JP4760652B2 - Method for producing Ga-containing nitride crystal and method for producing semiconductor device using the same - Google Patents

Description

  The present invention relates to a method for producing a Ga-containing nitride crystal and a method for producing a semiconductor device using the same.

  A compound crystal of a Group 13 metal typified by gallium nitride (GaN) and nitrogen is useful as a material used in a light emitting diode, a laser diode, an electronic device for high frequency, and the like. Currently, in the case of GaN, the size of a GaN crystal produced by a known method is about 10 mm (for example, see Non-Patent Document 1), and its application to semiconductor devices is insufficient. As a practical method for producing a GaN crystal, a method of performing vapor phase epitaxial growth by MOCVD (Metal-Organic Chemical Vapor Deposition) method on a substrate such as a sapphire substrate or silicon carbide has been proposed (for example, non-patent) Reference 2).

  However, in the above method, since GaN crystals are epitaxially grown on different substrates having different lattice constants and thermal expansion coefficients, the obtained GaN crystals have many lattice defects. When such a GaN crystal having many lattice defects is used, the operation of the electronic device is adversely affected, and satisfactory performance for use in an application field such as a blue laser cannot be expressed. For this reason, in recent years, it has been strongly desired to improve the quality of GaN crystals grown on a substrate and to establish a manufacturing technique for GaN bulk single crystals.

Currently, the heteroepitaxial GaN crystal growth method by the vapor phase method requires a complicated and long process in order to reduce the defect concentration of the GaN crystal. For this reason, recently, vigorous research has been conducted on single crystallization of GaN. For example, a high pressure method in which nitrogen and Ga are reacted under high temperature and high pressure (for example, see Non-Patent Document 3), Ga and NaN _3. Have been proposed (for example, see Non-Patent Document 4), a flux growth method (for example, see Non-Patent Documents 1, 5, and 6), and the like.
Alkali metals are often used for the flux growth method. However, the crystal growth rate is slow and only a plate-like crystal having a size of about 10 mm is obtained, and the crystal growth mechanism and the cause of the crystal growth stopping at a size of about 10 mm are unknown. There are many points. On the other hand, attempts have been made to generate GaN by oxidizing nitrogen ions on the Ga surface used as an electrode in molten salt (for example, see Non-Patent Document 7), but the process leading to industrialization has not been established. . Furthermore, a method for synthesizing GaN by the ammonothermal method (see, for example, Non-Patent Document 8) has also been reported, but there are problems with the crystal size and the number of lattice defects, and it has not been industrialized.

In various GaN synthesis methods, Ga metal is frequently used as a synthesis raw material. For example, in Patent Document 1, a high-purity metal Ga, powder GaN, Li ₃ N, and the like, which are raw materials, are placed in a crucible and heated to synthesize a GaN single crystal. Ga metal has a melting point of 29.8 ° C. and often exists as a supercooled liquid at room temperature. In addition, Ga metal in a liquid state at room temperature has an extremely high surface tension and hardly mixes with other nitride raw materials. For this reason, when Ga metal and a nitride raw material are charged into a reaction vessel such as a crucible to synthesize GaN, the raw materials cannot be mixed together, and therefore, the nitride raw material must be placed around the Ga metal. In such a state, the contact area between the raw materials is small, the progress of the reaction is slow, and unevenness can occur depending on the location, so that the target GaN cannot be obtained efficiently. On the other hand, in Patent Document 2, an attempt is made to synthesize GaN by forming a liquid phase containing Ga metal by using a Ga-Li alloy having a very low Li content. However, the target GaN could not be obtained efficiently because it was not sufficiently mixed with the nitride raw material.
Chinese Patent Publication No. 1288079 JP 2006-045052 A Applied Physics, Volume 71, Issue 5 (2002), p. 548 J. Appl. Phys. 37 (1998) 309 J. Crystal Growth 178 (1977) 174 J. Crystal Growth 218 (2000) 712 J. Crystal Growth 260 (2004) 327 Metal Vol.73 No.11 (2003) 1060 Abstracts of 29th Molten Salt Chemistry Conference (1997), p. 11 Acta Physica Polonica A Vol.88 (1995) 137

