JP2007238348A - Method for manufacturing crystal using supercritical solvent and apparatus for manufacturing crystal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a crystal and an apparatus for manufacturing a crystal that can prevent a source material from soaring by heat convection of a solvent and can manufacture a high-quality crystal with high source material efficiency even when a powder source material is used. <P>SOLUTION: The method for manufacturing a crystal comprises growing a crystal in a reaction chamber by using (1) a solvent in a supercritical state and/or a sub-critical state and (2) a source material, wherein the reaction chamber is equipped with a crucible as a source material filling unit to be filled with the source material, and the filling amount of the source material in the crucible is controlled to satisfy h≥D/2 (h representing the distance from the upper end of the crucible to the upper surface of the source material filling the crucible and D representing the inner diameter of the crucible), or the crucible has a cap having one or more openings. An apparatus is provided to be used for the above method. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a crystal manufacturing method and a crystal manufacturing apparatus by a solvothermal method, and in particular, using a solid mineralizer and a nitrogen-containing solvent such as ammonia, gallium nitride (hereinafter referred to as the chemical formula “GaN” A crystal having excellent crystallinity by an ammonothermal method or the like for crystal growth of a nitride such as a group 13 element (hereinafter referred to as “group 13 element”) of the periodic table represented by The present invention relates to a crystal manufacturing method and a crystal manufacturing apparatus that can be manufactured.

  The solvothermal method is a general term for crystal manufacturing methods using a solvent in a supercritical state and / or a subcritical state, and is called a hydrothermal method (hydrothermal synthesis method) or ammonothermal method depending on the type of solvent used. The

  In the solvothermal method, a temperature difference is provided in a high-temperature and high-pressure system containing raw materials, a solvent, a seed crystal, a mineralizer, and the like, and crystal growth is performed by utilizing the difference in crystal solubility of the raw materials in the solvent due to this temperature difference. Is what you do. In order to perform single crystal growth with good crystallinity by the solvothermal method, it is necessary to maintain an appropriate crystal growth rate. In order to maintain an appropriate growth rate of the crystal, it is important that the raw material is sufficiently dissolved in the solvent.

  Conventionally, of the solvothermal method, crystal growth of quartz using the hydrothermal method is not a powder raw material, but a material called “Lasca” that is crushed into a certain size is used as a raw material. In the case of quartz, even when a bulk material is used, a sufficient dissolution rate of the material can be obtained and a large crystal can be grown.

  However, in the ammonothermal method for growing GaN, it is difficult to obtain a bulk material and it is common to use a powder material. For example, as a first stage, after synthesizing a GaN microcrystal raw material corresponding to the raw material, as a second stage, GaN single crystal growth is realized using this as a raw material (see, for example, Patent Document 1). As the GaN microcrystal raw material, a powder having an average particle diameter of about 1 to 5 μm is used. Also, from the viewpoint of increasing the dissolution rate of the raw material by increasing the contact area between the raw material and the solvent, a powder raw material having a large surface area is often used.

However, when the powder raw material is used, if the thermal convection of the solvent is large, there is a problem that the powder raw material rises and adheres to the seed crystal to generate crystal defects. For this reason, research and development of solidifying the raw material (granulation) in order to prevent the powder raw material from flying up is generally in progress. However, an appropriate binder that hardens the raw material has not been developed yet, and development of a means for preventing the new powder raw material from rising is desired.
JP-A-2003-277182 Paragraph Nos. [0009] to [0010]

  The present invention prevents the raw material from rising due to the thermal convection of the solvent, which is a problem in the prior art as described above, and can produce high-quality crystals even when a powder raw material is used. An object is to provide a high crystal production method and a crystal production apparatus.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a crucible as a raw material filling portion and adjusted the raw material filling amount of the crucible or used a lid having an opening in the crucible. It has been found that the raw material can be prevented from rising due to heat convection. The gist of the present invention is as follows.

(1) A crystal production method in which a crystal is grown using (1) a solvent in a supercritical state and / or a subcritical state, and (2) a raw material in a reaction vessel,
The reaction vessel includes a crucible as a raw material filling part for filling the raw material, and the amount of raw material charged into the crucible satisfies the following formula (1).
h ≧ D / 2 Formula (1)
(In formula (1), h represents the distance from the upper end of the crucible to the top surface of the filled raw material, and D represents the inner diameter of the crucible.)

(2) The crystal manufacturing method according to (1), wherein the crucible has a lid having one or more openings.

(3) A crystal production method in which a crystal is grown using (1) a supercritical and / or subcritical solvent, and (2) a raw material in a reaction vessel,
The crystal production method, wherein the reaction vessel includes a crucible as a raw material filling portion for filling the raw material, and the crucible has a lid having one or more openings.

(4) The method for producing a crystal according to (3), wherein a filling amount of the raw material into the crucible satisfies the following formula (1).
h ≧ D / 2 Formula (1)
(In formula (1), h represents the distance from the upper end of the crucible to the top surface of the filled raw material, and D represents the inner diameter of the crucible.)

(5) The crystal manufacturing method according to any one of (1) to (4), wherein the raw material filling unit includes a plurality of crucibles.

(6) The crystal manufacturing method according to any one of (2) to (5), wherein the opening ratio of the lid of the crucible satisfies the following formula (2).

5 ≦ (S _n / S ₀ ) × 100 ≦ 80 Formula (2)
(Wherein (in 2), S _n represents the opening area of the lid with the crucible, S ₀ represents the internal horizontal cross-sectional area of the crucible.)

(7) The crystal production method according to any one of (1) to (6), wherein a particle diameter of the raw material is 10 nm to 10 mm.

(8) The crystal production method according to any one of (1) to (7), wherein the obtained crystal is a single crystal.

(9) The crystal production method according to any one of (1) to (8), wherein the obtained crystal is a periodic table group 13 element nitride.

(10) The crystal production method according to any one of (1) to (9), wherein the solvent is a nitrogen-containing solvent.

(11) The crystal production method according to any one of (1) to (10), wherein the reaction vessel is an autoclave.

