JP5032406B2 - Group III nitride crystal growth method - Google Patents

Group III nitride crystal growth method Download PDF

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JP5032406B2
JP5032406B2 JP2008186976A JP2008186976A JP5032406B2 JP 5032406 B2 JP5032406 B2 JP 5032406B2 JP 2008186976 A JP2008186976 A JP 2008186976A JP 2008186976 A JP2008186976 A JP 2008186976A JP 5032406 B2 JP5032406 B2 JP 5032406B2
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JP2010024089A (en
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康二 上松
昌紀 森下
晴子 田中
伸介 藤原
勇介 森
孝友 佐々木
史朗 川村
康夫 北岡
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Sumitomo Electric Industries Ltd
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Description

本発明は、液相法、特にフラックス法によるＩＩＩ族窒化物結晶の成長方法に関する。 The present invention, liquid phase method, relates to growth method of a group III nitride crystal according to particular flux method.

ＩＩＩ族窒化物結晶は、各種半導体デバイスの基板などに広く用いられている。近年、各種半導体デバイスを効率的に製造するために、大型で転位密度の低いＩＩＩ族窒化物結晶が求められている。   Group III nitride crystals are widely used for substrates of various semiconductor devices. In recent years, in order to efficiently manufacture various semiconductor devices, a large group III nitride crystal having a low dislocation density has been demanded.

ＩＩＩ族窒化物結晶を成長させる方法としては、ＨＶＰＥ（ハイドライド気相成長）法、ＭＯＣＶＤ（有機金属化学気相堆積）法などの気相法、高圧溶液法、フラックス法などの液相法などがある。ここで、液相法は、気相法に比べて、その結晶成長において有毒なガスを使用しないため環境保護の面で優れている。   As a method for growing a group III nitride crystal, there are a gas phase method such as HVPE (hydride vapor phase epitaxy) method, MOCVD (metal organic chemical vapor deposition) method, a liquid phase method such as high pressure solution method and flux method. is there. Here, the liquid phase method is superior to the gas phase method in terms of environmental protection because no toxic gas is used in crystal growth.

かかる液相法においてＩＩＩ族窒化物結晶を成長させる方法として、国際公開ＷＯ２００５／１０３３４１号パンフレット（特許文献１）は、ＩＩＩ族元素と、窒素と、アルカリ金属およびアルカリ土類金属の少なくとも一方とを含む結晶原料液を用いて、ＩＩＩ族窒化物結晶を成長させる装置および方法を開示する。
国際公開ＷＯ２００５／１０３３４１号パンフレット（特許文献１）に開示されているＩＩＩ族窒化物結晶の製造装置は、結晶原料液を配置するための反応容器と、反応容器を収容する耐圧容器と、この反応容器に窒素含有ガスを供給するための窒素含有ガス供給装置と、この窒素含有ガス供給装置から反応容器に窒素含有ガスを導入する配管と、反応容器から耐圧容器に窒素含有ガスを排出する配管と、を備え、反応容器に導入された窒素含有ガスのうちＩＩＩ族窒化物結晶の成長により消費されなかった窒素含有ガスが反応容器から排出される構造を有する装置である。 As a method for growing a group III nitride crystal in such a liquid phase method, International Publication WO2005 / 103341 (Patent Document 1) discloses a group III element, nitrogen, and at least one of an alkali metal and an alkaline earth metal. Disclosed is an apparatus and a method for growing a group III nitride crystal using a crystal raw material liquid containing the same.
An apparatus for producing a group III nitride crystal disclosed in International Publication WO2005 / 103341 (Patent Document 1) includes a reaction vessel for placing a crystal raw material liquid, a pressure vessel containing the reaction vessel, and this reaction. A nitrogen-containing gas supply device for supplying the nitrogen-containing gas to the vessel, a pipe for introducing the nitrogen-containing gas from the nitrogen-containing gas supply device to the reaction vessel, and a pipe for discharging the nitrogen-containing gas from the reaction vessel to the pressure vessel The nitrogen-containing gas that has not been consumed by the growth of the group III nitride crystal among the nitrogen-containing gas introduced into the reaction vessel is discharged from the reaction vessel.