  As described above, when using metal Ga (Patent Document 1) or Ga-Li alloy (Patent Document 2) having a very low Li content, it cannot be mixed uniformly with a solid nitride material. The Ga-containing nitride cannot be efficiently and uniformly crystal-grown. Metal Ga is difficult to mix even when the other raw materials are solid or liquid. Also, Ga metal solids have high hardness and are difficult to grind. Furthermore, most of Ga-containing nitride raw materials need to be handled under an inert gas because they react with air, and grinding and mixing while cooling under an inert gas are industrially difficult and impractical. .

  In addition, when using a plurality of Ga-containing nitride raw materials without being pulverized and mixed, for example, when a solid nitride raw material is placed on the metal Ga, the contact area between the metal Ga and the nitride raw material Therefore, the target Ga-containing nitride cannot be efficiently grown. Further, since the raw material is uneven as a whole, the crystal growth of the Ga-containing nitride does not occur uniformly. Further, even when a seed crystal substrate is used, the seed crystal substrate must be put into a non-uniform raw material, and uniform crystal growth cannot be desired.

  In order to solve the above problems, the present invention provides a method for producing a Ga-containing nitride capable of uniformly growing a high-quality Ga-containing nitride uniformly by an industrially available method. With the goal.

  Furthermore, another object of the present invention is to provide a method for manufacturing a semiconductor device such as a light emitting diode, a laser diode, and a high frequency electronic device using the above manufacturing method.

  As a result of intensive studies in view of the above problems, the present inventors have completed the present invention. That is, the object of the present invention is achieved by the following method for producing a Ga-containing nitride crystal.

[1] It includes a step of growing a crystal containing Ga-containing nitride by heating a mixture obtained by pulverizing and mixing at least an alloy containing an alkali metal element or alkaline earth metal element and Ga metal and a nitride raw material. A process for producing a Ga-containing nitride characterized by the following.

[2] The method for producing a Ga-containing nitride according to [1], wherein an average particle size of the alloy and the nitride raw material in the mixture is 1 mm or less.

[3] The method for producing a Ga-containing nitride according to [1] or [2], wherein the composition of the alloy is Ga _1-x Li _x (0.03 <x <1).

[4] The method for producing a Ga-containing nitride according to any one of [1] to [3], wherein the nitride raw material contains at least one of GaLi ₃ N _{2 and} GaN.

[5] The method for producing a Ga-containing nitride according to any one of [1] to [4], wherein the mixture is in a pellet form.

[6] The Ga-containing nitride according to any one of [1] to [5], wherein the mixture is prepared by pulverizing and mixing the alloy and the nitride raw material in an inert gas. Manufacturing method.

[7] The method for producing a Ga-containing nitride according to any one of [1] to [6], wherein the mixture is prepared by pulverizing the alloy and the nitride raw material.

[8] The method for producing a Ga-containing nitride according to any one of [1] to [7], wherein the Ga-containing nitride is crystal-grown on a seed crystal surface or a substrate.

[9] A method for producing a semiconductor device, comprising a step of producing a Ga-containing nitride crystal by the method for producing a Ga-containing nitride according to any one of [1] to [8].

  According to the method for producing a Ga-containing nitride of the present invention, high-quality Ga-containing nitride can be efficiently and uniformly crystal-grown. That is, by using an alloy containing an alkali metal element or an alkaline earth metal element and Ga metal and a nitride material pulverized and mixed, the reactivity between the alloy and the nitride material is improved, and the efficiency It is possible to carry out crystal growth of a desired Ga-containing nitride. In addition, there is no unevenness in the entire raw material, and crystal growth of the Ga-containing nitride tends to occur uniformly.