(12) A crystal production apparatus comprising a reaction vessel, wherein in the reaction vessel, (1) a solvent in a supercritical state and / or a subcritical state, and (2) a raw material is used to grow a crystal,
The reaction vessel is provided with a crucible as a raw material filling part for filling the raw material, and the amount of raw material charged into the crucible satisfies the following formula (1).

h ≧ D / 2 Formula (1)
(In Formula (1), h shows the distance from the upper end of a crucible to the raw material upper surface with which it filled, and D shows the inner diameter of a crucible.
)

(13) The crystal manufacturing apparatus according to (12), wherein the crucible has a lid having one or more openings.

(14) A crystal production apparatus comprising a reaction vessel, wherein (1) a solvent in a supercritical state and / or a subcritical state, and (2) a raw material are used to grow crystals.
The crystal production apparatus, wherein the reaction vessel includes a crucible as a raw material filling portion for filling the raw material, and the crucible has a lid having one or more openings.

(15) The crystal manufacturing apparatus according to (14), wherein a filling amount of the raw material into the crucible satisfies the following formula (1).

h ≧ D / 2 Formula (1)
(In Formula (1), h shows the distance from the upper end of a crucible to the raw material upper surface with which it filled, and D shows the inner diameter of a crucible.
)

(16) The crystal manufacturing apparatus according to any one of (12) to (15), wherein the raw material filling unit includes a plurality of crucibles.

(17) The crystal manufacturing apparatus according to any one of (13) to (16), wherein the opening ratio of the lid of the crucible satisfies the following formula (2).

5 ≦ (S _n / S ₀ ) × 100 ≦ 80 Formula (2)
(Wherein (in 2), S _n represents the opening area of the lid with the crucible, S ₀ represents the internal horizontal cross-sectional area of the crucible.)

(18) The crystal manufacturing apparatus according to any one of (12) to (17), wherein a particle diameter of the raw material is 10 nm to 10 mm.

(19) The crystal manufacturing apparatus according to any one of (12) to (18), wherein the solvent is a nitrogen-containing solvent.

(20) The crystal production apparatus according to any one of (12) to (19), wherein the reaction vessel is an autoclave.

  By the crystal production method and the crystal production apparatus of the present invention, it is possible to prevent the raw material from rising due to the thermal convection of the solvent. Thereby, even if it is a case where the raw material of a powder is used, the quality of a crystal | crystallization can be improved and the use efficiency of a raw material can be improved.

  Hereinafter, the crystal production method and the crystal production apparatus of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, 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 first aspect of the present invention is a crystal production method in which a crystal is grown using (1) a solvent in a supercritical state and / or a subcritical state and (2) a raw material in the reaction vessel, Is provided with a crucible as a raw material filling part for filling the raw material, and the amount of raw material charged into the crucible satisfies the following formula (1).
h ≧ D / 2 Formula (1)
(In formula (1), h represents the distance from the upper end of the crucible to the top surface of the filled raw material, and D represents the inner diameter of the crucible.)

  The second aspect of the present invention is a crystal production method in which a crystal is grown using (1) a supercritical and / or subcritical solvent and (2) a raw material in a reaction vessel, The reaction vessel includes a crucible as a raw material filling portion for filling the raw material, and the crucible has a lid having one or more openings.

  Crystal manufacturing method and crystal manufacturing apparatus used therefor for the first and second inventions (hereinafter referred to as “the present invention” when including the first invention and the second invention) Uses a crucible satisfying the above formula (1) as a raw material filling part or a crucible having a lid having one or more openings as a raw material filling part to prevent the raw material from rising due to thermal convection of the solvent. can do. For this reason, even when a powder raw material is used, it is possible to prevent a crystal raw material from adhering to the seed crystal and cause crystal defects and the like. The use efficiency can be improved. Further, according to the present invention, the contact between the raw material and the solvent can be controlled to some extent, so that the dissolution rate of the raw material can be adjusted.

  The present invention has a limitation in the shape of the raw material due to the difficulty of obtaining a bulk raw material among the solvothermal methods, and is suitable for a method using a powder raw material, particularly an ammonothermal method for growing GaN. Can be suitably used. The reaction vessel in the present invention is not particularly limited as long as it can be applied to crystal growth using a solvent in a supercritical state and / or a subcritical state (hereinafter referred to as “supercritical solvent”). For example, an autoclave is preferable.

  First, the case where an autoclave is used as an apparatus used in the crystal production apparatus of the present invention and the production method of the present invention will be described with reference to FIGS. However, the present invention is not limited to these embodiments.

  FIG. 1 is a schematic view showing a crystal production apparatus of the present invention using a plurality of crucibles. In FIG. 1, a crystal production apparatus 1 has an autoclave used for an ammonothermal method, and is composed of a reaction vessel (autoclave) 2 and a conduit 3. The reaction vessel 2 has a crystal growth region 4 and a raw material filling region 5, and a baffle plate 6 is provided at the boundary. The reaction vessel 2 is provided with a five-stage ladder-like support 8 having three crucibles 7 each filled with a powdery raw material in the crystal filling region 5, and further the raw material dissolution rate. The mineralizer 10 for improving the temperature is filled so as to fill between the crucibles 7. The plurality of crucibles 7 have the same shape and volume. The crystal growth region 4 of the reaction vessel 2 is provided with a plurality of seed crystals 9. 1 to 3, the reaction vessel 2 and the crucible 7 are assumed to be cylindrical. In the following drawings, the direction from the top to the bottom of the page is the direction of gravity.

  A plurality of heaters 11 and thermocouples 12 are provided in the vicinity of the outside of the reaction vessel 2 in order to provide a temperature difference in the high-temperature and high-pressure system. The autoclave 1 is configured such that the temperature can be controlled by dividing the reaction vessel 2 into a plurality of zones by a heater 11 and a thermocouple 12 (in FIG. 1, it is divided into two zones, upper and lower with respect to the paper surface). The output can be changed every time. This temperature difference is set so that the solubility curve becomes a lower temperature as it goes to the upper part of the autoclave 1 when the solubility curve has a positive slope (the higher the temperature, the higher the solubility).

In the autoclave 1, after vacuum degassing from the state shown in FIG. 1, a supercritical solvent such as NH ₃ is filled into the reaction vessel 2 through the conduit 3, and the temperature is increased between the crystal growth region 4 and the raw material filling region under high pressure. Raise the temperature while making a difference. Furthermore, after the temperature of the reaction vessel 2 reaches a predetermined temperature, a desired single crystal can be deposited in the form of a seed crystal by holding for a certain period of time.