すなわち、国際公開ＷＯ２００５／１０３３４１号パンフレット（特許文献１）に開示されているＩＩＩ族窒化物結晶の製造装置においては、室温に配置されている窒素含有ガス供給装置から十分に加熱された反応容器内の結晶原料液に窒素含有ガスが供給されるため、結晶原料液の温度が変動する。また、反応容器内部ではアルカリ金属の一部が気化しており、その蒸気が窒素含有ガスの供給ならびに排出に伴い、反応容器の内部から外部へと漏れ出す。そのため、結晶原料液の液量が変動する。かかる結晶原料液の温度および液量の変動により、高品質のＩＩＩ族窒化物結晶を安定して成長させることが困難であるという問題点がある。
国際公開ＷＯ２００５／１０３３４１号パンフレット That is, in the III-nitride crystal manufacturing apparatus disclosed in the pamphlet of International Publication WO2005 / 103341 (Patent Document 1), the inside of a reaction vessel sufficiently heated from a nitrogen-containing gas supply apparatus arranged at room temperature. Since the nitrogen-containing gas is supplied to the crystal raw material liquid, the temperature of the crystal raw material liquid varies. Further, a part of the alkali metal is vaporized inside the reaction vessel, and the vapor leaks from the inside of the reaction vessel to the outside with the supply and discharge of the nitrogen-containing gas. Therefore, the liquid amount of the crystal raw material liquid varies. There is a problem that it is difficult to stably grow a high-quality group III nitride crystal due to variations in the temperature and amount of the crystal raw material liquid.
International Publication WO2005 / 103341 Pamphlet

本発明は、上記ＩＩＩ族窒化物結晶の製造装置の問題点を解決して、高品質のＩＩＩ族窒化物結晶を安定して成長させることができるＩＩＩ族窒化物結晶の成長方法を提供することを目的とする。 The present invention is to solve the problems of the manufacturing device for the Group III nitride crystal, the growth method of a group III nitride crystal of high quality III-nitride crystal can be grown stably For the purpose.

本発明は、ＩＩＩ族金属とアルカリ金属とを含む溶媒を収容する反応容器と、反応容器を収容する耐圧容器と、反応容器および耐圧容器に窒素含有ガスを供給する窒素含有ガス供給装置と、窒素含有ガス供給装置から耐圧容器に窒素含有ガスを導入する第１配管と、第１配管の途中の第１部分から反応容器に窒素含有ガスを導入する第２配管と、を備える成長装置を用いたＩＩＩ族窒化物結晶の成長方法であって、反応容器にＩＩＩ族金属とアルカリ金属とを含む溶媒を収容する工程と、反応容器に窒素含有ガスを供給してＩＩＩ族窒化物結晶を成長させる工程と、を備え、ＩＩＩ族窒化物結晶を成長させる工程において、ＩＩＩ族窒化物結晶の成長により消費された量の窒素含有ガスを供給するＩＩＩ族窒化物結晶の成長方法である。 The present invention relates to a reaction vessel containing a solvent containing a Group III metal and an alkali metal, a pressure vessel containing the reaction vessel, a nitrogen-containing gas supply device for supplying a nitrogen-containing gas to the reaction vessel and the pressure vessel, nitrogen A growth apparatus comprising a first pipe for introducing a nitrogen-containing gas from a contained gas supply device into a pressure-resistant vessel and a second pipe for introducing a nitrogen-containing gas into a reaction vessel from a first part in the middle of the first pipe was used. A method for growing a group III nitride crystal, the step of containing a solvent containing a group III metal and an alkali metal in a reaction vessel, and the step of growing a group III nitride crystal by supplying a nitrogen-containing gas to the reaction vessel And in the step of growing a group III nitride crystal, a method for growing a group III nitride crystal is provided in which an amount of nitrogen-containing gas consumed by the growth of the group III nitride crystal is supplied.

