JP2013100207A - Regenerating method of member used for manufacturing periodic table group 13 metal nitride semiconductor crystal, and manufacturing method of periodic table group 13 metal nitride semiconductor crystal - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem in which the members of a reaction vessel or the like used for manufacturing a periodic table group 13 metal nitride semiconductor crystal sometime progress changing in quality and/or deterioration by the use of repeating and/or for a long time, and are necessary to be exchanged, however that invites the increase of the production cost if exchanging frequently for a new member.SOLUTION: The member that has changed in quality and/or has been deteriorated is processed so that the color value (L* value) and/or the expansion coefficient may become numerical values of a given range, thereby the member can be regenerated so as to be reused for manufacturing the group 13 nitride semiconductor crystal.

Description

  The present invention relates to a method for regenerating a member used for manufacturing a periodic table group 13 metal nitride semiconductor crystal and a manufacturing method for a periodic table group 13 metal nitride semiconductor crystal.

  Periodic table Group 13 metal nitride semiconductors typified by gallium nitride have a large band gap, and the transition between bands is a direct transition type. It has been put to practical use as a light emitting element on the short wavelength side. These elements are preferably manufactured using a high-quality substrate made of the same kind of material and having a low dislocation density, and a manufacturing technique of a periodic table group 13 metal nitride semiconductor crystal that can be such a substrate is used. It has been actively studied. As typical production methods, vapor phase epitaxial growth methods such as halide vapor phase epitaxy (HVPE) and metal organic chemical vapor deposition (MOCVD) are generally known. From the above viewpoint, etc., studies on a liquid phase epitaxial growth method such as a sodium flux method are also in progress.

  Regarding liquid phase epitaxial growth methods such as the sodium flux method, the problem that reaction vessels used for production swell, infiltrate and deteriorate has been reported, and ceramics made of titanium nitride or zirconium nitride have been reported as a method for solving such problems. It has been proposed to use a manufactured reaction vessel (see Patent Document 1). In addition, since a ceramic reaction vessel is inferior in workability and mechanical durability, a metal member containing a Group 4-6 element in the periodic table with a nitride layer formed on the surface (reaction vessel, stirring blade, seed) It has been proposed to use a crystal holding rod, a seed crystal holding table, a baffle, a gas introduction pipe and a valve (see Patent Document 2). It has been reported that the use of such a member having excellent corrosion resistance and workability can greatly reduce the manufacturing cost.

JP 2006-265069 A International Publication No. 2010/140665

A material excellent in corrosion resistance is selected as a member such as a reaction vessel used for the production of the Group 13 metal nitride semiconductor crystal of the periodic table, but deterioration and / or deterioration progresses by repeated and / or long-time use. There are things to do. Since the member that has reached such a state may adversely affect the growth of the semiconductor crystal, it needs to be replaced. However, if the member is frequently replaced with a new member, the manufacturing cost increases.
In order to deal with such a problem, it is conceivable to increase the durability of the member as one countermeasure. However, if a deteriorated and / or deteriorated member can be easily regenerated, this is also effective in reducing the manufacturing cost. Can be a good tool.
That is, the present invention relates to a method for regenerating a member used for producing a deteriorated and / or deteriorated periodic table group 13 metal nitride semiconductor crystal, and a periodic table group 13 using the regenerated member. It is an object of the present invention to provide a method for producing a metal nitride semiconductor crystal.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have obtained a numerical value having a color value (particularly L ^* value) and / or an expansion coefficient in a specific range for members that have undergone alteration and / or deterioration. It has been found that the process can be reused in the production of Group 13 metal nitride semiconductor crystals of the periodic table without adversely affecting the crystal growth.

That is, the present invention is as follows.
(1) A method for regenerating a deteriorated and / or deteriorated member used for producing a Group 13 metal nitride semiconductor crystal of the periodic table, wherein the color value (L ^* value) is less than 40 and / or from an unused state. Preparation step for preparing a member including a deteriorated / deteriorated portion having an expansion coefficient of 1.0% or more, and a color value (L ^* value) of 40 or more and / or an expansion coefficient of 1.0. A method for regenerating a member, comprising a treatment step of less than%.
(2) The method for regenerating a member according to (1), wherein the member contains at least one selected from Group 4 to 6 elements of the periodic table, Sc, Y, Ni, and Pd.
(3) The member is composed of a metal or an alloy containing at least one selected from Group 4 to 6 elements of the periodic table, Sc, Y, Ni and Pd, and 90% by weight or more thereof (2 The method for regenerating a member according to (4).
(4) The method for regenerating a member according to any one of (1) to (3), wherein the member has a film formed on a surface thereof.
(5) The method for regenerating a member according to (4), wherein the coating is a nitride containing at least one selected from Group 4 to 6 elements of the periodic table.
(6) The member according to any one of (1) to (5), wherein the member is at least one selected from a reaction vessel, a stirring blade, a seed crystal holding rod, a seed crystal holding table, a baffle, a gas introduction pipe, and a valve. Method for regenerating the member.
(7) The member regeneration method according to any one of (1) to (6), wherein the treatment step includes a vacuum heat treatment.
(8) The method for regenerating a member according to any one of (4) to (7), wherein the processing step includes a film re-forming process.
(9) The member according to any one of (1) to (6), wherein the production of the Group 13 metal nitride semiconductor crystal of the periodic table is a production method in which a component containing a hydrogen element is present in the reaction system. Playback method.
(10) A periodic table group 13 metal produced by using a member regenerated by the method for regenerating a member according to any one of (1) to (9) and / or an apparatus including the member. A method for producing a nitride semiconductor crystal.
(11) The periodic table according to (10), including a step of producing a solution or melt containing a raw material and a solvent, and a growth step of epitaxially growing a periodic table group 13 metal nitride semiconductor crystal in the solution or melt. A method for producing a Group 13 metal nitride semiconductor crystal, wherein the step of producing the melt or solution and / or the growth step is performed by the method for regenerating a member according to any one of (1) to (9). The manufacturing method of a periodic table group 13 metal nitride semiconductor crystal performed using the reproduced | regenerated member and / or the apparatus containing the said member.
(12) The method for producing a periodic table group 13 metal nitride semiconductor crystal according to (10) or (11), wherein a component containing a hydrogen element is present in the reaction system.

  According to the present invention, an altered and / or deteriorated member used for the production of a periodic table group 13 metal nitride semiconductor crystal can be regenerated to a state that does not adversely affect crystal growth, and the member can be reused. By doing so, the manufacturing cost of the periodic table group 13 metal nitride semiconductor crystal can be reduced.

