JP2005263535A - Method for manufacturing single crystal of group iii element nitride, and reaction vessel used therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing efficiently a group III element nitride, e.g. gallium nitride or aluminum nitride, with high quality. <P>SOLUTION: A group III element such as gallium or aluminum and an alkali metal such as sodium are put into a crucible in a nitrogen gas atmosphere and thermally melted under pressure, thus growing a single crystal. The crucible used here is (A) one made of a nitrogen-free material having a melting point or decomposition temperature of 2,100°C or higher or (B) one made of at least one material selected from the group consisting of rare earth oxides, alkaline earth metal oxides, W, SiC, diamond, and diamond-like carbon, this material preferably being, for example, Y<SB>2</SB>O<SB>3</SB>. The above yielded single crystal, as illustrated with a photograph (A) of the figure, is colorless and transparent and has a high quality and a maximum diameter of 2 cm or more. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a single crystal of a group III element nitride such as gallium nitride (GaN) or aluminum nitride (AlN) and a reaction vessel used therefor.

Group III nitride semiconductors are used in fields such as heterojunction high-speed electronic devices and optoelectronic devices (semiconductor lasers, light-emitting diodes, sensors, etc.), and gallium nitride (GaN) is particularly attracting attention. Conventionally, in order to obtain a single crystal of gallium nitride, gallium and nitrogen gas are directly reacted (see Non-Patent Document 1). However, in this case, ultrahigh temperature and high pressure of 1300 to 1600 ° C. and 8000 to 17000 atm (0.81 to 1.72 MPa) are required. In order to solve this problem, a technique for growing a gallium nitride single crystal in sodium (Na) flux (hereinafter also referred to as “Na flux method”) has been developed (for example, Patent Documents 1 to 4, Non-Patent Documents). 2 and 3). According to this method, the heating temperature is greatly reduced to 600 to 800 ° C., and the pressure can be reduced to about 50 atm (about 5 MPa). However, this method has a problem that the obtained single crystal is blackened, which causes a problem in quality, and crystal growth may stop in the middle. These problems are not limited to gallium nitride, but also apply to other Group III element nitride semiconductors.
JP 2000-327495 A JP 2001-102316 A JP 2003-23829 A JP 2003-292400 A J. et al. Phys. Chem. Solids, 1995, 56, 639 Japanese Journal of Crystal Growth 30, 2, pp38-45 (2003) J. et al. J. et al. Appl. Phys. 42, ppL879-L881 (2003)

  The present invention has been made in view of such circumstances, and provides a production method that is transparent, has a low dislocation density, has a high quality, and can produce a bulky large group III element nitride single crystal in a high yield. Is the purpose.

In order to achieve the above object, the method for producing a group III element nitride single crystal of the present invention is characterized in that in a flux containing an alkali metal, at least one group III element selected from the group consisting of Ga, Al and In and nitrogen (N) is a production method for growing a group III element nitride single crystal by reacting in a reaction vessel, and the material of the reaction vessel is at least one of the following (A) and (B): It is a manufacturing method using the reaction container which is the material of this.
(A) Nitrogen-free material having a melting point or decomposition temperature of 2100 ° C. or higher (B) At least one material selected from the group consisting of rare earth oxides, alkaline earth metal oxides, W, SiC, diamond and diamond-like carbon

  The present inventors have made a series of studies in order to achieve the above object. In the process, attention was paid to the reaction vessel, and various investigations were made. Conventional reaction vessels such as alumina crucibles were dissolved by flux containing alkali metal, and the eluted material became impurities, which led to crystal quality and growth. I found out that it would have an adverse effect. It was also found that when a nitrogen-based material such as a BN crucible is used, crystal nuclei are generated on the surface, which also adversely affects the quality and growth of the crystal. Based on these findings, further research has been conducted. When a reaction vessel formed of at least one of the above materials (A) and (B) is used, it can be dissolved even when it comes into contact with a flux containing alkali metal. In addition, the inventors have found that generation of crystal nuclei on the wall of the reaction vessel is prevented, and the present invention has been achieved. By the production method of the present invention, it is possible to produce a high-quality single crystal of a large group III element nitride that is transparent, has a low dislocation density, and has a high quality. In the present invention, the “nitrogen-free material” refers to a material that does not use nitrogen as a forming material.