  The manufacturing method of the semiconductor device of this invention has the process of manufacturing Ga containing nitride using the manufacturing method of Ga containing nitride of this invention. Thereby, according to this invention, the semiconductor device which can respond to a high frequency can be manufactured.

Below, the manufacturing method of the Ga containing nitride of this invention and the manufacturing method of the semiconductor device using the manufacturing method are demonstrated in detail. The description of the constituent elements described below may be made based on representative examples of 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. In this specification, “on the substrate” includes the surface of the formed Ga-containing nitride crystal as well as the surface of the substrate of sapphire, SiC, ZnO or the like.

[Method for producing Ga-containing nitride]
The method for producing a Ga-containing nitride of the present invention comprises heating a mixture obtained by pulverizing and mixing at least an alloy containing an alkali metal element or an alkaline earth metal element and Ga metal, and a nitride raw material. It is characterized by crystal growth of an object.
According to the method for producing a Ga-containing nitride of the present invention, an alloy containing an alkali metal element or alkaline earth metal element and Ga metal (hereinafter, sometimes referred to as “alloy in the present invention”), and nitride. Since a mixture obtained by pulverizing and mixing raw materials (hereinafter sometimes referred to as “mixture in the present invention”) is used, the reactivity between the alloy and the nitride raw material is high, and there is no unevenness in the raw material. Crystal growth of the target Ga-containing nitride can be performed efficiently and uniformly.

[blend]
As described above, the method for producing a Ga-containing nitride of the present invention is characterized by using a mixture obtained by pulverizing and mixing the alloy according to the present invention and a nitride raw material. In the mixture of the present invention, Ga metal is used as an alloy with an alkali metal element or an alkaline earth metal element. Ga metal solids are high in hardness and difficult to grind, but alloys of Ga metal and alkali metals are easier to grind than Ga metal solids, and their melting point is higher than Ga metal. Therefore (for example, in the case of a Ga—Li alloy containing 50 atomic% of Li, the melting point is 730 ° C.), it is possible to perform pulverization and mixing without cooling with a cooling gas.

[Alloy containing alkali metal element or alkaline earth metal element and Ga metal]
The alloy in the present invention is an alloy containing an alkali metal element (Li, Na, K, Rb, Cs, Fr) or an alkaline earth metal element (Be, Mg, Ca, Sr, Ba, Ra) and Ga metal. is there.

The composition of the alloy in the present invention varies depending on the alkali metal element or alkaline earth metal element, but has a solidity (grindability) that can be mixed with other powder raw materials and inhibits the formation of Ga-containing nitrides. It is preferable to select from the viewpoint of not. Further, as will be described below, the alloy composition affects the reaction rate and also affects the crystal quality of the Ga-containing nitride as a product, so it is preferable to select an appropriate range. Specific examples of the alloy in the present invention include a Ga—Li alloy, a Ga—Na alloy, a Ga—Mg alloy, a Ga—Ca alloy, and the like. The alloy in the present invention is preferably used according to the elements in the nitride raw material. In particular, an alloy having a composition of Ga _1-x Li _x (0.03 <x <1) is preferable as the alloy in the present invention. In the case of a Ga—Li alloy, as shown in Table 1, the melting point (freezing point) varies significantly depending on the Li content. In order for the Ga—Li alloy to have pulverizable solidity, in consideration of supercooling and the like, the Li content must be at least 3 atomic%, preferably 5 atomic% or more, more preferably 10 atomic%. As mentioned above, 20 atomic% or more is more preferable.

