystal growth conditions such as raw materials, mineralizers, seed crystals, solvents, temperature, and pressure as disclosed in JP-A-2009-263229 can be preferably used. The entire disclosure of this publication is incorporated herein by reference.
- a seed crystal as the nucleus of crystal growth.
- the same kind as the crystal to grow is used preferably.
- Specific examples of the seed crystal include nitride single crystals such as gallium nitride (GaN), aluminum nitride (AlN), indium nitride (InN), and mixed crystals thereof.
- the seed crystal can be determined in consideration of the lattice matching with the crystal to be grown.
- a seed crystal a single crystal obtained by epitaxial growth on a heterogeneous substrate such as sapphire and then exfoliated, a single crystal obtained by crystal growth of Na, Li, Bi as a flux from a metal such as Ga, a liquid phase
- LPE method epitaxy method
- the specific method of the epitaxial growth is not particularly limited, and for example, a hydride vapor phase growth method (HVPE) method, a metal organic chemical vapor deposition method (MOCVD method), a liquid phase method, an ammonothermal method, or the like is adopted. be able to.
- HVPE hydride vapor phase growth method
- MOCVD method metal organic chemical vapor deposition method
- liquid phase method an ammonothermal method, or the like
- a mineralizer In the crystal growth process of the present invention, it is preferable to use a mineralizer. Since the solubility of the crystal raw material in a solvent containing nitrogen such as ammonia is not high, a mineralizer is used to improve the solubility.
- the mineralizer used may be a basic mineralizer or an acidic mineralizer.
- Basic mineralizers include alkali metals, alkaline earth metals, compounds containing rare earth metals and nitrogen atoms, alkaline earth metal amides, rare earth amides, alkali nitride metals, alkaline earth metal nitrides, azide compounds, and other hydrazines.
- Class of salts Preferably, it is an alkali metal amide, and specific examples include sodium amide (NaNH 2 ), potassium amide (KNH 2 ), and lithium amide (LiNH 2 ).
- the compound containing a halogen element is preferable.
- mineralizers containing halogen elements include ammonium halide, hydrogen halide, ammonium hexahalosilicate, and hydrocarbyl ammonium fluoride, tetramethylammonium halide, tetraethylammonium halide, benzyltrimethylammonium halide, halogen
- alkylammonium salts such as dipropylammonium halide and isopropylammonium halide
- alkyl metal halides such as sodium alkyl fluoride, alkaline earth metal halides and metal halides.
- an additive (mineralizing agent) containing a halogen element is preferably an alkali halide, an alkaline earth metal halide, a metal halide, an ammonium halide, or a hydrogen halide, more preferably a halogenated.
- Alkalis, ammonium halides, group 13 metal halides and hydrogen halides are preferred, and ammonium halides, gallium halides and hydrogen halides are particularly preferred.
- the ammonium halide include ammonium chloride (NH 4 Cl), ammonium iodide (NH 4 I), ammonium bromide (NH 4 Br), and ammonium fluoride (NH 4 F).
- a mineralizer containing fluorine element and at least one selected from other halogen elements composed of chlorine, bromine and iodine is preferably used. These may be used individually by 1 type, and may mix and use multiple types suitably.
- the combination of halogen elements contained in the mineralizer may be a combination of two elements such as chlorine and fluorine, bromine and fluorine, iodine and fluorine, chlorine and bromine and fluorine, chlorine and iodine and fluorine, bromine and A combination of three elements such as iodine and fluorine may be used, or a combination of four elements such as chlorine, bromine, iodine and fluorine may be used.
- the combination and concentration ratio (molar concentration ratio) of the halogen elements contained in the mineralizer used in the present invention are the type, shape and size of the nitride crystal to be grown, and the type, shape and size of the seed crystal used. It can be appropriately determined depending on the reaction apparatus, the temperature conditions and pressure conditions employed, and the like.
- a mineralizer containing no halogen element can be used together with a mineralizer containing a halogen element.
- a mineralizer containing a halogen element For example, it is used in combination with an alkali metal amide such as NaNH 2 , KNH 2 or LiNH 2. You can also.
- a halogen element-containing mineralizer such as ammonium halide and a mineralizer containing an alkali metal element or alkaline earth metal element are used in combination, it is preferable to increase the amount of the halogen element-containing mineralizer.
- the mineralizer containing an alkali metal element or alkaline earth metal element is preferably 0.01 parts by mass or more, and 0.1 parts by mass More preferably, it is more preferably 0.2 parts by mass or more, more preferably 50 parts by mass or less, more preferably 20 parts by mass or less, and more preferably 5 parts by mass or less. More preferably.
- the mineralizer can be used after being purified and dried as necessary.
- the purity of the mineralizer is usually 95% or higher, preferably 99% or higher, more preferably 99.99% or higher.
- the amount of water and oxygen contained in the mineralizer is desirably as small as possible, and the content thereof is preferably 1000 ppm or less, more preferably 10 ppm or less, and further preferably 1.0 ppm or less. preferable.
- aluminum halide, phosphorus halide, silicon halide, germanium halide, zinc halide, arsenic halide, tin halide, antimony halide, bismuth halide, etc. are used in a reaction vessel. May be present.
- the molar concentration of the halogen element contained in the mineralizer with respect to the solvent is preferably 0.1 mol% or more, more preferably 0.3 mol% or more, and further preferably 0.5 mol% or more.
- the molar concentration of the halogen element contained in the mineralizer is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. If the concentration is too low, the solubility tends to decrease and the growth rate tends to decrease. On the other hand, when the concentration is too high, there is a tendency that the solubility becomes too high and the generation of spontaneous nuclei increases, or the control becomes difficult because the supersaturation degree becomes too high.
- a raw material containing an element constituting a semiconductor crystal to be grown on a seed crystal is used.
- a raw material containing a periodic table 13 group metal is used.
- Preferred is a polycrystalline raw material of a group 13 nitride crystal and / or a group 13 metal, and more preferred is gallium nitride and / or metal gallium.
- the polycrystalline raw material does not need to be a complete nitride, and may contain a metal component in which the group 13 element is in a metal state (zero valence) depending on conditions.
- gallium nitride Is a mixture of gallium nitride and metal gallium.
- the method for producing the polycrystalline raw material is not particularly limited.
- a nitride polycrystal produced by reacting a metal or an oxide or hydroxide thereof with ammonia in a reaction vessel in which ammonia gas is circulated can be used.
- a metal compound raw material having higher reactivity a compound having a covalent MN bond such as a halide, an amide compound, an imide compound, or galazan can be used.
- a nitride polycrystal produced by reacting a metal such as Ga with nitrogen at a high temperature and a high pressure can also be used.
- the amount of water and oxygen contained in the polycrystalline raw material used as the raw material in the present invention is preferably small.
- the oxygen content in the polycrystalline raw material is usually 10,000 ppm or less, preferably 1000 ppm or less, particularly preferably 1 ppm or less.
- the ease of mixing oxygen into the polycrystalline raw material is related to the reactivity with water or the absorption capacity.
- the worse the crystallinity of the polycrystalline raw material the more active groups such as NH groups exist on the surface, which may react with water and partially generate oxides or hydroxides. For this reason, it is usually preferable to use a polycrystalline material having as high crystallinity as possible.
- the crystallinity can be estimated by the half width of powder X-ray diffraction.
- a solvent containing nitrogen is preferably used as the solvent used in the crystal growth step.
- the solvent containing nitrogen include a solvent that does not impair the stability of the grown nitride single crystal.