  Next, the present invention will be described in detail.

As described above, in the present invention, the material of the reaction vessel is at least one of the materials (A) and (B). Examples of the rare earth and alkaline earth metals include Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Be, Mg, Ca, Sr, Ba, Ra. The material of the reaction vessel is preferably at least one selected from the group consisting of Y ₂ O ₃ , CaO, MgO and W. Among these, Y ₂ O ₃ is most preferable as the material of the reaction vessel. The reaction vessel is preferably in direct contact with the flux or group III element, and the reaction vessel may be a crucible.

In the present invention, group III elements are gallium (Ga), aluminum (Al), and indium (In). Among these, gallium and aluminum are preferable. The group III element may be used alone or in combination of two or more. The group III element nitride single crystal is preferably a gallium nitride (GaN) single crystal or an aluminum nitride (AlN) single crystal. The group III element nitride single crystal is a single crystal represented by a composition formula Al _x Ga _y In _1-xy N (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ x + y ≦ 1). It may be. The conditions shown below are particularly preferable for producing a single crystal of gallium nitride or a single crystal of aluminum nitride, but can be similarly applied to the production of other group III element nitride single crystals.

  In the present invention, the alkali metal is sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr), and the alkaline earth metal is calcium (Ca), strontium ( Sr), barium (Br) and radium (Ra). These may be used alone or in combination of two or more. Among these, Na, Ca, K, Rb, and Cs are preferable, and Na and Ca are more preferable. The addition ratio of alkali metal and alkaline earth metal is appropriately determined depending on the type. The addition ratio of the alkali metal to the group III element is, for example, 0.1 to 99.9 mol%, preferably 1 to 99 mol%, more preferably 5 to 98 mol%. The molar ratio when using a mixed flux of alkali metal and alkaline earth metal is, for example, alkali metal: alkaline earth metal = 99.99 to 0.01: 0.01 to 99.99, preferably 99. .9 to 0.05: 0.1 to 99.95, more preferably 99.5 to 1: 0.5 to 99.

  In the present invention, the reaction conditions are, for example, a temperature of 100 to 1500 ° C. and a pressure of 100 Pa to 20 MPa, preferably a temperature of 300 to 1200 ° C. and a pressure of 0.01 MPa to 10 MPa, and more preferably a temperature of 500 to 1100. C., pressure 0.1 MPa to 6 MPa.

In the present invention, the nitrogen (N) -containing gas is, for example, nitrogen (N ₂ ) gas, ammonia (NH ₃ ) gas, etc., and these may be mixed, and the mixing ratio is not limited. In particular, use of ammonia gas is preferable because the reaction pressure can be reduced.

In the production method of the present invention, a group III element nitride (for example, gallium nitride, aluminum nitride) is prepared in advance, the mixed flux is brought into contact therewith, and a new group III element is formed using the group III element nitride as a nucleus. It is preferable to grow a nitride single crystal (for example, a gallium nitride single crystal or an aluminum nitride single crystal). The most important feature of this manufacturing method is that a large size single crystal can be manufactured quickly. That is, in this method, the larger the single crystal that becomes the nucleus, the faster the large single crystal can be obtained. For example, when thin-film gallium nitride is used as the nucleus, a gallium nitride single crystal grows in the thickness direction in the same area. For example, when the thin film having a maximum diameter of 5 cm is used, the equivalent area is obtained. If a gallium nitride single crystal grows from several μm to several mm in the thickness direction, a sufficiently large bulk gallium nitride can be obtained. The same applies to the case where thin film aluminum nitride or the like is used as the nucleus. The group III element nitride serving as the nucleus is represented by a composition formula Al _x Ga _y In _1-xy N (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ x + y ≦ 1). It may be a thing.