It is a conceptual diagram of the apparatus which nitrides the member surface. It is a conceptual diagram of the manufacturing apparatus used for the manufacturing method of the periodic table group 13 metal nitride semiconductor crystal of this invention. It is a conceptual diagram of the apparatus which vacuum-processes a member.

  A method for regenerating a member used for manufacturing a periodic table group 13 metal nitride semiconductor crystal and a manufacturing method for a periodic table group 13 metal nitride semiconductor crystal of the present invention will be described in detail below. Unless it is contrary, it is not limited to these contents.

<Regeneration method of member used for production of periodic table group 13 metal nitride semiconductor crystal>
The present invention is a member used for the manufacture of a periodic table group 13 metal nitride semiconductor crystal (hereinafter sometimes referred to as “group 13 nitride semiconductor crystal”), which has been altered and / or deteriorated by use. This is a method of regenerating the member in the above to a state that does not adversely affect the crystal growth.
The present inventors clarified the following contents (a) to (c) for members used for manufacturing, while proceeding with studies on a method for manufacturing a Group 13 nitride semiconductor crystal.
(A) The color of the member changes and / or the member expands cumulatively (temporarily due to heating or the like) by repeated and / or long-term use in the production of a Group 13 nitride semiconductor crystal. It is not an expansion but an expansion in an unused state in observation at room temperature)
The expansion of the member is caused by absorbing the components present in the reaction system, and is used in the production method in which components containing hydrogen element (H ₂ , NH ₃ , CH _4, etc.) are present in the reaction system. In some cases, it has become clear that hydrogen is taken up in particular. It has been clarified that the color change of the member is caused by the deterioration of the film formed on the member or the member surface or the occurrence of micro cracks or voids on the surface.
(B) When crystal growth is performed using a member in which a color value (L ^* value) has changed to a specific value and / or has a portion expanded to a specific size, a group 13 nitride semiconductor crystal The principle that the crystal growth rate decreases is not fully clarified, but the member or the coating formed on the member surface deteriorates or the member expands to cause the member to expand. This is probably because impurities are easily released and crystal growth is hindered by the released impurities.
(C) By treating the member so that the color value (L ^* value) and / or the expansion coefficient are within a specific range, the member does not adversely affect the crystal growth, that is, the state of deterioration and / or deterioration. It is clear that the member in the above can be regenerated to a state that does not adversely affect the crystal growth, and the color value (L ^* value) and the expansion rate can be used as an index for regenerating the member. It was.

Although the present invention is a method for regenerating a member used for manufacturing a Group 13 nitride semiconductor crystal, the method for manufacturing a Group 13 nitride semiconductor crystal targeted by the present invention is not particularly limited, and halide vapor phase growth is possible. For any growth method such as vapor phase epitaxy such as metal organic chemical vapor deposition (MOCVD) or liquid phase epitaxy such as melt growth, high pressure solution method, flux method, and low temperature method Is applicable. However, as described above, since the influence of taking in hydrogen is large with respect to the expansion of the member, it is particularly suitable for a production method in which a component containing a hydrogen element exists in the reaction system. Examples of the “component containing hydrogen element” include H ₂ , NH ₃ , hydrocarbons such as CH ₄ , C ₂ H ₆ , C ₃ H ₈ , hydrogen halides such as HF, HCl, HBr, HI, etc. Is mentioned. In particular, when utilizing in a liquid phase epitaxial growth method containing H ₂ in the reaction system, the method for regenerating a member of the present invention can be suitably used. Further, the type of the Group 13 nitride semiconductor crystal to be manufactured is not particularly limited, and in addition to a nitride composed of one type of Group 13 metal such as GaN, AlN, InN, two or more types of GaInN, GaAlN, etc. Examples include composite nitrides made of Group 13 metals.

The member targeted by the regeneration method of the present invention is not particularly limited as long as it is used for the production of a Group 13 nitride semiconductor crystal, but is exposed to an atmospheric gas, a solution, a melt, or the like in the crystal growth process. Possible members can be mentioned. Specifically, a reaction vessel, a stirring blade, a seed crystal holding rod, a seed crystal holding table, a baffle, a gas introduction pipe, a valve, and the like can be given.

The material of the member targeted by the regeneration method of the present invention is not particularly limited as long as it can be used for the production of a Group 13 nitride semiconductor crystal, but the member may take in hydrogen as described above. It has high affinity with hydrogen and is particularly suitable for a member containing a metal element that can form a hydride. Specifically, a member containing at least one selected from Group 4 to 6 elements of the periodic table (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W), Sc, Y, Ni and Pd, A member containing at least one selected from Group 4 to 6 elements of the periodic table, more preferably Group 4 elements (Ti, Zr, Hf) of the periodic table is more preferable. Among them, a member containing an element whose standard generation energy ΔG ^f _{0 of the} hydride is less than 0 is preferable. In particular, Ti and Zr have standard formation free energies ΔG ^f ₀ of their hydrides of −80.3 kJ / mol and −128.8 kJ / mol, respectively, and are highly compatible with hydrogen. Particularly preferred.

  The member used for manufacturing the Group 13 nitride semiconductor crystal is preferably a material rich in workability and mechanical durability, and the member is more preferably composed mainly of metal (bulk metal). . Specifically, 90% by weight or more, more preferably 99% by weight or more of the member is made of a metal or alloy containing at least one selected from Group 4 to 6 elements of the periodic table, Sc, Y, Ni and Pd. It is preferable.

Further, the member targeted by the regeneration method of the present invention may be one in which a film is formed on the member surface. The coating may be a coating intentionally formed in order to improve the corrosion resistance of the member, or may be a coating formed so as to be stabilized against an exposed environment. The thickness of the coating is also not particularly limited, and is usually about 10 nm to 1 mm, preferably 100 nm to 100 μm, and more preferably 1 μm to 10 μm. Examples of the component of the coating include a metal layer, an oxide layer, a nitride layer, etc. Among them, a nitride layer exhibiting excellent corrosion resistance particularly with respect to the manufacturing conditions of the Group 13 nitride semiconductor crystal. Is preferably formed, and a nitride layer including at least one selected from Group 4 to 6 elements of the periodic table is particularly preferably formed. Among these, the member in which the nitride layer containing a periodic table group 4 element such as Ti or Zr is formed has a deterioration value and / or deterioration state of the member, and a color value (L ^(* Value) has a very high correlation with the value.