In the present invention, a reaction in the case of using a Ga—Li alloy and using Li ₃ N or GaLi ₃ N ₂ as a nitride raw material is basically represented by the following formula or the like.
Ga + Li ₃ N = GaN + 3Li (1)
_{Ga + GaLi 3 N 2 = 2GaN} + 3Li (1) '

  If the proportion of Li in the Ga—Li alloy is too high, the chemical formulas (formulas (1) and (1) ′) may reach equilibrium, which may inhibit the production of GaN. In addition, when Ga alone is used, the reaction rapidly proceeds to the right first, and the GaN crystal may be deposited too quickly to produce a poor quality crystal. It is preferable to use a Ga—Li alloy instead of Ga since the reaction to the right proceeds relatively slowly and a good quality GaN crystal is easily generated. For the above reasons, the Li concentration in the Ga—Li alloy is preferably 3 atomic% to 50 atomic%, more preferably 5 atomic% to 30 atomic%. In the present invention, the equilibrium of the chemical formula may always be advanced to the right by removing Li from the reaction field by an electrochemical method or the like (see JP-A-2006-45052).

[Nitride raw materials]
The nitride raw material used in the present invention becomes a nitrogen source when growing a Ga-containing nitride. The nitride raw material is a nitride of a metal element other than Ga, or a composite nitride of a metal element other than Ga and Ga. Preferable specific examples of the nitriding raw material in the present invention include Li ₃ N, Mg ₃ N ₂ , Ca ₃ N ₂ , GaN, GaLi ₃ N ₂ , GaMg ₃ N ₃ , Ca ₃ Ga ₂ N _{3 and the} like. These may be used in combination. In the present invention, it is particularly preferable that the nitride raw material contains at least one of GaLi ₃ N ₂ or GaN.

[Other ingredients]
In the method for producing a Ga-containing nitride of the present invention, when a substance other than Ga metal is used for the purpose of doping, by adding a substance other than the Ga metal to the alloy or the nitride raw material in the present invention, The objective can be achieved within the manufacturing process of the present invention.

[Ga-containing nitride]
The Ga-containing nitride obtained by the method for producing a Ga-containing nitride of the present invention mainly indicates GaN. However, the Ga-containing nitride in the present invention may have other compositions.

[Particle size of alloy and nitride raw material after grinding (mixture in the present invention)]
A smaller particle size is preferable because the contact area between the raw materials is high. For this reason, the average particle size of the alloy and the nitride raw material in the present invention in the mixture in the present invention is preferably 1 mm or less, more preferably 0.5 mm or less, and further preferably 0.1 mm or less. Here, the particle size means the longest diameter among the particles, and the average particle size is expressed by the sum of the particle sizes of each particle / the number of particles, which indicates the average particle size. It is. The average particle diameter is obtained by randomly selecting 100 or more grains, measuring each particle diameter, and calculating the average value.

  The alloy and nitride raw material used in the present invention mostly react with moisture in the air, and it is difficult to use a general particle size distribution meter. For this reason, as a means for confirming the particle size of the particles in the mixture in the present invention, a method of directly observing with an optical microscope can be mentioned. These particle size measurements are desirably performed under an inert gas such as Ar, and are desirably performed quickly when performed in air.

[Raw material crushing and mixing method]
When preparing the mixture in the present invention, the alloy and nitride raw material in the present invention often reacts with at least one of moisture, oxygen, and nitrogen in the air, so pulverization and mixing in an inert gas such as argon. It is desirable to do. In particular, since lithium alloys react with nitrogen to form nitrides at room temperature and at high temperatures, when lithium alloys are used, they must not be pulverized or mixed in a nitrogen atmosphere.

  When preparing the mixture in the present invention, for example, the alloy may be pulverized and mixed, for example, by first pulverizing each raw material and then mixing them to prepare the mixture in the present invention. Crushing and mixing may be performed simultaneously, that is, the alloy and the nitride raw material may be mixed while being pulverized to produce the mixture in the present invention. The latter is preferable because the particle diameters of the raw materials are easily uniform and can be mixed more uniformly.