- the solvent include ammonia, hydrazine, urea, amines (for example, primary amines such as methylamine, secondary amines such as dimethylamine, tertiary amines such as trimethylamine, and ethylenediamine. Diamine) and melamine. These solvents may be used alone or in combination.
- the amount of water and oxygen contained in the solvent is desirably as small as possible, and the content thereof is preferably 1000 ppm or less, more preferably 10 ppm or less, and further preferably 0.1 ppm or less.
- ammonia is used as a solvent, the purity is usually 99.9% or more, preferably 99.99% or more, more preferably 99.999% or more, and particularly preferably 99.9999% or more. .
- the whole is heated to bring the inside of the reaction vessel into a supercritical state and / or a subcritical state.
- the supercritical state means a liquid state having a density substantially equal to the critical density near the critical temperature.
- the raw material filling part the raw material is melted as a supercritical state, and in the crystal growth part, the temperature is changed so as to be in the subcritical state, and crystal growth utilizing the difference in solubility between the supercritical state and the subcritical state raw material is also performed. Is possible.
- the reaction mixture In the supercritical state, the reaction mixture is generally kept at a temperature higher than the critical point of the solvent.
- the critical point is a critical temperature of 132 ° C. and a critical pressure of 11.35 MPa.
- the “supercritical state” includes such a state exceeding the critical pressure. Since the reaction mixture is enclosed in a constant volume reaction vessel, the increase in temperature increases the pressure of the fluid. In general, if T> Tc (critical temperature of one solvent) and P> Pc (critical pressure of one solvent), the fluid is in a supercritical state.
- the pressure in the reaction vessel is preferably 120 MPa or more, more preferably 150 MPa or more, and further preferably 180 MPa or more, from the viewpoints of crystallinity and productivity.
- the pressure in the reaction vessel is preferably 700 MPa or less, more preferably 500 MPa or less, further preferably 350 MPa or less, and particularly preferably 300 MPa or less from the viewpoint of safety.
- the pressure is appropriately determined depending on the filling rate of the solvent volume with respect to the temperature and the volume of the reaction vessel. Originally, the pressure in the reaction vessel is uniquely determined by the temperature and the filling rate, but in practice, the raw materials, additives such as mineralizers, temperature heterogeneity in the reaction vessel, and free volume Depending on the presence of
- the lower limit of the temperature range in the reaction vessel is preferably 500 ° C. or higher, more preferably 515 ° C. or higher, and further preferably 530 ° C. or higher from the viewpoint of crystallinity and productivity.
- the upper limit value is preferably 700 ° C. or less, more preferably 650 ° C. or less, and further preferably 630 ° C. or less.
- the temperature of the raw material dissolution region in the reaction vessel is preferably higher than the temperature of the crystal growth region.
- ) between the raw material dissolution region and the crystal growth region is preferably 5 ° C. or more, more preferably 10 ° C.
- the optimum temperature and pressure in the reaction vessel can be appropriately determined depending on the type and amount of mineralizer and additive used during crystal growth.
- the injection rate of the solvent into the reaction vessel that is, the filling rate is the free volume of the reaction vessel, that is, the polycrystalline raw material and the seed crystal are used in the reaction vessel.
- Based on the liquid density at the boiling point of the remaining volume of solvent it is usually 20% or more, preferably 30% or more, more preferably 40% or more, and usually 95% or less, preferably 80% or less, more preferably 70% or less.
- the growth of the semiconductor crystal in the reaction vessel is performed by heating the reaction vessel with an electric furnace having a thermocouple or the like to bring the reaction vessel into a subcritical state and / or a supercritical state of a solvent such as ammonia. This is done by holding.
- the heating method and the rate of temperature increase to a predetermined reaction temperature are not particularly limited, but are usually performed over several hours to several days. If necessary, the temperature can be raised in multiple stages, or the temperature raising speed can be changed in the temperature range. It can also be heated while being partially cooled.
- reaction temperature is measured by a thermocouple provided so as to be in contact with the outer surface of the reaction vessel and / or a thermocouple inserted into a hole having a certain depth from the outer surface. It can be estimated in terms of temperature.
- the average value of the temperatures measured with these thermocouples is taken as the average temperature.
- an average value of the temperature of the raw material melting region and the temperature of the crystal growth region is defined as the average temperature.
- a pretreatment can be added to the seed crystal.
- the pretreatment include subjecting the seed crystal to a meltback process, polishing the growth surface of the seed crystal, and washing the seed crystal.
- the reaction time after reaching the specified temperature varies depending on the type of semiconductor crystal, the raw material used, the type of mineralizer, and the size and amount of the crystal to be produced, but it is usually several hours to several hundred days. Can do.
- the reaction temperature may be constant, or the temperature may be gradually raised or lowered.
- the temperature is lowered.
- the temperature lowering method is not particularly limited, but the heating may be stopped while the heating of the heater is stopped and the reaction vessel is installed in the furnace as it is, or the reaction vessel may be removed from the electric furnace and air cooled. If necessary, quenching with a refrigerant is also preferably used.
- the reaction vessel is opened.
- the predetermined temperature at this time is not particularly limited, and is usually ⁇ 80 ° C. or higher, preferably ⁇ 33 ° C. or higher, and is usually 200 ° C. or lower, preferably 100 ° C. or lower.
- the valve may be opened by connecting a pipe to the pipe connection port of the valve connected to the reaction vessel, leading to a vessel filled with water or the like. Furthermore, if necessary, remove the ammonia solvent in the reaction vessel sufficiently by applying a vacuum, etc., then dry, open the reaction vessel lid, etc., and generate nitride crystals and unreacted raw materials and mineralization. Additives such as agents can be removed.
- the coating film forming step at least a part of the surface inside the reaction vessel and the surface of the member used inside the reaction vessel is coated with a platinum group-group 13 metal alloy to form a platinum group-group 13 metal alloy. This is a step of forming a film.
- Platinum group-Group 13 metal alloys are extremely stable against supercritical and / or subcritical solvents such as supercritical ammonia solvents and solutions in which mineralizers and raw materials are dissolved.
- a platinum group-group 13 metal alloy When at least a part of the surface and the surface of a member used inside the reaction vessel is coated with a platinum group-group 13 metal alloy, the reaction vessel and the member are not corroded, and the resulting nitride crystal It is possible to reduce impurities therein. Since impurities are further reduced, 50% or more of the total area of the surface inside the reaction vessel and the surface of the member used inside the reaction vessel is preferably covered, more preferably 70%. More preferably, it is 80% or more, particularly preferably 90% or more, and 100% may be coated.
- the platinum group-group 13 metal alloy coating is not particularly limited as long as it is an alloy containing a platinum group element and a group 13 element, and may contain other metals as long as the effects of the present invention are exhibited.
- a metal that functions as a dopant for a nitride crystal such as Si, Ca, Mg, or Zn, may be included.
- platinum group constituting the platinum group-group 13 metal alloy film examples include ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt).
- Ru ruthenium
- Rh rhodium
- Pr palladium
- Pd osmium
- Ir iridium
- Pt platinum
- a metal containing at least Pt is preferable.
- group 13 metal constituting the platinum group-group 13 metal alloy film examples include aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). Preferably there is.
- platinum group-group 13 metal alloy examples include Ga 3 Pt 5 , Ga 3 Pt 2 , GaPt, Ga 2 Pt, Ga 2 Pt, GaPt 2 , and GaPt 3 .
- the group metal alloy film is preferably a film containing one or more alloys selected from Ga 3 Pt 5 , Ga 3 Pt 2 , GaPt, Ga 2 Pt, Ga 2 Pt, GaPt 2 and GaPt 3 .