  As a method for forming a film on the surface of the member, a vapor deposition method such as PVD (Physical Vapor Deposition) and CVD (Chemical Vapor Deposition), or a method in which a layer to be a film is separately prepared and bonded to the surface of the member Furthermore, a known method such as a method of converting the composition of the member surface itself into a coating composition can be appropriately employed. Among these, since the shape of the member is not limited and a film can be formed relatively easily, a method of converting the composition of the member surface itself into the composition of the film is preferable.

A method for forming a nitride layer will be described as an example of a method for converting the composition of the member surface described above into a coating composition. As a method for nitriding the composition of the member surface itself, for example, a stable nitride layer can be formed by heating and holding in a nitrogen atmosphere at 100 to 1500 ° C., preferably 700 ° C. or higher. In this case, it is preferable to flow 1 to 10000 cm ³ / min of N ₂ gas in an amount converted to normal temperature and normal pressure, and it is more preferable to flow 10 to 1000 cm ³ / min of N ₂ gas. In addition, a method using alkali metal nitride, alkaline earth metal nitride, or the like as a nitriding agent can be used. As a condition of such a method, a stable nitride layer can be formed by heating and holding the member at a temperature of usually 200 to 1500 ° C., preferably 600 to 800 ° C. in the presence of a nitriding agent.

The present invention is a method of reproducing a member in a state of deterioration and / or deterioration so that it can be reused. In order to grasp the state of deterioration and / or deterioration of a member, the “color value (L ^* value)” is used. And / or “expansion rate” as an index.
“Color value (L ^* value)” means a lightness index measured based on the L ^* a ^* b ^* color system recommended by the International Commission on Illumination (CIE). “Value (L ^* value)” means a value measured by a cross-light metering method in accordance with JIS Z8722 in particular. The color of the member is mainly caused by the chemical composition of the member or the member surface, but is greatly influenced by the structure of the member surface, for example, a micro-sized uneven structure. The inventors of the present invention used to manufacture a Group 13 nitride semiconductor crystal, and confirmed that micro cracks and voids were generated on the surface of the member by the progress of deterioration and / or deterioration. It has been found that / or the deterioration is highly correlated with the color of the member, particularly the lightness (L ^* value). That is, by observing the L ^* value among the color values of the member, it is possible to easily grasp the degree of deterioration and / or deterioration of the member.
Further, “expansion rate” means a rate of change in dimensions such as length, width, and height in the present invention. Specifically, this corresponds to a numerical value calculated by measuring a dimension in an unused state and a dimension in a current state (after expansion) and applying it to the following calculation formula [1]. In the case of a member having a shape such as a cylinder, in addition to the vertical, horizontal, and height, the target dimensions can be the inner diameter, outer diameter, depth, and the like, and are not limited to specific dimensions. The “unused state” means that the member is not exposed to the atmospheric gas, melt or solution in crystal growth. Even if it is not actually used for the production of a Group 13 nitride semiconductor crystal, it is conceivable that the member deteriorates due to exposure to an atmospheric gas or a melt, or absorbs components present in the reaction system. . Note that a film forming process (for example, nitriding process) described later is not included in the use.

  The color value can be measured using a known device, for example, a colorimetric color difference meter, a spectral color difference meter, or a chromaticity meter. In measurement, it is desirable to measure the color value using a cross light metering method based on JIS Z8722.

  The dimension measuring method used for calculating the expansion coefficient can be measured using, for example, a ruler, a measure, a caliper, a laser displacement meter, or an image photographing / image processing apparatus.

The member recycling method of the present invention is “preparing to prepare a member including a deteriorated / degraded portion having a color value (L ^* value) of less than 40 and / or an expansion rate from an unused state of 1.0% or more. Process ”. “The color value (L ^* value) is less than 40 and / or the expansion rate from the unused state is 1.0% or more”, that is, alteration to the point where there is a possibility of adversely affecting the crystal growth. This means a state in which the deterioration has progressed, and the “altered / degraded portion” means a region in the member in which the quality has deteriorated and / or deteriorated to such a state. Since the present invention is a method for regenerating a member that has been deteriorated and / or deteriorated to a state that does not adversely affect crystal growth, it is necessary to actually prepare such a member as a precondition for regeneration. That is, the “preparing step of preparing a member” corresponds to an act of preparing a member that has been deteriorated and / or deteriorated to the point where it may adversely affect crystal growth. In addition, in this process, for a member whose alteration and / or deterioration state is unknown, the region where the “color value (L ^* value) is less than 40” and / or the member “expansion coefficient is 1.0% or more The work which confirms whether the area | region which is "" may exist may be included.

Note that the threshold value of the color value (L ^* value) may be reset as appropriate depending on the material of the member, the type of coating on the surface, and the like. "Color values (L ^* value)" especially altered and / or high state correlated with deterioration in members nitride layer containing a periodic table Group 4 element is formed, "color values (L ^* value ) Is less than 40 ", it is possible to accurately determine the state of alteration and / or deterioration. Even when a member in which a nitride layer mainly containing elements other than Group 4 elements of the periodic table is used is used, it is possible to apply the color value (L ^* value) threshold value. In addition, by determining the range of color values (L ^* values) that are separately suitable depending on the material of the member, the type of coating on the surface, etc., it is possible to more accurately determine the state of deterioration and / or deterioration of the member.

色彩値（Ｌ^*値）の変化率を指標とする場合、通常、変化率が３０％以上で、結晶成長
に悪影響を与える可能性があるところまで変質及び／又は劣化が進行した状態と判断することができる。なお、周期表第１３族金属窒化物半導体結晶の製造に用いる部材として、表面に被膜が形成された部材を用いる場合には、「未使用の状態の部材」とは、被膜形成前の部材ではなく、被膜形成後の部材を意味する。従って、「色彩値（Ｌ^*値）の変化率
が３０％以上である変質・劣化部を含む部材」を準備する工程であってもよい。 Also, instead of using color values (L ^* value) may be directly utilized the rate of change of color values is calculated by the following equation [2] (L ^* value).

When the change rate of the color value (L ^* value) is used as an index, it is usually judged that the change rate is 30% or more and the state of deterioration and / or deterioration has progressed to the point where it may adversely affect the crystal growth. be able to. In addition, when a member having a film formed on the surface is used as a member used for manufacturing the Group 13 metal nitride semiconductor crystal of the periodic table, the “unused member” is a member before the film is formed. It means the member after film formation. Therefore, it may be a step of preparing “a member including a deteriorated / degraded portion whose color value (L ^* value) change rate is 30% or more”.