  As a method for pulverizing each raw material, there are a method of grinding with a hand or a machine using a mortar or the like, a method of using a machine such as a stamp mill, a ball mill, a blender, etc., which can be appropriately used according to each raw material. Moreover, as a mixing method of each raw material, the above-mentioned pulverization method can be used as it is (they are mixed by pulverizing the alloy and nitride raw material in the present invention together), mixer, mix rotor, pot mill, stirrer, etc. There are methods using these mixing devices, and each of these methods can be used as appropriate. The material of the container (mortar, pestle, pulverized ball, etc.) used for pulverizing and mixing each raw material is mainly high in hardness and has high pulverizing ability, although it depends on the type of raw material to be pulverized and mixed. It is required that a part of the container is not mixed into the raw material by pulverization or mixing. Specific examples of containers used for pulverizing and mixing each raw material include mullite, high alumina, agate, stainless steel, tungsten carbide, diamond and the like. Among these, tungsten carbide is preferable because of its high hardness and relatively low cost.

[Processing after mixing]
You may use the mixture in this invention obtained by the said mixing in a reaction container with the state grind | pulverized as it is. In the case where the adhesion of fine particles to the seed crystal substrate is a concern, it is preferable that the mixture is pressed and solidified into a pellet before being put into the reaction vessel.

[Crystal growth]
According to the method for producing a Ga-containing nitride of the present invention, the Ga-containing nitride is produced by heating the mixture according to the present invention and crystal growth of the Ga-containing nitride.
Crystal growth of the Ga-containing nitride is preferably performed by growing the crystal on the seed crystal surface or the substrate. As a crystal growth method, a top seed crystal method, a temperature gradient method, a crucible rotation method, a seed crystal rotation method, a slow temperature reduction method, or the like can be adopted.

  In the method for producing a Ga-containing nitride of the present invention, a nitride raw material is brought into contact with the alloy in the present invention to be reacted. At this time, it is preferable to use a Ga-containing nitride crystal or substrate as a seed crystal for crystal growth. The shape of the seed crystal is not particularly limited, and may be a flat plate shape or a rod shape. Further, it may be a seed crystal for homoepitaxial growth or a seed crystal for heteroepitaxial growth. Specific examples include seed crystals of Ga-containing nitrides such as vapor-grown GaN, InGaN, and AlGaN. In addition, metal oxides such as sapphire, silica, ZnO, and BeO, silicon-containing materials such as SiC and Si, and materials used as a substrate in vapor phase growth of GaAs and the like can be given. The seed crystal and substrate material are preferably selected as close as possible to the lattice constant of the Ga-containing nitride crystal grown in the present invention. When a rod-shaped seed crystal is used, a bulk crystal is produced by first growing in the seed crystal portion, then performing crystal growth mainly in the horizontal direction, and then performing crystal growth in the vertical direction. You can also. When performing crystal growth in the horizontal direction, it is preferable to control the composition distribution of the Ga alloy in the horizontal direction so that crystal growth stops at an appropriate portion up to the side wall of the container.

[Reaction conditions]
In this invention, as temperature conditions at the time of heating the mixture in this invention, it is 200-1000 degreeC normally, Preferably it is 400-900 degreeC, More preferably, it is 600-800 degreeC. The heating time is usually 2 hours to 10 days, but if the crystal growth is comparable, shorter time is preferable because it leads to cost reduction. In the method for producing a Ga-containing nitride of the present invention, since the reaction is started after the raw materials are uniformly mixed in advance, the same crystal growth is preferable because the reaction time can be shortened. Further, the pressure during the reaction is usually 10 MPa or less, preferably 1 MPa or less, more preferably normal pressure. Since the present invention can be carried out at normal pressure, the apparatus is cheaper and safer than other high-pressure methods, which is very preferable industrially.