- These platinum group-group 13 metal alloy coatings may contain elements other than Ga and Pt as impurities. For example, as impurities, Si may be 10 ppm or less, Ir may be 500 ppm or less, and other platinum group elements may be 100 ppm or less.
- the thickness of the platinum group-group 13 metal alloy film formed in the film forming step is not particularly limited, but is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, further preferably 15 ⁇ m or more, particularly preferably 20 ⁇ m or more, Preferably it is 100 micrometers or less. If it is 5 ⁇ m or more, it is preferable because it is difficult to peel off even if the members are in contact with each other in the preparatory process for crystal growth, etc., and it is easy to handle, and if it is 100 ⁇ m or less, the coating itself becomes strong, It is preferable because it is difficult to peel off. When the coating forming process is performed a plurality of times, the platinum group-Group 13 metal alloy coating tends to become thicker as the number of times increases.
- the method for forming the platinum group-group 13 metal alloy film is not particularly limited.
- the platinum group-group 13 metal alloy film can be formed by increasing the temperature and pressure in an environment where the platinum group metal and the group 13 metal are present in the reaction vessel. .
- the platinum group metal present in the reaction vessel is the surface of the reaction vessel or the member itself, a platinum group-group 13 metal alloy film is efficiently formed on the portion to be coated with the platinum group-group 13 metal alloy. This is preferable because it can be performed.
- the Group 13 metal present in the reaction vessel may be derived from the raw material when the Group 13 metal is used as the raw material.
- a platinum group metal or a group 13 metal may be placed in the reaction vessel as a raw material for the platinum group-group 13 metal alloy coating, in addition to the crystal raw material and the reaction vessel material.
- the temperature at which the film is formed is preferably 400 ° C. or higher, more preferably 450 ° C. or higher, further preferably 500 ° C. or higher, particularly preferably 530 ° C. or higher, and 700 ° C. or lower. Preferably, it is 670 ° C. or lower, more preferably 650 ° C. or lower. It is preferable for it to be at least the lower limit because a more stable film can be formed.
- the pressure for forming the coating is preferably 80 MPa or more, more preferably 100 MPa or more, further preferably 120 MPa or more, and preferably 700 MPa or less, more preferably 500 MPa or less, and still more preferably. 400 MPa or less, particularly preferably 300 MPa or less. It is preferable for it to be at least the lower limit because a more stable film can be formed.
- a supercritical solvent, a mineralizer, or the like may be present in the reaction vessel, and the process can be simplified if the film forming process is simultaneously performed at least in part of the crystal growth process. It is preferable to use the same conditions as the crystal growth step.
- the film forming step may be performed in a state where a platinum group-Group 13 metal alloy film is already formed on the surface inside the reaction vessel and the surface of the member used inside the reaction vessel.
- the concentration of these substances is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less.
- Specific methods for reducing these substances include nitrogen purge in the reaction vessel and evacuation. Nitrogen purging and evacuation are preferably performed in combination.
- the reaction vessel may be heated together with evacuation.
- a gas such as oxygen can be efficiently removed from the reaction vessel, it is preferable to use a capsule made of a platinum group or an alloy containing a platinum group as the reaction vessel.
- a capsule made of an alloy containing Pt can be preferably used.
- a capsule made of a Pt—Ir alloy can be preferably used.
- the removal of oxygen in the reaction vessel can be achieved by implementing the technique described in WO2010 / 0779814.
- a mineralizer as a gas because oxygen is hardly accompanied when the mineralizer is introduced, so that oxygen in the reaction vessel can be reduced.
- the hydrogen halide gas when hydrogen halide gas is introduced into the reaction vessel, the hydrogen halide itself may be a mineralizer, or it is reacted with ammonia filled in the reaction vessel to be halogenated as a mineralizer. Ammonium may be made.
- the inside of the reaction vessel is set to a temperature of 400 to 700 ° C. and a pressure of 100 to 700 MPa in the presence of supercritical ammonia and a Group 13 metal can be preferably employed.
- the concentration of the platinum group metal element contained as an impurity in the crystal is not more than 10 times, preferably not more than 5 times that of the group 13 nitride semiconductor crystal grown in the absence of the platinum group metal.
- a group 13 nitride semiconductor crystal can be provided.
- the group 13 nitride semiconductor crystal grown in the absence of platinum group metal is, for example, thirteenth obtained by hydride vapor phase epitaxy (HVPE) using a crystal growth apparatus not containing platinum group metal.
- HVPE hydride vapor phase epitaxy
- Group nitride semiconductor crystals may be mentioned. According to such a method, since the platinum group metal does not exist in the growth atmosphere, it is considered that the platinum group metal is not contained in the obtained crystal.
- a group 13 nitride semiconductor crystal that can be used as a reference by the HVPE method will be described.
- the production method is not particularly limited to this, and the crystal is grown in the absence of a platinum group metal. It only has to be.
- a group 13 nitride semiconductor crystal can be grown by the HVPE method using the apparatus shown in FIG.
- the manufacturing apparatus shown in FIG. 3 includes a susceptor 108 on which a base substrate is placed and a reservoir 106 in which a group III nitride material to be grown is placed.
- introduction pipes 101 to 105 for introducing gas into the reactor 100 and an exhaust pipe 109 for exhausting are installed.
- a heater 107 for heating the reactor 100 from the side surface is installed.
- Reactor material gas type of ambient gas
- quartz sintered boron nitride, stainless steel, or the like is used.
- a preferred material is quartz.
- the reactor 100 is filled with atmospheric gas in advance before starting the reaction.
- the atmospheric gas include inert gases such as hydrogen, nitrogen, He, Ne, and Ar. These gases may be mixed and used.
- the material of the susceptor 108 is preferably carbon, and more preferably the surface is coated with SiC.
- the shape of the susceptor 108 is not particularly limited as long as the growth base substrate used in the present invention can be installed. However, it is preferable that no structure exists near the crystal growth surface during crystal growth. . If there is a structure that can grow in the vicinity of the crystal growth surface, a polycrystal adheres to the structure, and HCl gas is generated as a product to adversely affect the crystal to be grown.
- the contact surface between the base substrate and the susceptor 108 is preferably separated from the crystal growth surface of the base substrate by 1 mm or more, more preferably 3 mm or more, and further preferably 5 mm or more.
- the reservoir 106 is charged with a Group 13 nitride material to be grown.
- a raw material to be a Group 13 source is added.
- the raw material to be a Group 13 source include Ga, Al, In and the like.
- a gas that reacts with the raw material put in the reservoir 106 is supplied from an introduction pipe 103 for introducing the gas into the reservoir 106.
- HCl gas can be supplied from the introduction pipe 103.
- the carrier gas may be supplied from the introduction pipe 103 together with the HCl gas.
- the carrier gas include hydrogen, nitrogen, an inert gas such as He, Ne, and Ar. These gases may be mixed and used.
- a raw material gas serving as a nitrogen source is supplied. Usually, NH 3 is supplied.
- a carrier gas is supplied from the introduction pipe 101.
- the carrier gas the same carrier gas supplied from the introduction pipe 103 can be exemplified. This carrier gas also has an effect of separating the source gas nozzle and preventing the polycrystal from adhering to the nozzle tip.
- a dopant gas can be supplied from the introduction pipe 102, and HCl for cleaning the inside of the reactor by etching polycrystals or the like can be supplied from the introduction pipe 105.