The member recycling method of the present invention is also characterized by including a “processing step of setting the color value (L ^* value) of the altered / degraded portion to 40 or more and / or the expansion rate to less than 1.0%”. . “Color value (L ^*
The value) is 40 or more and / or the expansion rate is less than 1.0%, that is, it means that there is a low possibility of adversely affecting the crystal growth, and the “processing step” is such a state. It means that it is a step of appropriately processing the member in order to regenerate it. Such a treatment process is not particularly limited as long as the color value (L ^* value) and / or the expansion rate of the altered / degraded portion is within the above specific range, and the specific treatment method is particularly It is not limited. Whether or not there is a region having a “color value (L ^* value) of less than 40” and / or a region having a “expansion coefficient of 1.0% or more” for the member after the processing is performed. The work of confirming may be included.

As a state having a low possibility of adversely affecting the crystal growth, the color value (L ^* value) is preferably 45 or more, more preferably 50 or more, and the expansion coefficient is 0.8% or less. It is preferably 0.5% or less, and more preferably 0.2% or less. Therefore, in the processing step, the color value (L ^* value) and / or the expansion rate is
It is more preferable to carry out so that it may become the said range. The upper limit of the color value (L ^* value) is not particularly limited, but is usually 100 or less. Further, the lower limit of the expansion coefficient is not particularly limited, but it is usually 0.0% or more.
Similarly to the above-described “preparing step for preparing the member”, the threshold value of the color value (L ^* value) may be reset as appropriate depending on the material of the member, the type of the coating on the surface, and the color value ( instead of using L ^* value) directly, or by utilizing a change rate of the color value calculated by the above equation [2] (L ^* value). As described above, even when a member in which a nitride layer mainly containing elements other than Group 4 elements of the periodic table is used is used, it is possible to apply the threshold value of the color value (L ^* value). However, depending on the material of the member, the type of coating on the surface, etc., another suitable color value (L ^* value)
By determining the range, it is possible to determine the state of deterioration and / or deterioration of the member with higher accuracy. When the change rate of the color value (L ^* value) is used as an index, the change rate of the color value (L ^* value) is usually 30% or more, and / or the alteration and / or to the extent that it may adversely affect the crystal growth It can be determined that the deterioration has progressed. Therefore, the change rate of the color value (L ^* value) is 30
It is preferable to include a treatment step of less than%. Furthermore, as a state that does not adversely affect the crystal growth, the change rate of the color value (L ^* value) is preferably 20% or less, and more preferably 10% or less. Although a minimum is not specifically limited, Usually, setting it as 0.0% or more is mentioned.

The above processing step according to the present invention is a specific processing method as long as it is a step of “making the color value (L ^* value) of the altered / degraded part 40 or more and / or the expansion coefficient less than 1.0%”. Although there is no particular limitation, a process including a film reforming process and / or a vacuum heating process is preferable.

  The vacuum heat treatment is a treatment in which the member is subjected to reduced pressure (vacuum) and high temperature conditions in order to remove absorbed components from the member. As described above, in a production method in which a component existing in the reaction system, particularly a component containing a hydrogen element exists in the reaction system, by repeatedly and / or using it for a long time in the production of the group 13 nitride semiconductor crystal. When used, it has been confirmed to absorb hydrogen. The vacuum heat treatment can effectively remove components absorbed by the member, particularly hydrogen, and is a particularly effective means for reducing the volume of the expanded member.

The apparatus and conditions for performing the vacuum heat treatment are not particularly limited as long as the members can be exposed to reduced pressure and high temperature conditions. For example, the apparatus and conditions are implemented by using an apparatus as shown in FIG. can do. Further, the pressure condition in the vacuum heat treatment is not particularly limited as long as it is close to vacuum, but is preferably 1.0 × 10 ⁻² Torr or less, more preferably 1.0 × 10 ⁻³ Torr or less. . Moreover, the temperature conditions in vacuum heat processing are 100-1500 degreeC normally, Preferably it is 500-1200 degreeC, More preferably, it is 700-1000 degreeC. Furthermore, the processing time of the vacuum heat treatment is usually 12 hours or longer, preferably 24 hours or longer, more preferably 48 hours or longer.

The coating re-formation process means that a coating intentionally formed on the surface of the member in order to enhance the corrosion resistance of the member or a coating formed on the surface of the member that is stabilized against the exposed environment is a group 13 nitride. It may be peeled off or deteriorated due to the use of a member for the production of a physical semiconductor crystal, and this is a treatment performed for the purpose of repairing these and restoring the corrosion resistance. The method of re-forming the film is not particularly limited as long as it can be re-formed by the same operation as that of the film before use. However, as a step before re-forming the film, there is a step of removing the remaining film. It is preferably included. This is because in the state where the altered and / or deteriorated film remains, the re-formation of the film becomes non-uniform, and impurities are released from the remaining film, which may inhibit the crystal growth. As a specific method for removing the film, for example, when removing a metal nitride layer such as TiN, it can be performed by exposing it to an acidic solution such as hydrochloric acid. The re-forming process of the coating is a particularly effective means for increasing the color value (L ^* value) since it can improve the corrosion resistance of the member and remove micro cracks and voids generated on the surface of the member.

<Method for Producing Periodic Table Group 13 Metal Nitride Semiconductor Crystal of the Present Invention>
According to the member recycling method of the present invention, the member can be regenerated up to a state where the crystal growth is not adversely affected. However, the member regenerated by the regeneration method and / or the apparatus including the regenerated member can be used. A manufacturing method for manufacturing a group nitride semiconductor crystal is also one aspect of the present invention. By utilizing the method for regenerating a member of the present invention, the member can be accurately regenerated up to a state that does not adversely affect the crystal growth. By reusing such a member, the production of a Group 13 nitride semiconductor crystal is possible. Cost can be reduced.