本発明にかかるＩＩＩ族窒化物結晶の成長方法において、反応容器に窒素含有ガスを供給して反応容器を所定の内圧とした後に、耐圧容器に窒素含有ガスを供給することができる。また、反応容器の内圧を耐圧容器の内圧に比べて高くすることができる。また、窒素含有ガスにより、反応容器の内圧および前記耐圧容器の内圧を制御することができる。   In the group III nitride crystal growth method according to the present invention, the nitrogen-containing gas can be supplied to the pressure-resistant vessel after the nitrogen-containing gas is supplied to the reaction vessel to bring the reaction vessel to a predetermined internal pressure. Moreover, the internal pressure of the reaction vessel can be made higher than the internal pressure of the pressure vessel. Further, the internal pressure of the reaction vessel and the internal pressure of the pressure vessel can be controlled by the nitrogen-containing gas.

また、本発明は、ＩＩＩ族金属とアルカリ金属とを含む溶媒を収容する反応容器と、反応容器を収容する耐圧容器と、反応容器および耐圧容器に窒素含有ガスを供給する窒素含有ガス供給装置と、窒素含有ガス供給装置から耐圧容器に窒素含有ガスを導入する第１配管と、第１配管の途中の第１部分から反応容器に窒素含有ガスを導入する第２配管と、耐圧容器からガスを排出する第３配管と、第３配管の途中の部分に配置された圧力調整器と、第１配管の窒素含有ガス供給装置と第１部分との間の部分に配置されたガス流量調整器と、を備える成長装置を用いたＩＩＩ族窒化物結晶の成長方法であって、反応容器にＩＩＩ族金属とアルカリ金属とを含む溶媒を収容する工程と、反応容器に窒素含有ガスを供給してＩＩＩ族窒化物結晶を成長させる工程と、を備え、ＩＩＩ族窒化物結晶を成長させる工程において、ＩＩＩ族窒化物結晶の成長により消費された量の窒素含有ガスを供給し、窒素含有ガスにより、圧力調整器と、ガス流量調整器とを用いて、反応容器の内圧および耐圧容器の内圧が制御されているＩＩＩ族窒化物結晶の成長方法である。 The present onset Ming, III metals and a reaction vessel containing a solvent containing an alkali metal, a pressure vessel for accommodating the reaction vessel, the nitrogen-containing gas supply device for supplying a nitrogen-containing gas to the reaction vessel and pressure vessel A first pipe for introducing nitrogen-containing gas into the pressure vessel from the nitrogen-containing gas supply device, a second pipe for introducing nitrogen-containing gas into the reaction vessel from the first part in the middle of the first pipe, and gas from the pressure vessel The third pipe for discharging the gas, the pressure regulator arranged in the middle part of the third pipe, and the gas flow regulator arranged in the part between the nitrogen-containing gas supply device and the first part of the first pipe A method of growing a group III nitride crystal using a growth apparatus comprising: a step of containing a solvent containing a group III metal and an alkali metal in a reaction vessel; and supplying a nitrogen-containing gas to the reaction vessel Growing group III nitride crystals Comprising a step of, a, in the process of growing the Group III nitride crystal, to supply the amount of nitrogen-containing gas consumed by the growth of the group III nitride crystal, the nitrogen-containing gas, a pressure regulator, gas by using the flow regulator, a growing method of a group III nitride crystal the internal pressure of the inner pressure and resistant vessel anti reaction container unit is controlled.

本発明によれば、高品質のＩＩＩ族窒化物結晶を安定して成長させることができるＩＩＩ族窒化物結晶の成長方法を提供することができる。 According to the present invention, it is possible to provide a growth method of a group III nitride crystal of high quality III-nitride crystal can be grown stably.