- Gas introduction method The gases supplied from the introduction pipes 101 to 105 may be replaced with each other and supplied from different introduction pipes.
- the source gas and the carrier gas serving as a nitrogen source may be mixed and supplied from the same introduction pipe.
- a carrier gas may be mixed from another introduction pipe.
- the gas exhaust pipe 109 can be installed on the top, bottom, and side surfaces of the reactor inner wall. From the viewpoint of dust removal, it is preferably located below the crystal growth end, and more preferably a gas exhaust pipe 109 is installed on the bottom of the reactor as shown in FIG.
- Crystal Growth using the above production apparatus is usually performed at 950 ° C. or higher, preferably performed at 970 ° C. or higher, more preferably performed at 980 ° C. or higher, and performed at 990 ° C. or higher. Further preferred. Further, it is usually carried out at 1120 ° C. or less, preferably at 1100 ° C. or less, more preferably at 1090 ° C. or less, and further preferably at 1080 ° C. or less.
- the pressure in the reactor is preferably 10 kPa or more, more preferably 30 kPa or more, and further preferably 50 kPa or more. Moreover, it is preferable that it is 200 kPa or less, It is more preferable that it is 150 kPa or less, It is further more preferable that it is 120 kPa or less.
- Crystal growth rate The growth rate of crystal growth using the above-described manufacturing apparatus varies depending on the growth method, growth temperature, raw material gas supply amount, crystal growth plane orientation, etc., but generally 5 ⁇ m / h to 500 ⁇ m /
- the range of h is preferably 10 ⁇ m / h or more, more preferably 50 ⁇ m / h or more, and further preferably 70 ⁇ m or more.
- the growth rate can be controlled by appropriately setting the type of carrier gas, the flow rate, the supply port-crystal growth end distance, and the like.
- a nitride crystal was grown using the reactor shown in FIG. Crystal growth was performed using the RENE41 autoclave 1 (with an internal volume of about 345 cm 3 ) as a pressure vessel and the Pt—Ir capsule 20 as a reaction vessel. Capsule filling was performed in a sufficiently dry nitrogen atmosphere glove box. As raw material 8, 36 g of polycrystalline GaN particles were weighed and placed in the capsule lower region (raw material dissolution region 9). Next sufficiently dried purity of 99.99% NH 4 Cl as a mineralizer was poured into 2.0g weighed into capsules.
- a platinum baffle plate 5 (opening ratio: 15%) was placed between the lower raw material dissolution region 9 and the upper crystal growth region 6.
- Six hexagonal GaN single crystals (10 mm ⁇ 5 mm ⁇ 0.3 mm) grown by the HVPE method and one particulate crystal (about 5 mm ⁇ 5 mm ⁇ 5 mm) spontaneously nucleated by the HVPE method were used as the seed crystal 7.
- the main surface of the seed crystal was subjected to chemical mechanical polishing (CMP) finish, and the surface roughness was confirmed to be Rms of 0.5 nm by measurement with an atomic force microscope.
- These seed crystals 7 were suspended from a platinum seed crystal support frame by a platinum wire having a diameter of 0.2 mm and placed in the crystal growth region 6 above the capsule.
- a cap made of Pt—Ir was connected to the top of the capsule 20 by TIG welding, and the weight was measured.
- a valve similar to the valve 10 in FIG. 2 was connected to the tube attached to the upper part of the cap, and the valve was operated so as to communicate with the vacuum pump 11 to perform vacuum deaeration. Thereafter, the valve was operated so as to pass through the nitrogen cylinder 13 and the inside of the capsule was purged with nitrogen gas. The vacuum degassing and nitrogen purging were performed 5 times, and then the capsule was cooled with dry ice ethanol solvent while maintaining the vacuum state, and the valve was once closed.
- the valve of the conduit was operated so as to communicate with the NH 3 cylinder 12, the valve was opened again, NH 3 was filled without touching the outside air, and then the valve was closed again.
- the filling amount was confirmed from the difference in weight before and after NH 3 filling.
- the lid of the autoclave to which the valve 10 was attached was closed, and the weight of the autoclave 1 was measured.
- the conduit was connected to the vacuum pump 11 through the valve 10 attached to the autoclave, and the valve was opened to perform vacuum deaeration. Nitrogen gas purging was performed several times as in the capsule.
- the autoclave 1 was cooled with a dry ice methanol solvent while maintaining the vacuum state, and the valve 10 was once closed.
- the conduit was operated to lead to the NH 3 cylinder 12
- the valve 10 was opened again, and NH 3 was filled in the autoclave 1 without continuously touching the outside air, and then the valve 10 was closed again.
- the temperature of the autoclave 1 was returned to room temperature, the outer surface was sufficiently dried, and the weight of the autoclave 1 was measured.
- the weight of NH 3 was calculated from the difference from the weight before filling with NH 3 to confirm the filling amount.
- the autoclave 1 was stored in an electric furnace composed of a heater divided into two parts in the vertical direction.
- the temperature was raised over 9 hours so that the temperature of the crystal growth region on the outer surface of the autoclave was 590 ° C. and the temperature of the raw material dissolution region was 630 ° C. (temperature difference 40 ° C.). Held for hours.
- the pressure in the autoclave was 246 MPa. Further, the variation in the control temperature of the outer surface of the autoclave during the holding was ⁇ 0.3 ° C. or less.
- Example 2 In this embodiment, by using the NH 4 Cl reagent in the same manner as in Example 1 were carried out under operating conditions shown in Table 1. After completion of the operation, it was confirmed by visual observation that the capsule inner surface and the capsule inner member surface were covered with a dull silver film.
- Example 3 In this example, instead of NH 4 Cl reagent as a mineralizer, high purity HCl gas was introduced into the capsule and reacted with ammonia to generate NH 4 Cl in the capsule. By using HCl gas, it becomes possible to remove moisture and oxygen contained in the NH 4 Cl reagent.
- the other steps are the same as in Example 1, and the operating conditions are as shown in Table 1.
- Example 3 a Pt plate having a diameter of 21 mm, a thickness of 0.35 mm, and a weight of 2.3332 g was placed in the raw material dissolution region 9 at the bottom of the capsule in order to confirm the amount of Ga—Pt alloy coating formed.
- the Pt plate was taken out of the capsule and the surface was observed with the naked eye. As a result, a dull silver color was observed, confirming the formation of a Ga—Pt alloy coating. When the weight was measured, it was confirmed that the weight increased to 2.3615 g, 0.0283 g from before the addition.
- Example 4 In Examples 4 to 6, as in Example 3, instead of NH 4 Cl reagent as a mineralizer, high-purity HCl gas was introduced into the capsule and reacted with ammonia to generate NH 4 Cl in the capsule. And were carried out under the operating conditions shown in Table 1. In all of Examples 4, 5, and 6, it was confirmed by visual observation that the capsule inner surface and the capsule inner member surface were covered with a dull silver coating after the operation was completed.
- Example 7 In this example, NH 4 I was used as a mineralizer as shown in Table 1. The operating conditions are shown in Table 1. After the operation was completed, it was confirmed that the capsule inner surface and the capsule inner member surface were covered with a dull silver film. The coating was formed over the entire crystal growth region 6 in the upper part of the capsule and the raw material dissolution region 9 in the lower part of the capsule.
- Example 8 In this example, the Pt plate to which the GaPt alloy film was adhered in Example 3 was again put into the capsule.
- the operating conditions are as shown in Table 1. After the operation was completed, the Pt plate was taken out of the capsule and the surface was observed with the naked eye. As a result, the same dull silver color as before was observed and it was confirmed that a Ga—Pt alloy film was formed.