The group 13 nitride semiconductor crystal manufacturing method of the present invention can be produced by using the member regenerated by the above-described member regenerating method of the present invention and / or the apparatus including the regenerated member. The growth method, raw materials, conditions, etc. are not particularly limited, and a known method such as a typical halide vapor phase growth method (HVPE method) can be appropriately employed as a method for producing a Group 13 nitride semiconductor crystal.
In particular, a production method including the following steps, that is, a production method using a liquid phase epitaxial growth method can be exemplified as a preferable one. In the liquid phase epitaxial growth method, the member is easily deteriorated and / or deteriorated through the liquid phase, so that the regeneration method of the present invention can be effectively used.
(1) A step of producing a solution or melt containing a raw material and a solvent (2) A growth step of epitaxially growing a periodic table group 13 metal nitride semiconductor crystal in the solution or melt

  (1) The step of preparing a solution or melt containing a raw material and a solvent means a step of preparing a solution or melt for liquid phase used for epitaxial growth as a pre-stage of the growth step, and (2) solution Alternatively, the growth step of epitaxially growing the periodic table group 13 metal nitride semiconductor crystal in the melt means a growth step using a liquid phase epitaxial growth method. Specifically, the growth process using the liquid phase epitaxial method includes a temperature difference (Gradient Transport) method, a slow cooling method, a temperature cycling method, which are mainly used in the flux method, An accelerated crucible rotation technique, a top-seed solution growth method, a solvent transfer method and a variation thereof, a traveling-solvent floating-zone method, an evaporation method, etc. The method which combined these methods arbitrarily is mentioned. The details of these steps are not particularly limited and can be carried out by appropriately adopting known conditions, but the reaction vessel, stirring blade, seed crystal holding rod, seed crystal holding table, baffle, used in these steps, As the members such as the gas introduction pipe and the valve, those regenerated using the member regenerating method of the present invention are used. The solution or melt containing the raw material and the solvent does not need to be completely dissolved in the solvent, and may be a heterogeneous system in which the solid raw material is dispersed or present in the solution as a solid. In addition, the “liquid phase that is a solution or melt” in the growth step is not necessarily intended to be the same as the “solution or melt” in the step of producing the solution or melt. The “solution or melt” in the process of preparing the solution or melt is prepared for use in the growth process, but the “solution or melt” in the growth process includes a by-product generated by the reaction of epitaxial growth. This is because the composition may not be the same as the initial composition (before the start of epitaxial growth).

  As long as the production method of the present invention is performed using a member regenerated by the method for regenerating a member of the present invention and / or an apparatus including the regenerated member, the conditions in the growth step of (2) are particularly limited. However, as described above, under the condition where a component containing a hydrogen element exists in the reaction system, the member may take in hydrogen and adversely affect the crystal growth. Therefore, it is particularly effective in the manufacturing method having such a condition. It is. Below, the manufacturing method of the liquid phase epitaxial method in which hydrogen exists in a reaction system is mentioned as an example.

FIG. 2 is a conceptual diagram of a production apparatus used in a production method of a liquid phase epitaxial method in which hydrogen is present in the reaction system. In FIG. 2, 204 represents a reaction vessel, 201 represents a Li ₃ GaN ₂ composite nitride (solid) as a raw material, 202 represents a LiCl molten salt as a solvent, and 200 represents a gallium nitride crystal as a seed crystal. This manufacturing method is characterized in that hydrogen is contained in the gas phase, and crystal growth is performed using such hydrogen. (The gas phase also contains nitrogen)

In the growth process of such a manufacturing method, Li ₃ GaN ₂ composite nitride partially dissolved in the liquid phase reaches the surface of the seed crystal that is also present in the liquid phase, and the reaction represented by the following reaction formula [3] is performed. Wake up and crystal growth proceeds.

In addition, hydrogen and nitrogen in the gas phase are dissolved directly or in the liquid phase to hydrogenate and / or nitride the Li ₃ N produced by the above formula [3], thereby lithium hydride, lithium imide, or lithium An amide is formed. For example, lithium amide (LiNH ₂ ) is produced by a reaction represented by the following formula [4]. An increase in the Li ₃ N concentration in the vicinity of the gallium nitride crystal causes a decrease in the growth rate, and an abrupt decrease in the Li ₃ N concentration also leads to rapid GaN formation, leading to the generation of miscellaneous crystals and a decrease in crystallinity. Hydrogen and nitrogen play a role in appropriately controlling the growth rate, and are particularly important for obtaining a semiconductor crystal having high crystallinity. Note that the reactions that generate lithium hydride, lithium imide, and lithium amide are all equilibrium reactions, and Li ₃ N depends on the concentration of hydrogen and nitrogen.
The concentration can be adjusted.

[material]
The raw material used in the production method of the present invention can be appropriately set according to the target group 13 nitride semiconductor crystal. For example, as in the above-described Li ₃ GaN ₂ composite nitride, A compound nitride containing a Group 13 metal and a Group 1 metal and / or a Group 2 metal of the periodic table can be exemplified as a preferable example. In addition to Ga, Group 13 metals include Al, In, GaAl, GaIn, etc., and Group 1 metals and / or Group 2 metals include Na, Ca, Sr, Ba, Mg, etc., in addition to Li. Can be mentioned. As a composite nitride containing a Group 13 metal and a Group 1 metal and / or a Group 2 metal, in addition to Li ₃ GaN ₂ , Ca ₃ Ga ₂ N ₄ , B
_{a 3 Ga 2 N 4, Mg} 3 GaN 3, and the like. The composite nitride containing Group 13 metal and Group 1 metal and / or Group 2 metal is, for example, Group 13 metal nitride powder and Group 1 metal and / or Group 2 metal nitride powder. (For example, Li ₃ N, Ca ₃ N ₂ ), and then the temperature is raised to cause a solid phase reaction; an alloy containing a Group 13 metal and a Group 1 metal and / or a Group 2 metal is prepared. , A method of heating in a nitrogen atmosphere; For example, Li ₃ Ga
N ₂ can be manufactured by heat-treating a Ga—Li alloy at 600 to 800 ° C. in a nitrogen atmosphere.

  As a raw material other than the composite nitride containing the Group 13 metal and the Group 1 metal and / or the Group 2 metal, the Group 13 metal nitride itself can be used. In addition, for example, a mixed nitride film synthesized by reacting with nitrogen plasma by a reactive sputtering method using a target made of an alloy of a Group 13 metal and a Group 1 metal and / or a Group 2 metal may be mentioned. it can. Such a mixed nitride film is suitable when a nitride that is difficult to synthesize chemically is used.

  When the raw material is a solid under the conditions in the growth process, such a solid raw material need not be completely dissolved in the solvent. Even when a part is not dissolved but is present in the reaction vessel, the amount consumed by crystal growth is supplied to the solvent as needed. Further, the amount of the raw material with respect to the solvent is not particularly limited and can be appropriately set according to the purpose, but if it is within the range of 5 to 50% by weight, the efficiency for continuous production can be improved. Space in the reaction vessel can be secured.

[solvent]
Although the solvent used for the manufacturing method of this invention is not specifically limited, The solvent which has a metal salt as a main component is preferable. The content of the metal salt is preferably 50% by weight or more, more preferably 70% by weight or more, and still more preferably 90% by weight or more. In particular, a molten salt obtained by melting a metal salt is preferably used as a solvent.