  In the first aspect of the present invention, the raw material filling amount (charge amount) in the plurality of crucibles 7 satisfies the following formula (1).

h ≧ D / 2 Formula (1)
(In formula (1), h represents the distance from the upper end of the crucible to the top surface of the filled raw material, and D represents the inner diameter of the crucible.)

  The filling amount to the crucible in the first aspect of the present invention will be described with reference to FIG. FIG. 2 is a cross-sectional view for explaining the amount of raw material charged into the crucible. As shown in FIG. 2, the crucible 7 is filled with a powder raw material 13. As shown in the formula (1), the distance represented by the arrow h in FIG. 2 indicates the distance from the upper end of the crucible to the upper surface of the raw material filled in the crucible. Moreover, as shown in Formula (1), the arrow D in FIG. 2 shows the inner diameter of the crucible. In the first aspect of the present invention, when D / 2 represented by the above formula (1) is larger than h, the thermal convection of the solvent reaches the raw material surface in the crucible directly at an angle of 45 degrees or less. The component of the downward force to be pressed becomes weaker than the component that pushes the raw material in the horizontal direction, and the powder raw material cannot be prevented from rising. In the above formula (1), h ≧ D / 2 may be satisfied, but it is preferable that h ≧ D.

  When the cross-sectional shape is a perfect circle as in the crucible used in FIGS. 1 and 2, the inner diameter of the opening is directly D in equation (1). For example, when the cross-sectional shape of the crucible 7 is a polygon , The longest distance connecting the vertices is D in Equation (1). Moreover, when the cross-sectional shape of the crucible 7 is an ellipse, the major axis of the ellipse is D in the formula (1). The cross-sectional shape of the crucible in the first aspect of the present invention is preferably a perfect circle due to the symmetry of the thermal convection of the solvent.

  In the second aspect of the present invention, a crucible with a lid is used as the crucible 7 in FIG. The second present invention will be described with reference to FIG. FIG. 3 is a schematic view for explaining a crucible with a lid according to the second aspect of the present invention. As shown in FIG. 3A, a lid 14 is used for the crucible 7 in the second aspect of the present invention. The lid 14 is provided with a plurality of openings 15, and the lid 14 having the openings 15 can be prevented from being discharged out of the crucible 7 after having acted as an eaves. The lid 14 only needs to have at least one opening 15, and the number, size, and shape of the lid 14 are not particularly limited, but preferably satisfy the following formula (2).

5 ≦ (S _n / S ₀ ) × 100 ≦ 80 Formula (2)
(Wherein (in 2), S _n represents the opening area of the lid with the crucible, S ₀ represents the internal horizontal cross-sectional area of the crucible.)

In formula (2), Sn represents the opening area of the lid of the crucible, but when a plurality of openings are provided in the lid of one crucible, the sum of them is the opening area in formula (2). . In the case of using a plurality of crucibles in the second invention, the total opening area of the lid with each crucible becomes S _n, the sum of the internal horizontal cross-sectional area of the crucible becomes S _0. However, when a plurality of crucibles with the same shape as shown in FIG. 1 are used, the opening ratio considering all the crucibles obtained by the above equation (2) and the opening ratio of each crucible are the same numerical value. Any one aperture ratio may be obtained. The internal horizontal cross-sectional area of the crucible 7 indicates the internal horizontal cross-sectional area at the opening portion of the crucible 7.

When specifically described, the sum of the plurality of opening areas of the lid with the crucible 7 is, S _n becomes as shown in FIG. 3B, S0 is, the inner diameter of the crucible 7, the diameter, the internal horizontal cross-sectional area of the crucible 7. The second aspect of the present invention preferably satisfies 5 ≦ S _n / S ₀ × 100 ≦ 80, more preferably, the lower limit of S _n / S ₀ × 100 is 8% or more, more preferably 10%. The upper limit is preferably 50% or less, more preferably 30% or less. Thus, by adjusting the aperture ratio, the speed at which the dissolved raw material is transported from the raw material filling portion to the seed crystal by the convection of the solvent is adjusted, and an appropriate crystal growth rate can be maintained. In addition, about the opening part of the crucible with a lid | cover, an opening part can be changed according to the particle size of a raw material. In addition, raw materials having different particle diameters can be used in combination.

In the second aspect of the present invention, the shape of the cross-sectional area of the crucible is not particularly defined, and may be a polygon, a perfect circle, or an ellipse. Since the convection of the solvent is controlled by the opening shape of the lid, the shape is not particularly limited when there is a lid having an opening.
Also, the charged amount of the raw material is not limited to the crucible with a lid according to the second aspect of the invention, unlike the crucible without a cover according to the first aspect of the invention. However, it is preferable that the amount of charge satisfies the condition of the above formula (1) since it is more effective to secure a certain amount of space in the crucible and a large contact area with the solvent can be obtained. Thus, a crystal manufacturing method and a crystal manufacturing apparatus that satisfy the requirements of both the first invention and the second invention are also suitable.

  Hereinafter, the present invention will be described with reference to the drawings as appropriate, taking as an example an ammonothermal method of growing a group 13 nitride crystal using a nitrogen-containing solvent such as ammonia.

[Crystal production equipment]
(Reaction vessel)
The crystal production apparatus of the present invention has at least the reaction vessel of the present invention. An autoclave is suitable as the reaction vessel.
The structure of the autoclave (reaction vessel in the present invention) will be described. The autoclave is usually separated like a lid and a container and sealed with a gasket or the like. Moreover, you may have a recessed part for inserting a thermocouple etc. As shown in FIG. 1, the reaction vessel in the present invention includes an autoclave having a conduit.

  The autoclave is preferably capable of withstanding a pressure corresponding to the ultrahigh pressure of a supercritical solvent (for example, supercritical ammonia) during the temperature rising reaction. The material for forming the autoclave is not particularly limited as long as it has pressure resistance and erosion resistance. In particular, it is preferable to use a Ni-based alloy that can withstand high temperature and high pressure and has high erosion resistance against ammonia, and a Co-based alloy such as Stellite (registered trademark of Deloro Stellite Company, Inc.). It is particularly preferable to use an alloy. Specific examples include Inconel 625 (Inconel is a registered trademark of Huntington Alloys Canada Limited, hereinafter the same), Nimonic 90 (Nimonic is a registered trademark of Special Metals Wiggin Limited, the same hereinafter), RENE41 and the like.