- the weight of the Pt plate increased from 2.3615 g to 2.3744 g, and it was confirmed that the weight increased by 0.0129 g from before the charging.
- Example 9 In this example, the Pt plate with the Ga—Pt alloy coating adhered in Example 8 was again put into the capsule.
- the operating conditions are as shown in Table 1. After the operation was completed, the Pt plate was taken out of the capsule and the surface was observed with the naked eye. As a result, the same dull silver color as before was observed and it was confirmed that a Ga—Pt alloy film was formed.
- the weight of the Pt plate increased from 2.3744 g to 2.3855 g, and a weight increase of 0.0111 g was confirmed from before the charging.
- Example 10 In this example, the Pt plate with the Ga—Pt alloy coating adhered in Example 9 was again put into the capsule.
- the operating conditions are as shown in Table 1. After the operation was completed, the Pt plate was taken out of the capsule and the surface was observed with the naked eye. As a result, the same dull silver color as before was observed and it was confirmed that a Ga—Pt alloy film was formed.
- the weight of the Pt plate increased from 2.3853 g to 2.4006 g, confirming an increase in weight of 0.0153 g from before the charging.
- the GaPt alloy is stable in a high temperature and high pressure ammonothermal environment, and is not corroded.
- the corrosion of the capsule material Pt and the Pt alloy was suppressed, and the life of the capsule and the high purity of the crystal were achieved.
- the present invention is useful for growing a bulk single crystal of a group 13 element nitride, particularly a bulk single crystal of GaN. According to the production method of the present invention, it is possible to reduce impurities derived from reaction vessels and members in the obtained crystal, and it is possible to use a reaction vessel having a stable surface in crystal growth more than once, Significant improvements can be expected in both time and cost. Therefore, the present invention has very high industrial applicability.
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Abstract
Description
そこで、これらの貴金属よりもより安定な材料を反応容器に適用して、得られる窒化物結晶中の不純物を低減させる必要がある。
[1] 反応容器中で超臨界および/または亜臨界状態の溶媒存在下にて結晶成長を行う結晶成長工程、及び該反応容器表面並びに該反応容器内部で使用される部材の表面の少なくとも一部を白金族-第13族金属合金で被覆して白金族-第13族金属合金被膜を形成する被膜形成工程を有することを特徴とする、半導体結晶の製造方法。
[2] 反応容器中で超臨界及び/又は亜臨界状態の溶媒存在下で結晶成長を行って半導体結晶を製造する方法であって、該反応容器表面並びに該反応容器内部で使用される部材の表面の少なくとも一部が白金族-第13族金属合金被膜で被覆されていることを特徴とする、半導体結晶の製造方法。
[3] 前記白金族-第13族金属合金被膜が第13族金属として少なくともGaを含む、[1]または[2]に記載の半導体結晶の製造方法。
[4] 前記白金族-第13族金属合金被膜が白金族として少なくともPtを含む、[1]~[3]のいずれか1項に記載の半導体結晶の製造方法。
[5]前記反応容器内部の表面並びに前記反応容器内部で使用される部材の表面の総面積のうち、50%以上を白金族-第13族金属合金で被覆する、[1]~[4]のいずれか1項に記載の半導体結晶の製造方法。
[6] 前記結晶成長工程中の少なくとも一部で、前記被膜形成工程を同時に実施する、[1]に記載の半導体結晶の製造方法。
[7] 前記白金族-第13族金属合金被膜が、Ga3Pt5、Ga3Pt2、GaPt、Ga2Pt、Ga2Pt、GaPt2およびGaPt3からなる群より選ばれる1以上の合金を含む被膜である、[1]~[6]のいずれか1項に記載の半導体結晶の製造方法。
[8] 前記白金族-第13族金属合金被膜の厚みが5~100μmである、[1]~[7]のいずれか1項に記載の半導体結晶の製造方法。
[9] 前記結晶成長工程および/または前記被膜形成工程を複数回実施する、[1]に記載の半導体結晶の製造方法。
[10] 前記反応容器及び前記反応容器内部で使用される部材が、Pt又はPtを含む合金からなる、[1]~[9]のいずれか1項に記載の半導体結晶の製造方法。
[11] 前記被膜形成工程において、反応容器内を超臨界および/または亜臨界状態の溶媒及び第13族金属の存在下、温度400~700℃、圧力100~700MPaとして前記白金族-第13族金属合金被膜を形成する、[1]に記載の半導体結晶の製造方法。
[12] 前記白金族-第13族金属合金被膜が多結晶からなる、[1]~[11]のいずれか1項に記載の半導体結晶の製造方法。
[14] 前記反応容器が、白金族又は白金族を含む合金からなるカプセルである、[13]に記載の結晶製造装置。
[15] 記反応容器が、Pt-Ir合金を含む合金からなるカプセルである、[13]に記載の結晶製造装置。
[16] 前記耐圧性容器が白金族又は白金族を含む合金でライニングした内壁を有する、[13]~[15]のいずれか1項に記載の結晶製造装置。
[17] 記白金族-第13族金属合金被膜が、該反応容器内部の表面並びに該反応容器内部で使用される部材の表面の総面積のうち50%以上に存在する、[13]~[16]のいずれか1項に記載の結晶製造装置。
[18] 前記白金族-第13族金属合金被膜が第13族金属として少なくともGaを含む、[13]~[17]のいずれか1項に記載の結晶製造装置。