The type of the metal salt is not particularly limited as long as it does not inhibit crystal growth, but alkali metal such as Li, Na, K and / or alkaline earth metal halide such as Mg, Ca, Sr, carbonate, Examples thereof include nitrates and sulfurates. _{Specifically, LiCl, KCl, NaCl, CaCl} 2, BaCl 2, CsCl, LiBr, KBr, CsBr, LiF, KF, NaF, LiI, NaI, metal halides such as CaI _2, BaI ₂ preferably, LiCl, KCl, NaCl, CsCl, CaCl ₂ and BaCl ₂ are more preferable. The type of metal salt is not limited to one type, and a plurality of types of metal salts may be used in appropriate combination. Among these, it is more preferable to use lithium halide and a metal salt other than this together. The content of lithium halide is preferably 30% or more, more preferably 80% or more, based on the total amount of the metal salt.

In order to increase the solubility of a composite nitride containing a Group 13 metal and a Group 1 metal and / or a Group 2 metal element, for example, Li ₃ N, Ca ₃ N ₂ , Mg ₃ N ₂ , It is preferable that a nitride of alkali metal or alkaline earth metal such as Sr ₃ N ₂ or Ba ₃ N ₂ is contained in the solvent.

  Metal salts generally have a high hygroscopic property and therefore contain a large amount of moisture. In order to produce the Group 13 nitride semiconductor crystal of the present invention, it is necessary to remove impurities that can be an oxygen source such as moisture as much as possible, that is, it is preferable to purify the solvent in advance. Although the purification method is not particularly limited, for example, a method in which a reactive gas is blown into a solvent using an apparatus described in JP-A-2007-084422 can be mentioned. For example, when a metal salt that is solid at room temperature is used as a solvent, it is melted by heating to hydrogen chloride, hydrogen iodide, hydrogen bromide, ammonium chloride, ammonium bromide, ammonium iodide, chlorine, bromine, or iodine. Impurities such as moisture can be removed by bubbling with a reactive gas such as. It is particularly preferable to use hydrogen chloride for the molten salt of chloride.

[Seed crystal (underlying substrate)]
In order to obtain an industrially sufficient crystal, it is preferable to install a seed crystal in the liquid phase in which the epitaxial growth proceeds. The seed crystal is the same type as the target group 13 nitride crystal such as GaN, InGaN, AlGaN, etc., metal oxide such as sapphire, ZnO, BeO, silicon-containing material such as SiC, Si, or GaAs Etc. can be used. Considering the consistency with the Group 13 nitride semiconductor crystal grown in the present invention, the Group 13 nitride is most preferable. The shape of the seed crystal is not particularly limited, and may be a flat plate shape or a rod shape. In the case of using a rod-shaped seed crystal, it is possible to produce a bulk crystal by first growing in the seed crystal portion and then performing crystal growth in the vertical direction while also performing crystal growth in the horizontal direction. In order to efficiently grow the group 13 nitride semiconductor crystal on the seed crystal, it is preferable that no miscellaneous crystal is grown or attached around the seed crystal. A miscellaneous crystal is a crystal having a small particle diameter that grows other than on the seed crystal. When the miscellaneous crystal exists near the seed crystal, the group 13 nitride component in the liquid phase is grown on the seed crystal and the growth of the miscellaneous crystal. As a result, the growth rate of the group 13 nitride semiconductor crystal on the seed crystal cannot be sufficiently obtained.

[Temperature, pressure and other conditions]
The temperature at which the Group 13 nitride crystal is grown in the reaction vessel is usually 200 to 1000 ° C, preferably 400 to 850 ° C, more preferably 600 to 800 ° C. Further, the pressure in the reaction vessel when growing the Group 13 metal nitride crystal can be appropriately selected depending on the conditions and is not particularly limited. However, since the production apparatus is simple and can be produced industrially advantageously, It is 10 MPa or less, preferably 3 MPa or less, more preferably 0.3 MPa or less, more preferably 0.11 MPa or less, and usually 0.01 MPa or more, more preferably 0.09 MPa or more.

The hydrogen in the growth step may be sequentially supplied into the gas phase or a necessary amount may be prepared in advance in the reaction vessel, but it is preferable to supply hydrogen in the gas phase in succession. the gas flow rate typically 0.1~10000cm ³ / min in an amount in terms of normal temperature and normal pressure, preferably 1~5000cm ³ / min, more preferably 10~1000cm ³ / min. Nitrogen in the growth step may be sequentially supplied into the gas phase or a necessary amount may be prepared in advance in the reaction vessel. However, it is preferable to supply nitrogen sequentially in the gas phase. the flow rate of nitrogen gas usually 0.1~10000cm ³ / min in an amount in terms of normal temperature and normal pressure, preferably 1~5000cm ³ / min, more preferably 10~1000cm ³ / min. When the flow rates of hydrogen and nitrogen are in the above ranges, the concentration of by-products can be kept moderate. The hydrogen concentration in the gas phase is usually 0.001 to 99.9 mol%, preferably 0.1 to 99 mol%, more preferably 1 to 90 mol%, and the flow rates of hydrogen and nitrogen are appropriately adjusted so as to fall within this concentration range. Can be adjusted.

  In order to uniformly distribute hydrogen dissolved from the gas phase to the liquid phase in the solution or melt, it is desirable to stir the solution or melt. The stirring method is not particularly limited, but is a method of rotating and stirring the substrate, a method of rotating and stirring the stirring blade, a method of stirring by giving a flow by bubbling gas into the solution or melt, and a liquid feed pump And a method of creating a flow and stirring.

  The growth rate of crystal growth can be adjusted by the temperature, pressure, etc., and is not particularly limited, but is usually in the range of 0.1 μm / h to 1000 μm / h, preferably 1 μm / h or more, and 10 μm / h. h or higher is more preferable, and 100 μm / h or higher is further preferable.