The group III element nitride serving as the nucleus may be a single crystal or amorphous. Further, the form of the group III element nitride serving as the nucleus is not particularly limited, but for example, the form of a thin film is preferable. This thin film may be formed on a substrate. Examples of the material of the substrate include amorphous gallium nitride (GaN), amorphous aluminum nitride (AlN), sapphire, silicon (Si), gallium / arsenic (GaAs), gallium nitride (GaN), and aluminum nitride (AlN). ), Silicon carbide (SiC), boron nitride (BN), lithium gallium oxide (LiGaO ₂ ), zirconium boride (ZrB ₂ ), zinc oxide (ZnO), various glasses, various metals, boron phosphide (BP), MoS ₂ , LaAlO ₃ , NbN, MnFe ₂ O ₄ , ZnFe ₂ O ₄ , ZrN, TiN, gallium phosphide (GaP), MgAl ₂ O ₄ , NdGaO ₃ , LiAlO ₂ , ScAlMgO ₄ , Ca ₈ La ₂ (PO ₄ ) ₆ O ₂ etc. The thickness of the group III element nitride thin film serving as a nucleus is not particularly limited, and is, for example, in the range of 0.0005 to 100000 μm, preferably 0.001 to 50000 μm, and more preferably 0.01 to 5000 μm. The thin film can be formed on the substrate by, for example, metal organic vapor phase epitaxy (MOCVD), halide vapor phase epitaxy (HVPE), molecular beam epitaxy (MBE) or the like. Moreover, what formed thin films, such as a gallium nitride and aluminum nitride, on the board | substrate is marketed, You may use it. The maximum diameter of the thin film is, for example, 2 cm or more, preferably 3 cm or more, more preferably 5 cm or more, and the larger the better, the upper limit is not limited. In addition, since the standard of the bulk compound semiconductor is 2 inches, from this viewpoint, the size of the maximum diameter is preferably 5 cm. In this case, the range of the maximum diameter is, for example, 2 to 5 cm. , Preferably 3 to 5 cm, more preferably 5 cm. The maximum diameter is a line connecting a point on the outer periphery of the thin film surface with other points and is the length of the longest line.

In the manufacturing method, the group III element nitride prepared in advance may be dissolved by the flux before the nitrogen concentration increases. In order to prevent this, it is preferable that nitride is present in the flux at least at the initial stage of the reaction. Examples of the nitride include Ca ₃ N ₂ , Li ₃ N, NaN ₃ , BN, Si ₃ N ₄ , InN, and the like. These may be used alone or in combination of two or more. Good. The ratio of the nitride in the flux is, for example, 0.0001 mol% to 99 mol%, preferably 0.001 mol% to 50 mol%, and more preferably 0.005 mol% to 10 mol%.

In the production method of the present invention, impurities can be present in the mixed flux. In this way, an impurity-containing group III element nitride single crystal can be produced. Examples of the impurities include silicon (Si), alumina (Al ₂ O ₃ ) indium (In), aluminum (Al), indium nitride (InN), silicon oxide (SiO ₂ ), and indium oxide (In ₂ O ₃ ). Zinc (Zn), magnesium (Mg), zinc oxide (ZnO), magnesium oxide (MgO), germanium (Ge), and the like.

  Next, the apparatus of the present invention is a group III element nitride single crystal manufacturing apparatus used in the manufacturing method of the present invention, comprising a reaction vessel, a heating means for heating the reaction vessel, and the inside of the reaction vessel. And a pressurizing means for making the pressurized atmosphere, and the reaction vessel is the reaction vessel of the present invention.

  The manufacturing method of the present invention is carried out, for example, using the apparatus shown in FIG. As shown in FIG. 1 (A), this apparatus is an example of a manufacturing apparatus according to the present invention, and includes a gas cylinder 1, an electric furnace 4, and a pressure and heat resistant container 3 disposed in the electric furnace 4. . A pipe 21 is connected to the gas cylinder 1, and a pressure regulator 5 and a pressure regulation valve 25 are arranged on the pipe 21, and a leak pipe is attached from the middle, and a leak valve is provided at the end. 24 is arranged. The pipe 21 is connected to the pipe 22, and the pipe 22 is connected to the pipe 23, which enters into the electric furnace 4 and is connected to the pressure and heat resistant container 3. As shown in FIG. 1B, a reaction vessel 6 is disposed in the pressure and heat resistant vessel 3, in which a group III element such as gallium or aluminum, an alkali metal, and an alkali as necessary. An earth metal (arbitrary component) is arranged. As described above, the reaction vessel 6 is formed of at least one of the materials (A) and (B). The reaction vessel 6 may be a crucible.