  The composition ratio of these alloys depends on the temperature / pressure conditions of the solvent in the system, the reactivity with the various mineralizers contained in the system and their reactants, and / or the oxidizing power / reducing power, pH. What is necessary is just to select suitably according to conditions. As a method of using these as a material constituting the inner surface of the autoclave, a method of manufacturing the autoclave itself using these alloys, a method of forming a thin film as an inner cylinder and installing it in the autoclave may be used. A method of plating the inner surface of the material may also be used.

  In order to further improve the erosion resistance of the autoclave, the inner surface of the autoclave may be lined or coated using the superior erosion resistance of the noble metal. Further, the material of the autoclave itself can be a noble metal. Examples of the noble metal include Pt, Au, Ir, Ru, Rh, Pd, Ag, Os, and alloys containing these noble metals as main components. Among them, it is preferable to use Pt having excellent erosion resistance.

  When the inner surface of the autoclave is lined or coated with a noble metal, if it is difficult to line or coat the entire inner surface, it may be lined or coated on the upper part and / or the lower part of the autoclave. There may be parts that cannot be done.

  The autoclave is a crystal in which a baffle plate (baffle plate 6 in FIG. 1) is installed inside as required, and a raw material filling region filled with a raw material made of GaN polycrystalline nitride or the like and a seed crystal such as GaN are arranged. It is divided into growth regions. Hereinafter, the present invention may be described by taking GaN polycrystalline nitride as a raw material and GaN as a seed crystal as an example, but the present invention is not limited to this.

(Raw material filling part)
In the present invention, a crucible is used as a raw material filling part for filling the raw material into the reaction vessel. The number of crucibles is not particularly limited, and one or a plurality of crucibles can be used depending on the purpose, but a plurality of crucibles are preferably used. The material of the crucible is not particularly limited as long as it has contact resistance to a supercritical solvent such as supercritical ammonia, and examples thereof include pBN (Pyrolitic Boron Nitride), platinum, and iridium. The shape of the crucible is not particularly limited, but is preferably a cylindrical shape. Furthermore, the cross-sectional shape of the crucible may be polygonal or circular, but is preferably a perfect circle. However, when using a crucible with a lid like the crucible in the second aspect of the present invention, the cross-sectional shape of the crucible is not particularly limited. This is because when a crucible with a lid is used, the convection of the solvent is controlled by the opening shape of the lid. On the other hand, when a lid is not used, the cross-sectional shape is preferably a perfect circle from the symmetry of solvent convection.

  The depth of the crucible is not particularly limited, but in the first aspect of the present invention, the crucible must satisfy the above formula (1).

  Further, the crucible may be a basket (cage shape) having holes smaller than the particle size of the raw material, but preferably a box shape having one opening only on the upper surface.

  With respect to the amount of raw material charged, in the first aspect of the present invention, it is necessary that the raw material is filled into the crucible so as to satisfy the condition of the above formula (1). On the other hand, when using the crucible with a lid according to the second aspect of the present invention, there is no particular limitation on the filling amount of the raw material, but since a large contact area with the solvent of the raw material can be taken, a certain amount of space is provided in the crucible. It is preferable to ensure.

(Baffle plate)
The crystal manufacturing apparatus of the present invention may include at least one baffle plate to partition the crystal growth region and the raw material filling region. The baffle plate preferably has a hole area ratio of 2 to 20%. By controlling the aperture ratio of the baffle plate, it becomes easy to control the convection of the supercritical solvent and appropriately control the degree of supersaturation of GaN in the crystal growth region under the growth conditions.

  Here, “supersaturation” means a state in which the dissolution amount has increased more than the saturation state, and “supersaturation degree” means that the dissolution amount and saturation state in the supersaturation state are expressed by the following formula (3). The ratio with the amount of dissolution. In the solution growth method, it refers to the ratio between the amount of GaN dissolved in the crystal growth region that is supersaturated by GaN transport by convection from the raw material filling region and the amount of GaN dissolved in the saturation state of the crystal growth region. .

なお、本発明において、過飽和度は、原料窒化物の充填量、バッフル板の開孔率、原料充填領域と結晶成長領域との温度差等を適宜変更・選定することにより制御できる。

In the present invention, the degree of supersaturation can be controlled by appropriately changing and selecting the filling amount of the raw material nitride, the baffle plate opening ratio, the temperature difference between the raw material filling region and the crystal growth region, and the like.

  The baffle plate may be made of the same material as that of the autoclave. However, the surface of the baffle plate is made of nickel (Ni) or tantalum (Ta) in order to provide further erosion resistance and to refine the crystal. Further, it is preferable to be composed of titanium (Ti) niobium (Nb) or pBN. More preferred is a noble metal such as iridium (Ir), palladium (Pd), platinum (Pt), gold (Au), and most preferred is platinum (Pt).

[Crystal production]
In the case of the ammonothermal method, the crystal to be manufactured is a group 13 nitride crystal, which depends on the group 13 element in the raw material. It is preferable that the crystal to be manufactured is mainly a crystal of a single metal nitride of a group 13 element such as B, Al, Ga, In or a crystal of an alloy nitride (for example, GaInN, GaAlN), More preferred are gallium nitride crystals and aluminum nitride crystals.

  In addition, the manufactured crystal is a single crystal. The size of the single crystal obtained by the ammonothermal method depends on conditions such as the size of the autoclave and the size of the seed crystal, but an autoclave having an inner diameter of 100 mm can have a size of φ3 inches.

(material)
When the target product is a Group 13 nitrogen compound crystal, a polycrystalline material of Group 13 nitride crystal is usually used as the material. As the raw material, a raw material containing gallium nitride is preferable. The polycrystalline raw material does not need to be a complete nitride, and depending on the conditions, the group 13 element may contain a metal component in a metal state (that is, zero valence). For example, the crystal is gallium nitride. In some cases, a mixture of gallium nitride and metal gallium may be mentioned.