（実施形態１）
図１を参照して、本発明にかかるＩＩＩ族窒化物結晶の成長装置の一実施形態は、液相法によるＩＩＩ族窒化物結晶の成長装置であって、ＩＩＩ族金属とアルカリ金属とを含む溶媒１３２を収容する反応容器１２０と、反応容器１２０を収容する耐圧容器１１０と、反応容器１２０および耐圧容器１１０に窒素含有ガスを供給する窒素含有ガス供給装置１８０と、窒素含有ガス供給装置１８０から耐圧容器１１０に窒素含有ガスを導入する第１配管１２２と、第１配管１２２の途中の第１部分１２２ｓから反応容器１２０に窒素含有ガスを導入する第２配管１２４とを、備える。 (Embodiment 1)
Referring to FIG. 1, one embodiment of a group III nitride crystal growth apparatus according to the present invention is a group III nitride crystal growth apparatus by a liquid phase method, and includes a group III metal and an alkali metal. From the reaction vessel 120 containing the solvent 132, the pressure vessel 110 containing the reaction vessel 120, the nitrogen-containing gas supply device 180 supplying nitrogen-containing gas to the reaction vessel 120 and the pressure vessel 110, and the nitrogen-containing gas supply device 180 A first pipe 122 for introducing a nitrogen-containing gas into the pressure vessel 110 and a second pipe 124 for introducing the nitrogen-containing gas into the reaction vessel 120 from the first portion 122 s in the middle of the first pipe 122 are provided.

本実施形態のＩＩＩ族窒化物結晶の成長装置を用いることにより、ＩＩＩ族金属とアルカリ金属とを含む溶媒の温度および液量の変動を抑制して、高品質のＩＩＩ族窒化物結晶を安定して成長させることができる。   By using the group III nitride crystal growth apparatus of the present embodiment, it is possible to suppress variations in the temperature and liquid volume of a solvent containing a group III metal and an alkali metal, and to stabilize a high quality group III nitride crystal. Can grow.

図１を参照して、本実施形態のＩＩＩ族窒化物結晶の成長装置は、ＩＩＩ族金属とアルカリ金属を含む溶媒１３２を収容する反応容器１２０を備える。反応容器１２０内に溶媒１３２を直接配置しても、反応容器１２０内に坩堝１３０を配置してその坩堝１３０内に溶媒１３２を配置してもよい。この反応容器１２０は、反応容器本体１２０ａと反応容器蓋１２０ｂとで形成されており、反応容器本体１２０ａから反応容器蓋１２０ｂを開閉することにより、反応容器１２０に溶媒１３２、坩堝１３０などを出し入れすることができる。   Referring to FIG. 1, the group III nitride crystal growth apparatus of this embodiment includes a reaction vessel 120 that contains a solvent 132 containing a group III metal and an alkali metal. The solvent 132 may be arranged directly in the reaction vessel 120, or the crucible 130 may be arranged in the reaction vessel 120 and the solvent 132 may be arranged in the crucible 130. The reaction vessel 120 is formed of a reaction vessel main body 120a and a reaction vessel lid 120b. By opening and closing the reaction vessel lid 120b from the reaction vessel main body 120a, the solvent 132, the crucible 130 and the like are taken in and out of the reaction vessel 120. be able to.

反応容器本体１２０ａおよび反応容器蓋１２０ｂの材料は、耐熱性および機械的強度が高いものであれば特に制限はなく、ステンレス、耐熱鋼などが好ましく挙げられる。また、坩堝１３０の材料は、溶媒１３２および窒素含有ガスと反応せず、耐熱性および機械的強度が高いものであれば特に制限はなく、酸化アルミニウム（Ａｌ2Ｏ3）、単結晶サファイア、窒化ホウ素（ＢＮ）、熱分解窒化ホウ素（ＰＢＮ）、タングステン（Ｗ）、タンタル（Ｔａ）、酸化イットリウム（Ｙ2Ｏ3）、酸化カルシウム（ＣａＯ）、酸化マグネシウム（ＭｇＯ）などが好ましく挙げられる。 The materials for the reaction vessel main body 120a and the reaction vessel lid 120b are not particularly limited as long as they have high heat resistance and mechanical strength, and stainless steel, heat resistant steel, and the like are preferable. The material of the crucible 130 is not particularly limited as long as it does not react with the solvent 132 and the nitrogen-containing gas and has high heat resistance and high mechanical strength. Aluminum oxide (Al 2 O 3 ), single crystal sapphire, nitriding Preferred examples include boron (BN), pyrolytic boron nitride (PBN), tungsten (W), tantalum (Ta), yttrium oxide (Y 2 O 3 ), calcium oxide (CaO), and magnesium oxide (MgO).