In the present invention, the heating of the mixture in the present invention is usually carried out by putting the mixture in the present invention in a crucible. Specific examples of the material of the crucible include oxides such as magnesium oxide, calcium oxide, yttrium oxide, zirconium oxide, aluminum oxide and quartz, nitrides such as boron nitride, metals such as molybdenum and tungsten. it can. Of these, any one that can withstand the reaction temperature, does not react with the raw materials and the product, and does not mix with the product (Ga-containing nitride) may be used. If these performances are equivalent, relatively inexpensive oxides are industrially preferable.
In the method for producing a Ga-containing nitride according to the present invention, the mixture according to the present invention is heated to grow a crystal containing the Ga-containing nitride. Apply processing. Specifically, the acid treatment can be performed by putting the mixture after the reaction in an acid such as hydrochloric acid or nitric acid and heating at a temperature that does not boil for several hours.

[Method for Manufacturing Semiconductor Device]
The method for producing a Ga-containing nitride of the present invention can be used in a process for producing a Ga-containing nitride in a method for producing a semiconductor device. The raw materials, conditions, and apparatuses used in general semiconductor device manufacturing methods can be applied as they are for the raw materials, manufacturing conditions, and apparatuses in other processes. Examples of the semiconductor device include a light emitting diode, a laser diode, and a high frequency electronic device.

  The features of the present invention will be described more specifically with reference to the following 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]
A mixture obtained by mixing 0.15 g of GaLi ₃ N ₂ and 3 g of Ga-Li alloy containing 20 atomic% of Li in a crucible of magnesium oxide under an inert gas (argon gas) while pulverizing by thoroughly mixing in a mortar. Put. Under the present circumstances, when the particle | grains in a mixture were directly observed with the optical microscope, the average particle diameter was about 0.1 mm or less (FIG. 1). Next, the crucible was put in a quartz reaction tube and heated to 770 ° C. over 50 hours while gradually lowering the temperature from 780 ° C. under nitrogen flow. After heating, the contents were acid-treated to obtain 92 mg of transparent and plate-like GaN crystals. The yield of GaN converted from GaLi ₃ N ₂ was 87%.

[Example 2]
Under an inert gas (argon gas), the crucible magnesium oxide, placed liquid Ga3g, thereon, with a mortar and Gali alloy 0.36g containing GaLi ₃ N ₂ 0.15g and 20 atomic percent of Li The mixture mixed while being pulverized by mixing well was placed. Under the present circumstances, when the particle | grains in a mixture were directly observed with the optical microscope, the average particle diameter was about 0.1 mm or less. The crucible was placed in a quartz reaction tube and heated at 780 ° C. for 40 hours under nitrogen flow. After the heating, the contents were acid-treated to obtain 66 mg of transparent and plate-like GaN crystals. The yield of GaN converted from GaLi ₃ N ₂ was 62%.

[Example 3]
Under an inert gas (argon gas), a GaN seed crystal substrate is placed in a crucible of magnesium oxide, and 0.15 g of GaLi ₃ N ₂ and ₃ g of a Ga—Li alloy containing 15 atomic% Li are placed on the mortar. The mixture was mixed while being pulverized by thoroughly mixing. Under the present circumstances, when the particle | grains in a mixture were observed directly and directly with the optical microscope, the average particle diameter was about 0.1 mm or less. The crucible was placed in a quartz reaction tube and heated at 780 ° C. for 90 hours under nitrogen flow. After heating, the contents were acid-treated to obtain 28 mg of transparent and plate-like GaN crystals. The yield of GaN converted from GaLi ₃ N ₂ was 22%. Further, when the GaN seed crystal substrate was observed with an SEM, new crystal growth was confirmed.

[Comparative Example 1]
In Example 1, the same conditions as in Example 1 except that GaLi ₃ N ₂ and Ga—Li alloy were not mixed, Ga—Li alloy was first put in the crucible, and GaLi ₃ N ₂ was placed thereon. The experiment was conducted to obtain 0.3 mg of opaque and powdery GaN crystals. The yield of GaN was 0.3%.