  The production of a group III element nitride single crystal using this apparatus is performed, for example, as follows. First, a flux material such as a group III element such as gallium or aluminum or sodium is placed in the reaction vessel 6 and placed in the pressure and heat resistant vessel 3. This pressure and heat resistant container 3 is placed in the electric furnace 4 with the tip of the pipe 23 connected. In this state, the nitrogen-containing gas is sent from the gas cylinder 1 through the pipes (21, 22, 23) into the pressure-resistant and heat-resistant container 3 and heated in the electric furnace 4. The pressure in the pressure and heat resistant container 3 is adjusted by the pressure regulator 5. Then, by pressing and heating for a certain time, the material is melted to grow a group III element nitride single crystal. Thereafter, the obtained single crystal is taken out from the reaction vessel 6. In this manufacturing method, since the reaction vessel 6 is made of the above-described material, the reaction vessel 6 is not dissolved by the flux, and crystal nuclei can be prevented from being generated on the inner wall surface of the reaction vessel 6.

  When a group III element nitride is prepared in advance and a group III element nitride single crystal is grown using this as a nucleus, for example, a group III element nitride thin film formed on a substrate is placed in a reaction vessel in advance. In this case, a single crystal may be grown in the flux as described above.

Although the group III element nitride single crystal of the present invention can be manufactured by the manufacturing method as described above, the single crystal of the present invention is not limited to these manufacturing methods, and is manufactured by other manufacturing methods. Also good. As described above, gallium nitride is preferable as the group III element nitride of the present invention. In the gallium nitride of the present invention, the dislocation density is, for example, 10 ⁴ / cm ² or less, preferably 10 ² / cm ² or less, more preferably almost no dislocation (for example, 10 ¹ / cm ² or less). belongs to. Further, the length of the maximum diameter is, for example, 2 cm or more, preferably 3 cm or more, more preferably 5 cm or more, and the larger the better, the upper limit is not limited. In addition, since the standard of the bulk compound semiconductor is 2 inches, from this viewpoint, the size of the maximum diameter is preferably 5 cm. In this case, the range of the maximum diameter is, for example, 2 to 5 cm. , Preferably 3 to 5 cm, more preferably 5 cm. The maximum diameter is a line connecting a point on the outer periphery of the single crystal and other points and is the length of the longest line.

  Next, the semiconductor device of the present invention is a semiconductor device using a group III element nitride transparent single crystal. Examples of the semiconductor device of the present invention include a field effect transistor, a light emitting diode (LED), and a semiconductor laser (LD). As another semiconductor device using the single crystal of the present invention, for example, a semiconductor device having a simple structure in which a p-type semiconductor and an n-type semiconductor are simply joined, and the single crystal of the present invention is applied to the semiconductor. There are used ones, a semiconductor device using the single crystal of the present invention as an insulating layer, an insulating substrate, or an insulating semiconductor.

  Next, examples of the present invention will be described together with comparative examples. The following examples are examples of gallium nitride single crystals, but other group III element nitride single crystals can be manufactured in the same manner.