  The group 13 metal nitride crystal according to the present invention can be used for various applications. In particular, as a substrate for manufacturing a light emitting element on a relatively short wavelength side such as an ultraviolet to blue light emitting diode or a semiconductor laser, and a light emitting element on a relatively long wavelength side of green to red, it is further used for a semiconductor device such as an electronic device. It is also useful as a substrate.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

<Reference Example 1>
(Member film formation process (nitriding process))
The film forming process described below will be described with reference to FIG.
(1) Li ₃ GaN ₂ 1.5 which is a raw material (nitriding agent) 101 having a nitriding action in a reaction vessel 103 made of Ti (outer diameter 34 mm, inner diameter 30 mm, height 200 mm) in an Ar box.
g, and 15.0 g of LiCl as the solvent 102 were sequentially added.
(2) The reaction vessel 103 made of Ti was put into the reaction tube 104 made of quartz, and this was taken out from the Ar box.
(3) After the quartz reaction tube 104 was fixed to the electric furnace 109, the pressure inside the quartz reaction tube was reduced to less than 0.1 Torr through the gas introduction tube 108 using a vacuum pump.
(4) The valve 107 is opened, N ₂ gas is introduced from the gas introduction pipe 108, the inside of the quartz reaction pipe is set to the N ₂ atmosphere, the valve 106 is opened, and N ₂ gas is supplied through the gas exhaust pipe 105 to 100.
It was distributed at ccm / min.
(5) Using an electric furnace 109, the temperature inside the Ti reaction vessel 103 is raised from room temperature to 750 ° C. over 1 hour, and after melting LiCl, the temperature is maintained at 745 ° C. for 60 hours. The inner wall surface of the reaction vessel 103 was nitrided.
(6) After nitriding, the heating by the electric furnace 109 was stopped and naturally cooled, and the Ti reaction vessel 103 having the inner wall surface nitrided was taken out from the quartz reaction tube 104.
(7) LiCl adhering to the inside of the reaction vessel was dissolved in warm water, the inside of the reaction vessel was washed with pure water, and then the vessel was dried. It was confirmed that strong nitride was formed on the inner wall surface of the Ti reaction vessel 103 and there was no corrosion.

(Measurement of chromaticity of members after film formation (after nitriding))
After the formation of the coating (after nitriding treatment), the container bottom of the Ti reaction vessel 103 is cut out, and the portion of the nitride formed by the cross-light photometry method using a colorimetric color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd.) When the chromaticity was measured, the L ^* value was 53.36, the a ^* value was 8.53, and the b ^* value was 30.82.

(Crystal growth process)
The crystal growth process described below will be described with reference to FIG.
(1) A Ti reaction vessel 204 (outer diameter 34 mm, inner diameter 30 mm, height 200 mm) in which a film (nitride layer) is separately formed by the same method as in the film formation step (nitriding treatment step) is placed in an Ar box. In a Ti reaction vessel 204, Li ₃ G, which is a raw material 201 for GaN crystal growth, is placed.
1.44 g of aN ₂ and 14.4 g of LiCl as the solvent 202 were sequentially added.
(2) A Ti reaction vessel 204 is placed in a quartz reaction tube 205, a tungsten (W) seed crystal holding rod 208 and a Ta wire 203 using a GaN seed crystal 200 (length 5 mm × width 10 mm, thickness). After connecting 300 μm (non-polar surface) to the reaction tube 205 made of quartz, the reaction tube 205 made of quartz was taken out from the Ar box.
(3) After fixing the quartz reaction tube 205 to the electric furnace 211, the quartz reaction tube was evacuated to less than 0.1 Torr through the gas introduction tube 210 using a vacuum pump.
(4) Open the valve 209, introduce a H ₂ / N ₂ mixed gas with an H ₂ concentration of 10 vol% from the gas introduction pipe 210, and after returning the pressure in the quartz reaction tube, open the valve 207 and open the gas exhaust pipe 206. Then, a H ₂ / N ₂ mixed gas was circulated at 100 ccm / min.
(5) Using an electric furnace 211, the temperature of the Ti reaction vessel 204 is increased from room temperature to 745 ° C. over 1 hour to melt LiCl, and held at 745 ° C. for another 1 hour. Crystal 200 was placed in the melt. At that time, while rotating the seed crystal 200 through the seed crystal holding rod 208 at a speed of 100 rpm, the seed crystal 200 was held at 745 ° C. for 7 hours, and GaN crystal growth was performed on the seed crystal 200.
(6) After crystal growth, the seed crystal 200 on which the GaN crystal was grown was extracted from the melt, and heating by the electric furnace 211 was stopped, and then the quartz reaction tube 205 was naturally cooled.
(7) The seed crystal 200 was taken out from the quartz reaction tube 205, LiCl adhering to the surface was dissolved in warm water, washed with pure water, and then dried. When the weight of the seed crystal 200 after drying was measured, a weight increase of +3.4 mg was observed, and it was confirmed that the average crystal growth rate in the melt at a holding time of 7 hr was 37.8 μm / day. .

(Measurement of expansion coefficient of members)
When the same Ti reaction vessel 204 was used a plurality of times in the crystal growth method, GaN crystal growth on the seed crystal 200 hardly occurred when the accumulated usage time exceeded about 300 hours. At this time, when the height of the Ti reaction vessel 204 was measured, it was confirmed that the Ti reaction vessel was expanded to 204 mm (expansion rate 2.0%).

<Example 1>
The vacuum heat treatment process described below will be described with reference to FIG.
(Vacuum heat treatment process for members)
(1) The expanded Ti reaction vessel 301 (height 204 mm, weight 168.1249 g) shown in the reference example is placed in the quartz reaction tube 302, fixed to the electric furnace 304, and then using a vacuum pump. The quartz reaction tube was evacuated to less than 0.1 Torr through the gas introduction tube 303.
(2) While keeping the inside of the quartz reaction tube in a reduced pressure state, the electric furnace 304 is used to raise the temperature inside the Ti reaction vessel 301 from room temperature to 750 ° C. over 1 hour. The components absorbed in the Ti reaction vessel 301 were removed by performing vacuum heat treatment for a time. (3) After the vacuum heat treatment, heating by the electric furnace 304 was stopped, the quartz reaction tube 302 was naturally cooled, and the Ti reaction vessel 301 was taken out. When the height and weight of the Ti reaction vessel 301 were respectively measured, the height was 201 mm and the weight was 167.1320 g. The shrinkage of the Ti reaction vessel (expansion rate from 2.0% to 0.5%) accompanying the vacuum heat treatment. %) Was confirmed. It was confirmed that the Ti reaction vessel mainly absorbed hydrogen.

(Step of re-forming member film (re-nitriding step))
(1) A 35% hydrochloric acid aqueous solution is placed in the Ti reaction vessel 301 subjected to vacuum heat treatment, and this is heated and held at 100 ° C. for 3 hours on a hot plate to form nitridation formed on the inner surface of the Ti reaction vessel. The material layer was peeled off.
(2) This Ti reaction vessel 301 is purely washed and dried, and the inner surface of the Ti reaction vessel is again nitrided by the same method as the coating formation step (nitriding treatment step) shown in the reference example. It was.
As a result, it was confirmed that strong nitride was again formed on the inner wall surface.