  The production method of the polycrystalline raw material to be the raw material is not particularly limited. For example, a nitride polycrystalline produced by reacting a metal or its oxide or hydroxide with ammonia in a reaction vessel in which ammonia gas is circulated. Can be used. In addition, as 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. Furthermore, nitride polycrystal (for example, GaN) produced by reacting a metal such as Ga with nitrogen at a high temperature and a high pressure can also be used.

  In order to obtain a high quality crystal by crystal growth of the polycrystalline raw material, mixing of water and oxygen should be avoided as much as possible. Therefore, the oxygen content in the polycrystalline raw material is usually 5% by mass or less, preferably 2% by mass or less, and particularly preferably 0.5% by mass or less. The ease with which oxygen is mixed into the polycrystalline raw material is related to the reactivity with water or the absorption capacity. This is because the worse the crystallinity of the polycrystalline raw material, the more active groups such as NH groups exist on the surface and the like, and this may react with water to generate some oxides or hydroxides. For this reason, it is generally desirable to use a polycrystalline material having as high crystallinity as possible, and the crystallinity can be estimated by the half-value width of powder X-ray diffraction. The preferred polycrystalline raw material has a half-width of (100) diffraction line (2θ = about 32.5 ° for hexagonal gallium nitride), usually 0.25 ° or less, preferably 0.20 ° or less, more preferably 0. .17 ° or less.

  The raw material may be arranged separately from the mineralizer described later, or the mineralizer and the raw material may be mixed. Moreover, after installing a raw material in a raw material filling part, it can compress by pushing a raw material from the top etc. and can vent | release the air between raw materials. Further, the filling amount of the raw material into each crucible is not particularly limited in the case of the second invention, but in the case of the first invention, the capacity of the crucible so as to satisfy the requirement of the above formula (1). It is determined appropriately according to

  In addition, as the particle size of the raw material, the maximum value of the particle size is preferably 10 mm or less, and more preferably 1 mm or less. The minimum value of the particle size is usually preferably 10 nm, and more preferably 1 μm or more.

  Here, the “particle size” means those divided by a corresponding mesh screen. Further, the content mass% of the powder raw material can be calculated by measuring each mass by dividing it with a sieve.

(solvent)
When the crystal growth is growth of a nitride crystal by an ammonothermal method, the solvent is a nitrogen-containing solvent (for example, at least one compound selected from the group consisting of hydrazine N ₂ H ₄ , ammonia NH ₃ , amines, melamine) or can be filled with any solvent miscible with the nitride III-V, it is preferable to use ammonia NH ₃ in the solvent.

  In addition, before putting the nitrogen-containing solvent into the autoclave, it is also preferable to degas the autoclave or to put the nitrogen-containing solvent while circulating an inert gas such as nitrogen. At that time, the reaction vessel may be cooled below the boiling point of the nitrogen-containing solvent. Further, the concentration of water or oxygen contained in these solvents is preferably low, and these concentrations are preferably 1000 ppm or less, more preferably 100 ppm or less, and further preferably 10 ppm or less. The solvent may be used alone or in combination of two or more.

  When 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. Ammonia generally has a high affinity with water, so when ammonia is charged into an autoclave, it is easy to bring oxygen derived from water into the autoclave, resulting in an increase in the amount of mixed oxygen in the crystals produced and the resulting nitrogen. There is a possibility that the crystallinity of the compound crystal is deteriorated. Also from such a viewpoint, it is desirable to reduce the amount of water and oxygen contained in the ammonia solvent as much as possible, preferably 1000 ppm or less, more preferably 100 ppm or less, and particularly preferably 10 ppm or less.

  These solvents are used in the subcritical and / or supercritical state during crystal production. The supercritical state means a concentrated gas that is maintained above its critical temperature, and the critical temperature is a temperature at which the gas cannot be liquefied by pressure. In the supercritical state, the viscosity is generally low and it is more easily diffused than the liquid, but has the same solvating power as the liquid. The subcritical state refers to a liquid state having a density substantially equal to the critical density near the critical temperature. For example, in the raw material filling region, the raw material is melted as a supercritical state, and the crystal growth region is used to change the temperature so that it becomes a subcritical state. Is possible.

(Mineralizer)
In the present invention, a mineralizer can be used to increase the crystal growth rate during crystal growth. A mineralizer (or also called a solubilizer) is a substance for increasing the solubility of a raw material in a solvent and transferring the crystal raw material to a crystal growth region, and is well known in the art. The dissolution in this specification includes both physical dissolution and chemical dissolution.

  The mineralizer is usually a compound containing a halogen atom or an alkali metal, alkaline earth metal, or rare earth metal. Among these, from the viewpoint of preventing the generated crystals from containing oxygen, it is preferable to use those containing nitrogen atoms in the form of ammonium ions or amides as mineralizers. These mineralizers may be used alone or in combination of two or more. In order to prevent impurities from being mixed into the nitride crystal, the mineralizer is purified and dried if necessary. The purity of the mineralizer is usually 95% or more, preferably 98% or more, more preferably 99% or more, and particularly preferably 99.5% or more. It is desirable to reduce the water and oxygen contained in the mineralizer as much as possible. These concentrations are preferably 1000 ppm or less, and more preferably 100 ppm or less.

Mineralizers are divided into acidic mineralizers and basic mineralizers. Examples of the basic mineralizer include alkali metals, alkaline earth metals, rare earth metals and compounds containing nitrogen atoms, alkaline earth metal amides, rare earth amides, alkali nitride metals, alkaline earth metal nitrides, azide compounds, etc. Examples thereof include hydrazine 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 acidic mineralizer is a compound containing a halogen atom, and examples thereof include ammonium halides, such as ammonium chloride (NH ₄ Cl), ammonium iodide (NH ₄ I), ammonium bromide (NH ₄ Br). Of these, ammonium chloride (NH ₄ Cl) is preferred.

  In the case of the ammonothermal method using ammonia as a solvent, the acidic mineralizer is highly soluble in a supercritical ammonia solvent, has nitriding ability in ammonia, and reacts with noble metals such as Pt. An acidic mineralizer is more preferable because of its low nature.

  As for the use ratio of the mineralizer and the raw material, the mineralizer / group 13 metal element (molar ratio) is usually 0.001 to 100. For example, in the case of GaN, the mineralizer / Ga molar ratio is usually preferably in the range of 0.001 to 20, taking into consideration the types of additives such as raw materials and mineralizers and the target crystal size. Can be selected as appropriate.