Using the apparatus shown in FIG. 1, a gallium nitride single crystal was manufactured in the same manner as described above. That is, first, a substrate having a GaN thin film formed on the surface of the sapphire substrate by MOCVD was prepared. This substrate, gallium (1.0 g), and sodium (0.89 g) were put in a crucible made of Y ₂ O ₃ and grown in a nitrogen (N ₂ ) gas atmosphere at a growth temperature of 850 ° C. and a growth pressure of 30 atm (3 0.04 MPa) and a heating time of 96 hours under the conditions of growth time to grow a single crystal of gallium nitride, and after the growth was completed, the residue was treated with ethanol and water. As a comparative example, a single crystal of gallium nitride was manufactured under the same conditions as described above using an Al ₂ O ₃ crucible and a BN crucible. As a result, as shown in the photograph of FIG. 2 (A), in this example using a Y ₂ O ₃ crucible, a transparent and high-quality GaN single crystal can be obtained. The diameter was 2 cm or more, and as a result of examining by an etching method, there was almost no dislocation. On the other hand, in the comparative example using the crucible made of Al ₂ O ₃ (FIG. 2B) and the crucible made of BN (FIG. 2C), a blackened crystal was obtained. FIG. 2D is a photograph showing the inside of the BN crucible after crystal growth.
(Reference Example 1)
In this example, various crucible materials were examined for solubility in Na flux. Specifically, the materials shown in Table 1 below were placed in a container together with Ga (1.0 g) and Na (2.97 g), heated at 820 ° C. for 20 hours, and the change in weight before and after heating was evaluated. The results are also shown in Table 1 below.
(Table 1)
Crucible material Weight before heating (g) Weight after heating (g) Weight change Y ₂ O ₃ 1.215 1.215 0
ZrO ₂ 0.771 0.766 -0.005
TiO ₂ 1.341 0-1.341
CaO 0.636 0.635 -0.001
MgO 0.762 0.762 0
W 22.483 22.483 0
As shown in Table 1 above, it was found that Y ₂ O ₃ , CaO, MgO and W were hardly dissolved even in the Na flux. In contrast, ZrO ₂ and TiO ₂ were found to dissolve in the Na flux.
(Reference Example 2)
When the Na flux is used, Na reacts with moisture in the air or the like to generate NaOH, so that NaOH exists in the flux. In this example, various crucible materials were studied for their solubility in NaOH-containing Na flux. That is, the material shown in Table 2 below (surface area 2.5 to 3.0 cm ² ) was put in a container together with Ga (1.0 g), Na (2.97 g) and NaOH (0.26 g), and 20 at 820 ° C. After heating for a time, the weight change before and after heating was evaluated. The results are also shown in Table 2 below.
(Table 2)
Crucible material Weight before heating (g) Weight after heating (g) Weight change Y ₂ O ₃ 1.590 1.590 0
Al ₂ O ₃ 1.416 1.392 -0.023
As shown in Table 2 above, it was found that Y ₂ O ₃ does not dissolve even in the NaOH-containing Na flux, but Al ₂ O ₃ dissolves.
(Reference Example 3)
In this example, various crucible materials are examined for solubility in a mixed flux of Na and Ca. That is, the materials shown in Table 3 below were placed in a container together with Ga (1.0 g), Na (2.97 g) and Ca (0.26 g), heated at 820 ° C. for 20 hours, and the change in weight before and after heating was evaluated. did. The results are also shown in Table 3 below.
(Table 3)
Crucible material Weight before heating (g) Weight after heating (g) Weight change Y ₂ O ₃ 2.340 2.340 0
Al ₂ O ₃ 1.883 1.881 -0.002
As shown in Table 3 above, it was found that Y ₂ O ₃ does not dissolve even in the mixed flux of Na and Ca, but Al ₂ O ₃ dissolves.
(Reference Example 4)
In this example, the solubility of NaOH-containing Na and Ca in a mixed flux was examined for various crucible materials. That is, the materials shown in Table 4 below were placed in a container together with Ga (1.0 g), Na (2.97 g), Ca (0.26 g) and NaOH (0.26 g), and heated at 950 ° C. for 20 hours. The change in weight before and after heating was evaluated. The results are also shown in Table 4 below.
(Table 4)
Crucible material Weight before heating (g) Weight after heating (g) Weight change Y ₂ O ₃ 0.807 0.807 0
Al ₂ O ₃ as shown turned ragged weight unmeasurable Table _4, Y 2 _{O 3} is not dissolved even flux mixture of Na and Ca of NaOH _containing, Al 2 _{O 3} is found to be dissolved It was.

  As described above, according to the production method of the present invention, a high-quality and large transparent bulk group III element nitride single crystal can be produced in a high yield.

(A) And (B) is the schematic which shows the structure of an example of the manufacturing apparatus of this invention. FIG. 2 (A) is a photograph of a single crystal of gallium nitride obtained by an example of the production method of the present invention, and FIGS. 2 (B), (C) and (D) are single crystals obtained by the conventional method. It is a photograph of a crystal.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Gas cylinder 3 Pressure-resistant heat-resistant container 4 Electric furnace 5 Pressure regulator 6 Crucible 7 Material 11 Gallium nitride single crystal 12 Sapphire substrate 21, 22, 23 Pipe 24, 25 Valve

Claims (29)