また、本実施形態のＩＩＩ族窒化物結晶の成長装置において、反応容器１２０の周囲には反応容器１２０の内部を加熱するための加熱器１１２が配設されている。かかる加熱器１１２としては、特に制限はなく、Ｎｉ−Ｃｒ合金（ニクロム合金）、Ｆｅ−Ｃｒ−Ａｌ合金（カンタル合金）、ＳｉＣなどの電気を流すと熱を発する発熱体などが挙げられる。また、加熱器１１２の周囲には断熱材１１４が配設されている。かかる断熱材１１４の材料は、特に制限はなく、セラミックウール（たとえば、イソライト工業社製イソウール）などが挙げられる。   In the group III nitride crystal growth apparatus of this embodiment, a heater 112 for heating the inside of the reaction vessel 120 is disposed around the reaction vessel 120. There is no restriction | limiting in particular as this heater 112, The heat generating body etc. which generate | occur | produce heat when electricity, such as Ni-Cr alloy (nichrome alloy), Fe-Cr-Al alloy (kanthal alloy), and SiC, are flowed. A heat insulating material 114 is disposed around the heater 112. There is no restriction | limiting in particular in the material of this heat insulating material 114, For example, ceramic wool (For example, Isolite Kogyo isowool) etc. are mentioned.

また、本実施形態のＩＩＩ族窒化物結晶の成長装置は、反応容器１２０、加熱器１１２および断熱材１１４を収容する耐圧容器１１０を備える。この耐圧容器１１０は、耐圧容器本体１１０ａと耐圧容器蓋１１０ｂとで形成されており、耐圧容器本体１１０ａから耐圧容器蓋１１０ｂを開閉することにより、耐圧容器１１０に反応容器１２０などを出し入れすることができる。耐圧容器本体１１０ａおよび耐圧容器蓋１１０ｂの材料は、熱性および機械的強度が高いものであれば特に制限はなく、ステンレス、耐熱鋼などが好ましく挙げられる。   Further, the group III nitride crystal growth apparatus of the present embodiment includes a pressure vessel 110 that houses a reaction vessel 120, a heater 112, and a heat insulating material 114. The pressure vessel 110 is formed of a pressure vessel body 110a and a pressure vessel lid 110b, and the reaction vessel 120 and the like can be taken in and out of the pressure vessel 110 by opening and closing the pressure vessel lid 110b from the pressure vessel body 110a. it can. The material of the pressure vessel main body 110a and the pressure vessel lid 110b is not particularly limited as long as it has high heat resistance and mechanical strength, and stainless steel, heat resistant steel and the like are preferable.

また、本実施形態のＩＩＩ族窒化物結晶の成長装置は、反応容器１２０および耐圧容器１１０に窒素含有ガスを供給する窒素含有ガス供給装置１８０を備える。窒素含有ガス供給装置１８０は、窒素含有ガスを供給できるものであれば特に制限はなく、ガスボンベ、コンプレッサなどが好ましく挙げられる。   Further, the group III nitride crystal growth apparatus of this embodiment includes a nitrogen-containing gas supply device 180 that supplies a nitrogen-containing gas to the reaction vessel 120 and the pressure vessel 110. The nitrogen-containing gas supply device 180 is not particularly limited as long as it can supply a nitrogen-containing gas, and a gas cylinder, a compressor, and the like are preferable.