(Crystal growth process)
When GaN crystal growth was performed under the same conditions as in the reference example using the Ti reaction vessel 301 that had been subjected to the above regeneration treatment, a weight increase of +5.4 mg was observed in the grown seed crystal. It was confirmed that the average crystal growth rate in the liquid at a holding time of 7 hr was 73.7 μm / day. As a result of the above, the Ti reaction vessel 301 that has expanded and the nitride layer formed on the inner wall surface has deteriorated is regenerated by vacuum heat treatment and film reforming treatment (renitridation treatment) on the inner wall surface, and grows GaN crystals. Was confirmed to be able to be implemented again.

(Measurement of chromaticity of parts after reclaiming)
The bottom of the Ti reaction vessel 301 after the regeneration treatment was cut out, and the chromaticity of the portion where the nitride was formed was measured by the cross-photometry method using a colorimetric color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd.). The L ^* value was 45.63, the a ^* value was 6.73, and the b ^* value was 31.04.

<Example 2>
(Process for re-forming member film and crystal growth process)
A Ti reaction vessel (height 203.9 mm, expansion rate 1.95%) having the same usage history as the Ti reaction vessel used in Example 1 and expanded in the same manner is shown in Example 1. A GaN crystal was grown under the same conditions as in the reference example using a Ti reaction vessel in which only a film re-forming process (renitriding process) was performed without performing vacuum heat treatment. As a result, a weight increase of +2.8 mg was observed in the seed crystal after growth, and it was confirmed that the average crystal growth rate in the melt at a holding time of 7 hr was 35.7 μm / day. Thereby, the Ti reaction vessel in which the nitride layer formed on the inner wall surface is expanded and deteriorated can be regenerated to some extent by only the film re-forming process (re-nitriding process) on the inner wall surface, so that the GaN crystal growth can be performed again. It was confirmed that

<Comparative Example 1>
(Crystal growth process)
Regeneration treatment as shown in the example for an expanded Ti reaction vessel (height after expansion: 202 mm, expansion rate: 1.0%) having the same usage history as the Ti reaction vessel used in Example 1 When GaN crystal growth was performed without applying any of the above, no GaN crystal growth on the seed crystal was observed.

(Measure chromaticity of deteriorated and / or deteriorated parts)
When the bottom of the modified and / or deteriorated Ti reaction vessel was cut out and the surface that had deteriorated and / or deteriorated was observed, it was duller than the color immediately after nitriding treatment, and when the chromaticity was measured, the L ^* value was The value was 29.22, the a ^* value was 4.67, and the b ^* value was 10.23. The L ^* value and the b ^* value are greatly different from the values immediately after the nitriding treatment, and it was confirmed that the inner wall surface was deteriorated.

From the results of Table 1, it was confirmed that when a reaction vessel (member) having a color value (L ^* value) of less than 40 and an expansion coefficient of 1.0% or more was used, crystal growth did not proceed sufficiently. (Comparative Example 1). On the other hand, when a reaction vessel (member) having a color value (L ^* value) of 40 or more and an expansion coefficient of less than 1.0% is used after being subjected to vacuum heat treatment and / or renitridation treatment, it is unused. It is clear that crystal growth proceeds at a high growth rate as in the case of using the reaction vessel in the state.

101 Raw material (Li ₃ GaN ₂ )
102 Melt or solvent (LiCl)
103 reaction vessel 104 quartz reaction tube 105 gas exhaust tube 106 valve 107 valve 108 gas introduction tube 109 electric furnace 200 seed crystal (GaN)
201 Raw material (Li ₃ GaN ₂ )
202 Melt or solvent (LiCl)
203 Ta wire 204 Reaction vessel 205 Quartz reaction tube 206 Gas exhaust tube 207 Valve 208 Tungsten seed crystal holding rod 209 Valve 210 Gas introduction tube 211 Electric furnace 301 Reaction vessel 302 Quartz reaction tube 303 Gas introduction tube 304 Electric furnace

Claims (12)

A method for regenerating a deteriorated and / or deteriorated member used in the production of a Group 13 metal nitride semiconductor crystal of the periodic table,
Preparatory process for preparing a member including an altered / degraded portion having a color value (L ^* value) of less than 40 and / or an expansion rate from an unused state of 1.0% or more, and the color of the altered / degraded portion A method for regenerating a member, comprising a treatment step in which a value (L ^* value) is 40 or more and / or an expansion coefficient is less than 1.0%. The method for regenerating a member according to claim 1, wherein the member includes at least one selected from Group 4 to 6 elements of the periodic table, Sc, Y, Ni, and Pd. The member is a metal or alloy containing at least one selected from Group 4 to 6 elements of the periodic table, Sc, Y, Ni and Pd, 90% by weight or more of which is constituted. Method for regenerating the member. The method for regenerating a member according to any one of claims 1 to 3, wherein the member has a film formed on a surface thereof. The method for regenerating a member according to claim 4, wherein the coating is a nitride containing at least one selected from Group 4 to 6 elements of the periodic table. The member according to any one of claims 1 to 5, wherein the member is at least one selected from a reaction vessel, a stirring blade, a seed crystal holding rod, a seed crystal holding table, a baffle, a gas introduction pipe, and a valve. Playback method. The method for regenerating a member according to any one of claims 1 to 6, wherein the treatment step includes a vacuum heat treatment. The method for regenerating a member according to any one of claims 4 to 7, wherein the treatment step includes a film re-formation treatment. The method for regenerating a member according to any one of claims 1 to 8, wherein the production of the Group 13 metal nitride semiconductor crystal of the periodic table is a production method in which a component containing a hydrogen element is present in a reaction system. A periodic table group 13 metal nitride semiconductor manufactured using a member regenerated by the method for regenerating a member according to claim 1 and / or an apparatus including the member. Crystal production method. The periodic table group 13 according to claim 10, comprising a step of producing a solution or melt containing a raw material and a solvent, and a growth step of epitaxially growing a periodic table group 13 metal nitride semiconductor crystal in the solution or melt. A method for producing a metal nitride semiconductor crystal, comprising:
The step of producing the melt or solution and / or the growth step is performed using a member regenerated by the method for regenerating a member according to any one of claims 1 to 8 and / or an apparatus including the member. A method for producing a Group 13 metal nitride semiconductor crystal of the periodic table. The manufacturing method of the periodic table group 13 metal nitride semiconductor crystal of Claim 10 or 11 with which the component containing a hydrogen element exists in a reaction system.

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