A method for producing a group III element nitride single crystal, wherein in a flux containing an alkali metal, at least one group III element selected from the group consisting of Ga, Al and In and nitrogen (N) are contained in a reaction vessel. A method of growing a group III element nitride single crystal by reacting in the above, wherein the reaction vessel is a reaction vessel made of at least one of the following materials (A) and (B) Manufacturing method.
(A) Nitrogen-free material having a melting point or decomposition temperature of 2100 ° C. or higher (B) At least one material selected from the group consisting of rare earth oxides, alkaline earth metal oxides, W, SiC, diamond and diamond-like carbon The production method according to claim 1, wherein the material of the reaction vessel is at least one selected from the group consisting of Y ₂ O ₃ , CaO, MgO and W. The method according to claim 1, wherein a material of the reaction vessel is Y ₂ O ₃ . The production method according to claim 1, wherein the reaction vessel is a crucible. The manufacturing method according to claim 1, wherein the group III element is Ga, and the group III element nitride single crystal is a GaN single crystal. The manufacturing method according to any one of claims 1 to 4, wherein the group III element is Al, and the group III element nitride single crystal is an AlN single crystal. The alkali metal is at least one selected from the group consisting of sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr). Manufacturing method. The manufacturing method according to claim 1, wherein the flux further contains an alkaline earth metal. The method according to claim 8, wherein the alkaline earth metal is at least one selected from the group consisting of calcium (Ca), strontium (Sr), barium (Br), and radium (Ra). The manufacturing method according to claim 1, wherein the reaction conditions are a temperature of 100 to 1200 ° C. and a pressure of 100 Pa to 20 MPa. The production method according to claim 1, wherein a nitrogen (N) -containing gas is used as a nitrogen source. The production method according to claim 11, wherein the nitrogen (N) -containing gas is at least one of nitrogen (N ₂ ) gas and ammonia (NH ₃ ) gas. The method according to claim 11, wherein the nitrogen (N) -containing gas is ammonia (NH ₃ ) gas or a mixed gas of this and nitrogen (N ₂ ) gas. The group III element nitride is prepared in advance, the mixed flux is brought into contact therewith, and a new group III element nitride single crystal is grown using the group III element nitride as a nucleus. The manufacturing method as described. The production method according to claim 14, wherein the group III element nitride serving as a nucleus is single crystal or amorphous. The method according to claim 14 or 15, wherein the group III element nitride serving as a nucleus is in the form of a thin film. The manufacturing method according to claim 16, wherein the thin film is formed on a substrate. The manufacturing method according to any one of claims 14 to 17, wherein the maximum diameter of the group III element nitride serving as a nucleus is 2 cm or more. The manufacturing method according to claim 1, wherein impurities to be doped are present in the mixed flux. The impurities are silicon (Si), alumina (Al ₂ O ₃ ), indium (In), aluminum (Al), indium nitride (InN), silicon oxide (SiO ₂ ), indium oxide (In ₂ O ₃ ), zinc The method according to claim 19, wherein the method is at least one selected from the group consisting of (Zn), magnesium (Mg), zinc oxide (ZnO), magnesium oxide (MgO), and germanium (Ge). The manufacturing method according to any one of claims 1 to 20, wherein a transparent single crystal is grown. A group III element nitride transparent single crystal obtained by the production method according to claim 1. The group III element nitride transparent single crystal according to claim 22, which has a dislocation density of 10 ⁴ / cm ² or less, a maximum diameter of 2 cm or more, and is bulky. 24. A semiconductor device comprising the group III element nitride transparent single crystal according to claim 22 or 23. A reaction vessel used in the production method according to any one of claims 1 to 21, wherein the reaction vessel is formed of a nitrogen-free material having a melting point of 2000 ° C or higher. The material _is, Y ₂ O _{3, CaO,} reaction container according to claim 25, wherein at least one selected from the group consisting of MgO and W. It said material _is a reaction vessel of claim 26, wherein is Y 2 _{O 3.} The reaction container according to any one of claims 25 to 27, wherein the reaction container is a crucible. It is a manufacturing apparatus of the group III element nitride single crystal used for the manufacturing method of Claim 1, Comprising: The pressurization which makes the reaction container, the heating means which heats the said reaction container, and the said reaction container into a pressurized atmosphere The apparatus which is a reaction container in any one of Claim 25 to 28.

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