[19] 前記白金族-第13族金属合金被膜が白金族として少なくともPtを含む、[13]~[18]のいずれか1項に記載の結晶製造装置。
[20] 前記白金族-第13族金属合金被膜が、Ga3Pt5、Ga3Pt2、GaPt、Ga2Pt、Ga2Pt、GaPt2及びGaPt3からなる群より選ばれる1以上の合金を含む被膜である、[13]~[19]のいずれか1項に記載の結晶製造装置。
[21] 前記白金族-第13族金属合金被膜の厚みが5~100μmである、[13]~[20]のいずれか1項に記載の結晶製造装置。
[22] 前記反応容器及び前記反応容器内部で使用される部材が、Pt又はPtを含む合金からなる、[13]~[21]のいずれか1項に記載の結晶製造装置。
[23] 前記白金族-第13族金属合金被膜が多結晶からなる、[13]~[22]のいずれか1項に記載の結晶製造装置。
[24] 結晶中に不純物として含まれる白金族金属元素の濃度が、白金族金属の不存在下で結晶成長された第13族窒化物半導体結晶の10倍以下であることを特徴とする、超臨界および/または亜臨界状態の溶媒存在下にて結晶成長した第13族窒化物半導体結晶。
また、本発明の窒化物結晶は均一で高品質であるために、発光デバイスや電子デバイス用の半導体結晶等として有用である。
また、本発明の半導体結晶の製造方法の第二の様態は、反応容器中で超臨界及び/又は亜臨界状態の溶媒存在下で結晶成長を行って半導体結晶を製造する方法であって、該反応容器表面並びに該反応容器内部で使用される部材の表面の少なくとも一部が白金族-第13族金属合金被膜で被覆されている。
本発明の各工程は、少なくとも耐圧性容器内に、超臨界アンモニア雰囲気などの超臨界および/または亜臨界状態の溶媒存在下にて結晶成長を行うための反応容器が設置されてなる結晶製造装置を用いて行われる。該反応容器内部の表面及び該反応容器内部で使用される部材表面の少なくとも一部は白金族-第13族金属合金被膜で被覆されてなる。白金族-第13族金属合金被膜の詳細については、被膜形成工程の説明の項で詳述する。
「反応容器」とは、超臨界および/または亜臨界状態の溶媒がその内壁面に直接接触しうる状態で窒化物結晶の製造を行うための容器を意味し、耐圧性容器内部の構造そのものや、耐圧性容器内に設置されるカプセルなどを好ましい例として挙げることができる。
本発明の製造方法は、反応容器内部に部材を設置した状態で行うのが一般的である。ここでいう「部材」とは、アモノサーマル法により窒化物結晶を製造する際に容器中に設置するものであって、反応容器から分離することができるものを意味する。例えば、種結晶を保持するための育成枠、溶液の対流を制御するバッフル板、原料カゴ、種結晶を吊るすワイヤーなどを挙げることができる。本発明では、これら部材の表面も、上述のような耐腐食性に優れる材料によって覆うことが好ましい。
以下、本発明の製造方法の各工程について詳細に説明する。
結晶成長工程は、反応容器中で超臨界および/または亜臨界状態の溶媒存在下にて結晶成長を行う工程である。
結晶成長の条件としては、特開2009-263229号公報に開示されているような原料、鉱化剤、種結晶、溶媒、温度、圧力などの条件を好ましく用いることができる。該公開公報の開示全体を本明細書に引用して援用する。
白金族-第13族金属合金は、超臨界アンモニア溶媒などの超臨界および/または亜臨界状態の溶媒やこれに鉱化剤、原材料などが溶解した溶液に対して極めて安定なので、反応容器内部の表面並びに該反応容器内部で使用される部材の表面の少なくとも一部を白金族-第13族金属合金で被覆した場合には、反応容器や部材が腐食されることがなく、得られる窒化物結晶中の不純物を低減することが可能となる。不純物がより低減されることから、該反応容器内部の表面並びに該反応容器内部で使用される部材の表面の総面積のうち、50%以上が被覆されていることが好ましく、より好ましくは70%以上、さらに好ましくは80%以上、特に好ましくは90%以上であり、100%被覆されていてもよい。
白金族-第13族金属合金被膜を構成する第13族金属としては、アルミニウム(Al)、ガリウム(Ga)、インジウム(In)、タリウム(Tl)などが挙げられるが、少なくともGaを含む金属であることが好ましい。
なお、被膜形成工程が複数回実施される場合には、白金族-第13族金属合金被膜は回数を重ねるごとにより厚くなる傾向がある。
白金族-第13族金属合金被膜の形成方法は特に限定されず、たとえば反応容器内に白金族金属及び第13族金属が存在する環境下において、温度及び圧力を上げることによって形成することができる。
反応容器内に存在する白金族金属は、反応容器の表面や部材自体であると、白金族-第13族金属合金を被覆すべき部分に効率的に白金族-第13族金属合金被膜を形成することができるため好ましい。反応容器内に存在する第13族金属は、原材料として第13族金属を用いる場合には、原材料に由来するもので構わない。または、白金族-第13族金属合金被膜の原料として結晶の原材料や反応容器の材料とは別に、白金族金属や第13族金属を反応容器内に配置してもよい。
被膜を形成する際の圧力としては、80MPa以上とすることが好ましく、より好ましくは100MPa以上、さらに好ましくは120MPa以上であって、700MPa以下とすることが好ましく、より好ましくは500MPa以下、さらに好ましくは400MPa以下、特に好ましくは300MPa以下である。下限値以上であると、より安定な被膜を形成できるため好ましい。
被膜形成工程は、反応容器内部の表面並びに該反応容器内部で使用される部材の表面にすでに白金族-第13族金属合金被膜が形成されている状態で実施してもよい。
本発明の製造方法で得られる半導体結晶は、従来は除去し切れなかった白金族などの不純物を低減されている。特に、結晶中に不純物として含まれる白金族金属元素の濃度が、白金族金属の不存在下で結晶成長された第13族窒化物半導体結晶の10倍以下、好ましくは5倍以下であるような第13族窒化物半導体結晶を提供することができる。
ここで、白金族金属の不存在下で結晶成長された第13族窒化物半導体結晶とは、たとえば白金族金属を含まない結晶成長装置を用いるハイドライド気相成長法(HVPE)で得られる第13族窒化物半導体結晶が挙げられる。このような方法によれば、成長雰囲気内に白金族金属が存在しないため、得られる結晶中に白金族金属が含まれることはないと考えられる。
図3に示す装置を用いてHVPE法により第13族窒化物半導体結晶を成長させることができる。
図3の製造装置は、リアクター100内に、下地基板を載置するためのサセプター108と、成長させるIII族窒化物の原料を入れるリザーバー106とを備えている。また、リアクター100内にガスを導入するための導入管101~105と、排気するための排気管109が設置されている。さらに、リアクター100を側面から加熱するためのヒーター107が設置されている。
リアクター100の材質としては、石英、焼結体窒化ホウ素、ステンレス等が用いられる。好ましい材質は石英である。リアクター100内には、反応開始前にあらかじめ雰囲気ガスを充填しておく。雰囲気ガス(キャリアガス)としては、例えば、水素、窒素、He、Ne、Arのような不活性ガス等を挙げることができる。これらのガスは混合して用いてもよい。
サセプター108の材質としてはカーボンが好ましく、SiCで表面をコーティングしているものがより好ましい。サセプター108の形状は、本発明で用いる成長用下地基板を設置することができる形状であれば特に制限されないが、結晶成長する際に結晶成長面付近に構造物が存在しないものであることが好ましい。結晶成長面付近に成長する可能性のある構造物が存在すると、そこに多結晶体が付着し、その生成物としてHClガスが発生して結晶成長させようとしている結晶に悪影響が及んでしまう。下地基板とサセプター108の接触面は、下地基板の結晶成長面から1mm以上離れていることが好ましく、3mm以上離れていることがより好ましく、5mm以上離れていることがさらに好ましい。