  Further, if the mineralizer is not present above the baffle plate (crystal growth region), it may be arranged separately from the raw material, or the mineralizer and the raw material may be mixed. Furthermore, after the mineralizer is installed in the raw material filling region, the mineralizer can be compressed from above by compressing it to eliminate voids between the mineralizers.

  In the present invention, the mineralizer may be in the form of powder or molded solid, and is not particularly limited. Here, “molded” includes compression molding and the like such as “pelletizing”, and may be sintered after compression molding. At this time, the size and shape of the molded mineralizer can be appropriately selected according to the purpose.

(Seed crystal)
In the present invention, it is preferable to use a seed crystal in order to grow the crystal at a predetermined position. When a seed crystal is used, generation of a single crystal on the seed crystal is promoted, and a larger single crystal can be obtained. The seed crystal is usually loaded at the same time as or after filling with additives such as raw materials and mineralizers, and the seed crystal is fixed to a precious metal jig similar to the precious metal constituting the inner surface of the autoclave. If necessary, heating and deaeration after loading in an autoclave is also effectively used.

  When a single crystal of nitride is grown by an ammonothermal method, it is desirable to use the target single crystal of nitride, but it is not necessarily the same nitride as the target. However, in that case, it is a seed crystal having a lattice constant and / or crystal lattice that matches or matches the target nitride, or heteroepitaxy (ie, coincidence of crystallographic positions of some atoms). It is preferable to use a seed crystal composed of a single crystal material piece or a polycrystalline material piece coordinated so as to guarantee. Specific examples of the seed crystal include, for example, gallium nitride (GaN), a single crystal of GaN, a single crystal of nitride such as AlN, a single crystal of silicon carbide (SiC), and the like.

  The seed crystal can be determined in consideration of solubility in an ammonia solvent and reactivity with a mineralizer. For example, as a seed crystal of GaN, a single crystal obtained by epitaxial growth on a dissimilar substrate such as sapphire by MOCVD method or HVPE method (Hydride Vapor Phase Epitaxy), and then peeled off from metal Ga to Na A single crystal obtained by crystal growth using Li, Bi and flux as a flux, a single crystal obtained by homo / heteroepitaxial growth obtained by using the LPE method, a single crystal produced based on the solution growth method including the method of the present invention, and those A cut crystal or the like can be used.

[Production conditions]
Next, each condition for crystal growth in the present invention will be described. In the present invention, in order to produce crystals in a supercritical state and / or a subcritical state, the temperature is generally kept higher than the critical point of the solvent. When ammonia is used as a solvent, the critical point is a critical temperature of 132 ° C. and a critical pressure of 11.35 MPa. However, if the filling rate into the autoclave is high, the pressure far exceeds the critical pressure even at a temperature below the critical temperature. In the present invention, the supercritical state includes a state exceeding such a critical pressure. Since the reaction mixture is enclosed within a constant volume (container volume), an increase in temperature increases the pressure of the fluid. In general, the temperature T is in a supercritical state if T> Tc (Tc: critical temperature of the solvent) and pressure P> Pc (Pc: critical pressure of the solvent). Under the above conditions, formation of GaN microcrystals is observed. Actually, since the solubility of the polycrystalline raw material introduced into the solvent is very different between the subcritical condition and the supercritical condition, a sufficient growth rate of the GaN single crystal can be obtained under the supercritical condition. The reaction time depends in particular on the reactivity of the mineralizer and the thermodynamic parameters, ie temperature and pressure values.

  In the case of an ammonia solvent, the lower limit of the temperature range in the autoclave is usually 150 ° C. or higher, preferably 200 ° C. or higher, and particularly preferably 300 ° C. or higher. The upper limit is usually 800 ° C. or lower, preferably 700 ° C. or lower, and particularly preferably 650 ° C. or lower.

  The autoclave is divided into two overlapping zones, that is, a lower raw material filling region and an upper crystal growth region separated by a baffle plate. The temperature gradient ΔT between these two zones is 10-100 ° C. The direction of the gradient depends in particular on the solubility of the raw material as a function of temperature.

  During crystal growth, the autoclave is preferably maintained at a pressure in the range of about 15 MPa to 600 MPa. When the solvent is ammonia, the pressure range in the autoclave is usually 20 MPa or more as the lower limit, preferably 30 MPa or more, particularly preferably 50 MPa or more, and the upper limit is usually 500 MPa or less, preferably 400 MPa or less, particularly preferably 200 MPa or less. It is desirable to hold.

  The rate of injection of the ammonia solvent to achieve the above temperature range and pressure range in the autoclave, that is, the filling rate, is the free volume of the autoclave, i.e., when the raw material and seed crystal are used in the autoclave, Subtract the volume of the structure where it will be installed from the total volume of the autoclave, and if a baffle plate is to be installed, subtract the volume of the baffle plate to obtain the remaining volume of ammonia in the standard state. It is usually 20 to 95%, preferably 30 to 85%, more preferably 40 to 75%, based on the density (liquid density at the boiling point in the case of gas in the standard state).

  The reaction time after reaching a predetermined temperature depends on the type of nitride 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 months. Can do. During the reaction, the reaction temperature may be constant, or the temperature may be gradually raised or lowered. After a reaction time for producing desired crystals, the temperature is lowered. The method for lowering the temperature is not particularly limited, but the heating of the heater may be stopped and the autoclave may be allowed to cool as it is installed in the furnace, or the autoclave may be removed from the electric furnace and air cooled. If necessary, quenching with a refrigerant is also preferably used.

  After draining the solvent from the conduit, if necessary, remove the solvent in the autoclave sufficiently by vacuuming, etc., then dry, open the autoclave and grow the nitrogen compound crystals and unreacted raw materials and Additives such as mineralizers can be removed.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]
An autoclave made of Inconel 625 (approx. 110 ml) with an inner dimension of 20 mm in diameter and 350 mm in length with a platinum lining is used as a raw material in a pBN crucible having an inner diameter of 12 mm and a depth of 30 mm (99.99% made by CERAC). 4.8 g of GaN powder crystal (model number G-1030, particle size: 100 mesh (100 mesh is 150 μm or less according to JIS standard)) from the top of the crucible to a depth of 12 mm, 5 pieces of this crucible, total of GaN The weight was set to 24.0 g in the autoclave in a platinum ladder support with a space of 10 mm in the vertical direction and set in the autoclave, where the filling amount of the raw material in each crucible was h = 12 mm, D / 2 = 6 mm, which satisfies Expression (1).