[Comparative Example 2]
In Example 2, an experiment was performed under the same conditions as in Example 2 except that no Ga—Li alloy was used, and 14 mg of opaque and powdery GaN crystals were obtained. The yield of GaN was 14%.

[Comparative Example 3]
In Example 3, using a liquid Ga3g instead of Gali alloy, instead of Surimazeru a mortar, first put the Ga in the crucible, the same manner as in Example 3 except that carrying the Gali ₃ N ₂ thereon The experiment was conducted under the conditions, and 6 mg of opaque and powdery GaN crystals were obtained. The yield of GaN was 5%. Further, when the GaN seed crystal substrate was observed by SEM, no new crystal growth could be confirmed.

[Comparative Example 4]
In Example 3, a Ga—Li alloy containing 2 atomic% Li was used instead of a Ga—Li alloy containing 15 atomic% Li. Since the Ga-Li alloy containing 2 atomic% Li was solid at room temperature, it quickly became liquid when heated with a heater to weigh, but it did not become solid easily even after cooling to room temperature after weighing. It was. Reluctantly tried mixed in Gali ₃ N ₂ and mortar remain liquid but not immiscible well, as it is placed in a crucible, the same experiment as in Example 3 to obtain an opaque powdery GaN crystal 16 mg. The yield of GaN was 15%, which was lower than that of Example 3. When the GaN seed crystal substrate was observed with SEM, no new crystal growth could be confirmed.

  As described above, the comparative example in which the alloy containing Ga and the nitride raw material are not pulverized / mixed has a significantly lower yield than the examples, the size of the obtained GaN crystal is small, the transparency is low, and the seed crystal substrate No crystal growth occurred.

  According to the production method of the present invention, high-quality Ga-containing nitride can be uniformly crystal-grown efficiently. In addition, since the yield is high, it can be easily used industrially, and can be applied to a wide range of applications such as the manufacture of semiconductor devices capable of handling high frequencies. Therefore, the present invention has high industrial applicability.

2 is an optical micrograph of particles in a mixture prepared in Example 1. FIG.

Claims (10)

At least a Ga-containing nitride comprising a step of heating a mixture obtained by pulverizing and mixing an alloy containing an alkali metal element or alkaline earth metal element and Ga metal and a nitride raw material, and crystal-growing the Ga-containing nitride. A method for producing a Ga-containing nitride, characterized in that the alloy is an alloy solid having a melting point of 115 ° C. or higher . The Ga-containing material according to claim 1, wherein the alloy containing the alkali metal element or alkaline earth metal element and Ga metal is a Ga-Li alloy, a Ga-Na alloy, a Ga-Mg alloy, or a Ga-Ca alloy. A method for producing nitride. The method for producing a Ga-containing nitride according to claim 1 or 2 , wherein an average particle size of the alloy and the nitride raw material in the mixture is 1 mm or less. Method for producing a composition of the _{alloy, Ga 1-x Li x (} 0.03 ≦ x <1) Ga -containing nitride according to any one of claims 1-3, characterized in that the. The nitride raw material, GaLi ₃ N ₂ or the method of manufacturing the Ga-containing nitride according to any one of claims 1 to 4, characterized in that it comprises at least one of GaN. Method for producing a Ga-containing nitride according to any one of claims 1 to 5, characterized in that said mixture is pelletized. The said mixture is produced by grind | pulverizing and mixing the said alloy and the said nitride raw material in inert gas, The manufacturing method of Ga containing nitride of any one of Claims 1-6 characterized by the above-mentioned. . The method for producing a Ga-containing nitride according to any one of claims 1 to 7 , wherein the mixture is prepared by pulverizing the alloy and the nitride raw material. The method for producing a Ga-containing nitride according to any one of claims 1 to 8 , wherein the Ga-containing nitride is crystal-grown on a seed crystal surface or a substrate. A method for producing a semiconductor device, comprising a step of producing a Ga-containing nitride crystal by the method for producing a Ga-containing nitride according to any one of claims 1 to 9 .

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