リザーバー106には、成長させる第13族窒化物の原料を入れる。具体的には、第13族源となる原料を入れる。そのような第13族源となる原料として、Ga、Al、Inなどを挙げることができる。リザーバー106にガスを導入するための導入管103からは、リザーバー106に入れた原料と反応するガスを供給する。例えば、リザーバー106に第13族源となる原料を入れた場合は、導入管103からHClガスを供給することができる。このとき、HClガスとともに、導入管103からキャリアガスを供給してもよい。キャリアガスとしては、例えば水素、窒素、He、Ne、Arのような不活性ガス等を挙げることができる。これらのガスは混合して用いてもよい。
導入管104からは、窒素源となる原料ガスを供給する。通常はNH3を供給する。また、導入管101からは、キャリアガスを供給する。キャリアガスとしては、導入管103から供給するキャリアガスと同じものを例示することができる。このキャリアガスは原料ガスノズルを分離し、ノズル先端にポリ結晶が付着することを防ぐ効果もある。また、導入管102からは、ドーパントガスを供給することができ、導入管105からは、多結晶などをエッチングしてリアクター内をクリーニングするためのHClを供給する事ができる。
導入管101~105から供給する上記ガスは、それぞれ互いに入れ替えて別の導入管から供給しても構わない。また、窒素源となる原料ガスとキャリアガスは、同じ導入管から混合して供給してもよい。さらに他の導入管からキャリアガスを混合してもよい。これらの供給態様は、リアクター100の大きさや形状、原料の反応性、目的とする結晶成長速度などに応じて、適宜決定することができる。
ガス排気管109は、リアクター内壁の上面、底面、側面に設置することができる。ゴミ落ちの観点から結晶成長端よりも下部にあることが好ましく、図3のようにリアクター底面にガス排気管109が設置されていることがより好ましい。
上記の製造装置を用いた結晶成長は、通常は950℃以上で行い、970℃以上で行うことが好ましく、980℃以上で行うことがより好ましく、990℃以上で行うことがさらに好ましい。また、通常は1120℃以下で行い、1100℃以下で行うことが好ましく、1090℃以下で行うことがより好ましく、1080℃以下で行うことがさらに好ましい。リアクター内の圧力は10kPa以上であるのが好ましく、30kPa以上であるのがより好ましく、50kPa以上であるのがさらに好ましい。また、200kPa以下であるのが好ましく、150kPa以下であるのがより好ましく、120kPa以下であるのがさらに好ましい。
上記の製造装置を用いた結晶成長の成長速度は、成長方法、成長温度、原料ガス供給量、結晶成長面方位等により異なるが、一般的には5μm/h~500μm/hの範囲であり、10μm/h以上が好ましく、50μm/h以上がより好ましく、70μm以上であることがさらに好ましい。成長速度は、上記の他、キャリアガスの種類、流量、供給口-結晶成長端距離等を適宜設定することによって制御することができる。
1)白金族-第13族金属合金被膜の形成有無
各実施例にて結晶成長実施後の反応容器内部の表面を目視にて観察し、白金族-第13族金属合金被膜の形成有無を以下の2段階で評価した。
○:白金族-第13族金属合金被膜が形成されている。
金属光沢がなく、灰色に変色している。
×:白金族-第13族金属合金被膜が形成されていない。
結晶成長実施前と同様に金属光沢がある。
被膜は、X線回折測定を行い白金族-第13族金属の回折ピークの有無を確認した。また、EDSにより、白金族と第13族金属等の元素分析を行なった。
窒化物結晶中の白金族の元素分析をSIMSにより分析した。測定装置は二次イオン質量分析装置を使用した。リファレンスとして、Pt、Irの不存在下で結晶成長を行うためPt、Irの混入がないHVPE法で成長した結晶を使用した。
本実施例では、図2に示す反応装置を用いて窒化物結晶を成長させた。
RENE41製オートクレーブ1(内容積約345cm3)を耐圧容器として用い、Pt-Ir製カプセル20を反応容器として結晶成長を行った。カプセルへの充填作業は十分に乾燥した窒素雰囲気グローブボックス内にて行った。原料8として多結晶GaN粒子36gを秤量し、カプセル下部領域(原料溶解領域9)内に設置した。次に鉱化剤として十分に乾燥した純度99.99%のNH4Clを2.0g秤量しカプセル内に投入した。
本実施例では、実施例1と同様にNH4Cl試薬を用いて、表1に示す運転条件で実施した。運転終了後、目視によりカプセル内表面およびカプセル内部材表面は鈍い銀色の被膜で覆われていることを確認した。
本実施例では、鉱化剤としてNH4Cl試薬の代わりに、高純度HClガスをカプセル中に導入し、アンモニアと反応させ、カプセル内でNH4Clを生成させた。HClガスを用いることによりNH4Cl試薬に含まれる水分、酸素を除去することが可能となる。その他の工程は実施例1と同様で、運転条件は表1に示すとおりである。
実施例4~6では、実施例3と同様に、鉱化剤としてNH4Cl試薬の代わりに、高純度HClガスをカプセル中に導入し、アンモニアと反応させ、カプセル内でNH4Clを生成させ、表1に示す運転条件で実施した。実施例4、5、6のいずれも、運転終了後、目視によりカプセル内表面およびカプセル内部材表面は鈍い銀色の被膜で覆われていることを確認した。
本実施例では表1に示すように鉱化剤としてNH4Iを用いた。運転条件は表1に示した。運転終了後、カプセル内表面およびカプセル内部材表面は鈍い銀色の被膜で覆われていることが確認された。被膜はカプセル上部の結晶育成領域6とカプセル下部の原料溶解領域9の全てにわたって生成していた。
本実施例では、実施例3においてGaPt合金被膜が付着したPt板を再度カプセルに投入した。運転条件は表1に示すとおりである。
運転終了後、Pt板をカプセルから取り出し、表面を肉眼で観察したところ投入前と同様の鈍い銀色の着色が観察されGa-Pt合金被膜が形成されていることが確認された。Pt板の重量は2.3615gから2.3744gへ増加しており投入前よりも0.0129gの重量増が確認された。
本実施例では、実施例8においてGa-Pt合金被膜が付着したPt板を再度カプセルに投入した。運転条件は表1に示すとおりである。
運転終了後、Pt板をカプセルから取り出し、表面を肉眼で観察したところ投入前と同様の鈍い銀色の着色が観察されGa-Pt合金被膜が形成されていることが確認された。Pt板の重量は2.3744gから2.3855gへ増加しており投入前よりも0.0111gの重量増が確認された。
本実施例では実施例9においてGa-Pt合金被膜が付着したPt板を再度カプセルに投入した。運転条件は表1に示すとおりである。
運転終了後、Pt板をカプセルから取り出し、表面を肉眼で観察したところ投入前と同様の鈍い銀色の着色が観察されGa-Pt合金被膜が形成されていることが確認された。Pt板の重量は2.3853gから2.4006gへ増加しており投入前よりも0.0153gの重量増が確認された。
本実施例では、実施例10においてGa-Pt合金被膜が付着したPt板を再度カプセルに投入した。運転条件は表1に示すとおりである。
運転終了後、Pt板をカプセルから取り出し、表面を肉眼で観察したところ投入前と同様の鈍い銀色の着色が観察されGa-Pt合金被膜が形成されていることが確認された。Pt板の重量は2.4006gから2.4077gへ増加しており投入前よりも0.0071gの重量増が確認された。
上記実施例3、8、9、10、11に示したように、GaPt合金被膜が形成された後は、繰り返し使用により重量が微増を続ける。つまりGaPt合金は高温高圧のアモノサーマル環境下において安定であり、腐蝕されないことを示している。Ga-Pt合金によって被覆することでカプセル材料であるPtおよびPt合金の腐蝕を抑えカプセルの長寿命化と結晶の高純度化が達成された。
本実施例では実施例3と同様の工程で表1に示した条件で運転を行った。
運転終了後、カプセル内表面およびカプセル内部材表面は鈍い銀色の被膜で覆われていることが確認された。被膜はカプセル内の上部結晶析出領域と下部原料溶解領域の全てにわたって生成していた。
本実施例では実施例3と同様の工程で表1に示す条件で運転を行なった。
運転終了後、カプセル内表面およびカプセル内部材表面は鈍い銀色の被膜で覆われていることが確認された。被膜はカプセル内の上部結晶析出領域と下部原料溶解領域の全てにわたって生成していた。
本比較例では表1に示す条件で、カプセルを用いずに、内面にPtおよびPt-Ir合金でライニングされたオートクレーブを用いた。