Furthermore, after putting 8.0 g of 99.999% pure NH ₄ Cl sufficiently dried as a mineralizer into an autoclave, a baffle plate and a crystal growth part of a seed crystal (10 mm × 10 mm × 300 μm) were installed. The lid of the autoclave equipped with the valve was closed and the autoclave was weighed. Next, the conduit is connected to a vacuum pump through a valve attached to the autoclave, and after opening the valve and degassing the vacuum, the autoclave is cooled with dry ice methanol solvent while maintaining the vacuum state, and the valve is once turned on. Closed.

Next, after the conduit was operated so as to lead to the NH ₃ cylinder, the valve was opened again and NH ₃ was filled in the autoclave without continuously touching the outside air. After that, based on the flow rate control, NH ₃ was filled as a liquid corresponding to about 65% of the cavity of the autoclave (converted with an NH ₃ density of −33 ° C.), and the valve was closed again. Further, the temperature of the autoclave was returned to room temperature, and the increased amount of NH ₃ filled after the outer surface was sufficiently dried was measured.

  Subsequently, the autoclave was housed in an electric furnace composed of a heater divided into two parts in the vertical direction. The temperature of the lower outer surface of the autoclave is increased to 490 ° C. and the temperature of the upper outer surface is increased to 410 ° C. over 12 hours with a temperature difference. The temperature of the lower outer surface of the autoclave is increased to 490 ° C. After reaching 410 ° C., it was held at that temperature for an additional 240 hours. The pressure in the autoclave was about 130 MPa. Further, the temperature range during holding was ± 5 ° C. or less.

Thereafter, the temperature was lowered for about 8 hours until the temperature of the lower outer surface of the autoclave reached 150 ° C., and then the heating by the heater was stopped and the mixture was naturally cooled in an electric furnace. After confirming that the temperature of the lower outer surface of the autoclave had dropped to about room temperature, first, the valve attached to the autoclave was opened, and NH ₃ in the autoclave was removed. After that, weigh the autoclave and confirm that NH ₃ is discharged. Then, close the valve and connect it to the vacuum pump. The valve was then opened again and the autoclave NH ₃ was almost completely removed. Thereafter, the lid of the autoclave was opened and the inside was confirmed. As a result, a 285 μm-thick gallium nitride crystal was deposited on the entire 10 mm square seed crystal. In addition, in each crucible, no undissolved raw material was found, and the raw material was sufficiently dissolved. The obtained gallium nitride crystal was taken out and subjected to X-ray diffraction measurement. As a result, the crystal form was hexagonal and was C-axis oriented in the same orientation as the seed crystal.

[Example 2]
Using an autoclave made of Inconel 625 with an inner dimension of 30 mm in diameter and 700 mm in length (about 500 ml) with platinum inner lined, 20 g of the same GaN powder crystal as in Example 1 was used as a raw material in a platinum crucible of 22 mm in inner diameter and 30 mm in depth. Then, a lid having five symmetrically Ø3 mm holes was attached to this crucible, and five steps were set on a platinum ladder-like support with an interval of 10 mm in the vertical direction of each step. Therefore, a total of five crucibles and the total weight of GaN were 100 g. Since the raw material is filled up to a depth of 7.7 mm from the upper end, h = 7.7 mm, D / 2 = 11 mm, which does not satisfy the formula (1), but the opening ratio of the lid is about 9%, which satisfied the above formula (2).

Furthermore, after putting 40 g of 99.999% pure NH ₄ Cl sufficiently dried as a mineralizer into an autoclave, a baffle plate and a seed crystal (15 mm × 15 mm × 300 μm) crystal growth section were installed. The lid of the mounted autoclave was closed and the autoclave was weighed. Next, the conduit is connected to a vacuum pump through a valve attached to the autoclave, and after opening the valve and degassing the vacuum, the autoclave is cooled with dry ice methanol solvent while maintaining the vacuum state, and the valve is once turned on. Closed. Furthermore, after operating as leading to NH ₃ bomb was filled with NH ₃ in an autoclave without exposure to the outside air is continuously re-opening the valve. Based on the flow rate control, NH ₃ was filled as a liquid corresponding to about 50% of the cavity portion of the autoclave (converted with an NH ₃ density of −33 ° C.), and then the valve was closed again. Subsequently, the temperature of the autoclave was returned to room temperature, and the increased amount of NH ₃ filled after the outer surface was sufficiently dried was measured.

  Subsequently, the autoclave was housed in an electric furnace composed of a heater divided into two parts in the vertical direction. The temperature of the lower outer surface of the autoclave was raised to 480 ° C. and the temperature of the upper outer surface was increased to 430 ° C. over 18 hours with a temperature difference. After reaching 430 ° C., it was held at that temperature for a further 360 hours. The pressure in the autoclave was about 115 MPa. Further, the temperature range during holding was ± 5 ° C. or less.

Thereafter, the temperature was lowered for about 7 hours until the temperature of the lower outer surface of the autoclave reached 150 ° C., and then the heating by the heater was stopped and the mixture was naturally cooled in an electric furnace. After confirming that the temperature of the lower outer surface of the autoclave had dropped to almost room temperature, the valve attached to the autoclave was first opened, and NH ₃ in the autoclave was removed. Next, the autoclave was weighed to confirm the discharge of NH ₃ , and once the valve was closed and operated to pass through the vacuum pump, the valve was opened again, and NH ₃ in the autoclave was almost completely removed. Thereafter, the lid of the autoclave was opened and the inside was confirmed. As a result, a 410 μm thick gallium nitride crystal was deposited on the entire surface of the 15 mm square seed crystal.
Moreover, when the crucible in which the raw material was put was opened, 3-5 g of undissolved material was confirmed, but it can be said that the raw material was sufficiently dissolved.