運転終了後、カプセル内表面およびカプセル内部材表面は金属光沢を呈しており、Ga-Pt合金の生成は確認されなかった。
育成された結晶中のPt,IrをSIMSにて分析を行ったところ、Irは7.51×102counts/sec、Ptは2.74×102counts/secであった。
本実施例では鉱化剤としてNH4IとGaF3を用いて実施例1と同様の工程で表1に示した条件で運転を行った。なお、表1に記した鉱化剤濃度は、NH4IとGaF3の合計ハロゲン濃度である。
運転終了後、カプセル内表面には鈍い銀色の被膜で覆われていることが確認された。被膜はカプセル内の上部結晶析出領域と下部原料溶解領域の全てにわたって生成していた。
表2に、実施例7、12、13、比較例1とPt、Irの混入がないHVPE法で成長した結晶(リファレンスとして使用)のSIMS分析結果を示した。表2に示したように、実施例7、12、13はHVPE法で成長した結晶とほぼ同様結果が得られた。これにより、白金族-第13族金属の被膜を形成することで、育成された結晶中へのPt、Irの混入を低減できたことがわかる。一方、比較例1で育成した結晶については、HVPE法により成長した結晶と比較してPt、Irが10倍より多く含有されていることがわかった。
本明細書の開示事項は、2010年12月27日に出願された米国仮出願第61/427403号の主題に関係するものであり、当該出願の全記載事項を本明細書の一部としてここに引用することを明言する。また、本明細書において参照している全ての文献に記載されている事項も、本明細書の一部としてここに引用することを明言する。
2 オートクレーブ内面
3 ライニング
4 ライニング内面
5 バッフル板
6 結晶成長領域
7 種結晶
8 原料
9 原料溶解領域
10 バルブ
11 真空ポンプ
12 アンモニアボンベ
13 窒素ボンベ
14 マスフローメータ
20 カプセル
21 カプセル内面
100 リアクター
101 キャリアガス用配管
102 キャリアガス用配管
103 第13族原料用配管
104 窒素原料用配管
105 HClガス用配管
106 第13族原料用リザーバー
107 ヒーター
108 サセプター
109 排気管
G1 キャリアガス
G2 キャリアガス
G3 第13族原料ガス
G4 窒素原料ガス
G5 HClガス
Claims (24)
- 反応容器中で超臨界および/または亜臨界状態の溶媒存在下にて結晶成長を行う結晶成長工程、及び該反応容器表面並びに該反応容器内部で使用される部材の表面の少なくとも一部を白金族-第13族金属合金で被覆して白金族-第13族金属合金被膜を形成する被膜形成工程を有することを特徴とする、半導体結晶の製造方法。
- 反応容器中で超臨界及び/又は亜臨界状態の溶媒存在下で結晶成長を行って半導体結晶を製造する方法であって、該反応容器表面並びに該反応容器内部で使用される部材の表面の少なくとも一部が白金族-第13族金属合金被膜で被覆されていることを特徴とする、半導体結晶の製造方法。
- 前記白金族-第13族金属合金被膜が第13族金属として少なくともGaを含む、請求項1または2に記載の半導体結晶の製造方法。
- 前記白金族-第13族金属合金被膜が白金族として少なくともPtを含む、請求項1~3のいずれか1項に記載の半導体結晶の製造方法。
- 前記反応容器内部の表面並びに前記反応容器内部で使用される部材の表面の総面積のうち、50%以上を白金族-第13族金属合金で被覆する、請求項1~4のいずれか1項に記載の半導体結晶の製造方法。
- 前記結晶成長工程中の少なくとも一部で、前記被膜形成工程を同時に実施する、請求項1に記載の半導体結晶の製造方法。
- 前記白金族-第13族金属合金被膜が、Ga3Pt5、Ga3Pt2、GaPt、Ga2Pt、Ga2Pt、GaPt2およびGaPt3からなる群より選ばれる1以上の合金を含む被膜である、請求項1~6のいずれか1項に記載の半導体結晶の製造方法。
- 前記白金族-第13族金属合金被膜の厚みが5~100μmである、請求項1~7のいずれか1項に記載の半導体結晶の製造方法。
- 前記結晶成長工程および/または前記被膜形成工程を複数回実施する、請求項1に記載の半導体結晶の製造方法。
- 前記反応容器及び前記反応容器内部で使用される部材が、Pt又はPtを含む合金からなる、請求項1~9のいずれか1項に記載の半導体結晶の製造方法。
- 前記被膜形成工程において、反応容器内を超臨界および/または亜臨界状態の溶媒及び第13族金属の存在下、温度400~700℃、圧力100~700MPaとして前記白金族-第13族金属合金被膜を形成する、請求項1に記載の半導体結晶の製造方法。
- 前記白金族-第13族金属合金被膜が多結晶からなる、請求項1~11のいずれか1項に記載の半導体結晶の製造方法。
- 耐圧性容器内に、超臨界アンモニア雰囲気において結晶成長を行うための反応容器が設置されてなる結晶製造装置であって、該反応容器内部の表面及び該反応容器内部で使用される部材の表面の少なくとも一部が白金族-第13族金属合金被膜で被覆されてなることを特徴とする結晶製造装置。
- 前記反応容器が、白金族又は白金族を含む合金からなるカプセルである、請求項13に記載の結晶製造装置。
- 記反応容器が、Pt-Ir合金を含む合金からなるカプセルである、請求項13に記載の結晶製造装置。
- 前記耐圧性容器が白金族又は白金族を含む合金でライニングした内壁を有する、請求項13~15のいずれか1項に記載の結晶製造装置。
- 記白金族-第13族金属合金被膜が、該反応容器内部の表面並びに該反応容器内部で使用される部材の表面の総面積のうち50%以上に存在する、請求項13~16のいずれか1項に記載の結晶製造装置。
- 前記白金族-第13族金属合金被膜が第13族金属として少なくともGaを含む、請求項13~17のいずれか1項に記載の結晶製造装置。
- 前記白金族-第13族金属合金被膜が白金族として少なくともPtを含む、請求項13~18のいずれか1項に記載の結晶製造装置。
- 前記白金族-第13族金属合金被膜が、Ga3Pt5、Ga3Pt2、GaPt、Ga2Pt、Ga2Pt、GaPt2及びGaPt3からなる群より選ばれる1以上の合金を含む被膜である、請求項13~19のいずれか1項に記載の結晶製造装置。
- 前記白金族-第13族金属合金被膜の厚みが5~100μmである、請求項13~20のいずれか1項に記載の結晶製造装置。
- 前記反応容器及び前記反応容器内部で使用される部材が、Pt又はPtを含む合金からなる、請求項13~21のいずれか1項に記載の結晶製造装置。
- 前記白金族-第13族金属合金被膜が多結晶からなる、請求項13~22のいずれか1項に記載の結晶製造装置。
- 結晶中に不純物として含まれる白金族金属元素の濃度が、白金族金属の不存在下で結晶成長された第13族窒化物半導体結晶の10倍以下であることを特徴とする、超臨界および/または亜臨界状態の溶媒存在下にて結晶成長した第13族窒化物半導体結晶。
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JP2014189426A (ja) * | 2013-03-26 | 2014-10-06 | Mitsubishi Chemicals Corp | 周期表第13族金属窒化物多結晶およびそれを用いた周期表第13族金属窒化物単結晶の製造方法 |
JP2015140288A (ja) * | 2014-01-29 | 2015-08-03 | 三菱化学株式会社 | 窒化物結晶成長用容器および窒化物結晶の製造方法 |
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WO2012128263A1 (ja) * | 2011-03-22 | 2012-09-27 | 三菱化学株式会社 | 窒化物結晶の製造方法 |
CN106319629A (zh) * | 2016-09-19 | 2017-01-11 | 中原特钢股份有限公司 | 一种用于生产氮化镓晶体的超高压容器 |
CN108866628A (zh) * | 2017-05-11 | 2018-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | 掺杂Mg的p型Ⅲ族氮化物单晶及其制备方法和应用 |
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