[Comparative Example 1]
Using the same autoclave as in Example 2, 25 g of the same GaN powder crystal as in Example 1 was put as a raw material in a platinum crucible having an inner diameter of 27 mm and a length of 20 mm. The raw material was charged from the upper end of the crucible to a depth of 1.5 mm. Four steps were set on a platinum ladder support without any lids, with 15 mm intervals in the vertical direction of each step. Therefore, the total number of crucibles is 4, and the total weight of GaN is 100 g. Here, the filling amount of the raw material was h = 1.5 mm, D / 2 = 13.5 mm, and did not satisfy the formula (1).
Further, 40 g of 99.999% pure NH ₄ Cl sufficiently dried as a mineralizer was placed in an autoclave, and a baffle plate and a crystal growth part such as a seed crystal were installed. The same procedure as in Example 2 was repeated. Made growth.

After cooling to room temperature and discharging NH ₃ , the autoclave lid was opened and the inside was checked. The platinum crucible showed no undissolved material, but the seed crystal had grown gallium nitride crystals. Many needle-like growths differed from the crystal orientation of the seed crystals. This is because the supersaturation increases due to the adhesion to the seed crystal due to the movement of the powder raw material to the crystal growth region in the undissolved state, and the over-melting in the raw material filling region in the powder state, resulting in the growth of polynuclear nuclei. It seems that he was waking up.

  From the above results, in Examples 1 and 2, the raw material was prevented from rising due to the thermal convection of the solvent. Therefore, it is considered that the powder raw material has risen.

  Since the nitrogen compound crystal obtained by the crystal production method and the crystal production apparatus of the present invention has good crystallinity, it can be used as an epitaxial growth substrate when various devices are produced by VPE, MOCVD or the like.

It is the schematic which shows the crystal manufacturing apparatus of this invention using several crucibles. It is sectional drawing for demonstrating the filling amount of the raw material to a crucible. It is the schematic for demonstrating the crucible with a lid | cover in 2nd this invention.

Explanation of symbols

1 Crystal production equipment 2 Reaction vessel (autoclave)
3 Conduit 4 Crystal Growth Area 5 Raw Material Filling Area 6 Baffle Plate 7 Crucible 8 Ladder Support 9 Seed Crystal 10 Mineralizer 11 Heater 12 Thermocouple 13 Raw Material 14 Lid 15 Opening

Claims (20)

In a reaction vessel, (1) a supercritical and / or subcritical solvent, and (2) a crystal production method for growing a crystal using raw materials,
The reaction vessel includes a crucible as a raw material filling part for filling the raw material, and the amount of raw material charged into the crucible satisfies the following formula (1).
h ≧ D / 2 Formula (1)
(In formula (1), h represents the distance from the upper end of the crucible to the top surface of the filled raw material, and D represents the inner diameter of the crucible.)   The crystal manufacturing method according to claim 1, wherein the crucible has a lid having one or more openings. In a reaction vessel, (1) a supercritical and / or subcritical solvent, and (2) a crystal production method for growing a crystal using raw materials,
The crystal production method, wherein the reaction vessel includes a crucible as a raw material filling portion for filling the raw material, and the crucible has a lid having one or more openings. The crystal production method according to claim 3, wherein a filling amount of the raw material into the crucible satisfies the following formula (1).
h ≧ D / 2 Formula (1)
(In formula (1), h represents the distance from the upper end of the crucible to the top surface of the filled raw material, and D represents the inner diameter of the crucible.)   The said raw material filling part is provided with a some crucible, The crystal manufacturing method of any one of Claims 1-4 characterized by the above-mentioned. The crystal manufacturing method according to any one of claims 2 to 5, wherein the opening ratio of the lid of the crucible satisfies the following formula (2).
5 ≦ (S _n / S ₀ ) × 100 ≦ 80 Formula (2)
(Wherein (in 2), S _n represents the opening area of the lid with the crucible, S ₀ represents the internal horizontal cross-sectional area of the crucible.)   The crystal manufacturing method according to claim 1, wherein the raw material has a particle size of 10 nm to 10 mm.   The crystal production method according to claim 1, wherein the obtained crystal is a single crystal.   The crystal obtained according to any one of claims 1 to 8, wherein the obtained crystal is a periodic table group 13 element nitride.   The crystal production method according to claim 1, wherein the solvent is a nitrogen-containing solvent.   The crystal production method according to any one of claims 1 to 10, wherein the reaction vessel is an autoclave. A crystal production apparatus comprising a reaction vessel, wherein (1) a supercritical and / or subcritical solvent and (2) a raw material are used to grow crystals in the reaction vessel,
The reaction vessel is provided with a crucible as a raw material filling part for filling the raw material, and the amount of raw material charged into the crucible satisfies the following formula (1).
h ≧ D / 2 Formula (1)
(In formula (1), h represents the distance from the upper end of the crucible to the top surface of the filled raw material, and D represents the inner diameter of the crucible.)   The crystal manufacturing apparatus according to claim 12, wherein the crucible has a lid having one or more openings. A crystal production apparatus comprising a reaction vessel, wherein (1) a supercritical and / or subcritical solvent and (2) a raw material are used to grow crystals in the reaction vessel,
The crystal production apparatus, wherein the reaction vessel includes a crucible as a raw material filling portion for filling the raw material, and the crucible has a lid having one or more openings. The crystal manufacturing apparatus according to claim 14, wherein a filling amount of the raw material into the crucible satisfies the following formula (1).
h ≧ D / 2 Formula (1)
(In formula (1), h represents the distance from the upper end of the crucible to the top surface of the filled raw material, and D represents the inner diameter of the crucible.)   The crystal manufacturing apparatus according to claim 12, wherein the raw material filling unit includes a plurality of crucibles. The crystal manufacturing apparatus according to any one of claims 13 to 16, wherein the opening ratio of the lid of the crucible satisfies the following formula (2).
5 ≦ (S _n / S ₀ ) × 100 ≦ 80 Formula (2)
(Wherein (in 2), S _n represents the opening area of the lid with the crucible, S ₀ represents the internal horizontal cross-sectional area of the crucible.)   The crystal manufacturing apparatus according to any one of claims 12 to 17, wherein a particle diameter of the raw material is 10 nm to 10 mm.   The crystal production apparatus according to any one of claims 12 to 18, wherein the solvent is a nitrogen-containing solvent.   The crystal production apparatus according to any one of claims 12 to 19, wherein the reaction vessel is an autoclave.

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