また、本実施形態のＩＩＩ族窒化物結晶の成長装置は、窒素含有ガス供給装置１８０から耐圧容器１１０に窒素含有ガスを導入する第１配管１２２を備える。かかる第１配管１２２により、耐圧容器１１０への窒素含有ガスの導入が可能となる。ここで、第１配管１２２のガス出口１２２ｅ付近にはバルブ１２２ｖが配置されている。かかるバルブ１２２ｖの開閉により耐圧容器１１０への窒素含有ガスの導入が調節される。   Further, the group III nitride crystal growth apparatus of the present embodiment includes a first pipe 122 that introduces a nitrogen-containing gas from the nitrogen-containing gas supply apparatus 180 to the pressure vessel 110. With this first pipe 122, the nitrogen-containing gas can be introduced into the pressure vessel 110. Here, a valve 122v is disposed near the gas outlet 122e of the first pipe 122. The introduction of the nitrogen-containing gas into the pressure vessel 110 is adjusted by opening and closing the valve 122v.

また、本実施形態のＩＩＩ族窒化物結晶の成長装置は、第１配管１２２の途中の第１部分１２２ｓから反応容器１２０に窒素含有ガスを導入する第２配管１２４を備える。かかる第２配管１２４により、反応容器１２０への窒素含有ガスの導入が可能となる。   Further, the group III nitride crystal growth apparatus of the present embodiment includes a second pipe 124 for introducing a nitrogen-containing gas into the reaction vessel 120 from the first portion 122 s in the middle of the first pipe 122. The second pipe 124 can introduce the nitrogen-containing gas into the reaction vessel 120.

ここで、第２配管１２４は、その一端が反応容器１２０（さらに具体的には反応容器蓋１２０ｂ）に接続して固定されており、その他端が接続部１２４ｃによって第１配管１２２の第１部分１２２ｓに接続されている。また、第２配管１２４の反応容器１２０と接続部１２４ｃとの間にはバルブ１２４ｖが配置されている。これにより、反応容器１２０に固定されている第２配管１２４と第１配管１２２との分離および接続が可能となり、耐圧容器１１０外で反応容器１２０内にＩＩＩ族金属およびアルカリ金属を含む溶媒１３２を配置した後、反応容器１２０を耐圧容器１１０内に配置することができる。   Here, one end of the second pipe 124 is connected and fixed to the reaction vessel 120 (more specifically, the reaction vessel lid 120b), and the other end is connected to the first portion of the first pipe 122 by the connecting portion 124c. 122s. Further, a valve 124v is disposed between the reaction vessel 120 and the connection portion 124c of the second pipe 124. As a result, the second pipe 124 and the first pipe 122 fixed to the reaction vessel 120 can be separated and connected, and the solvent 132 containing a group III metal and an alkali metal is placed inside the reaction vessel 120 outside the pressure vessel 110. After placement, the reaction vessel 120 can be placed in the pressure vessel 110.

本実施形態のＩＩＩ族窒化物結晶の成長装置においては、反応容器１２０には、窒素含有ガスを導入するための第２配管１２４が接続されているが、反応容器１２０からガスを排出する配管はない。このため、溶媒１３２から気化したアルカリ金属の蒸気が反応容器１２０から外部に漏れることがなく、溶媒１３２の液量の変動が抑制される。また、反応容器１２０内の窒素含有ガスの圧力を制御することにより、ＩＩＩ族窒化物結晶の成長により消費された量の窒素含有ガスを第２配管１２４から導入することが可能となる。このため、溶媒１３２の温度の変動が抑制される。このように、溶媒１３２の温度および液量の変動が抑制されるため、高品質のＩＩＩ族窒化物結晶を安定して成長させることができる。   In the group III nitride crystal growth apparatus of the present embodiment, the reaction vessel 120 is connected to the second pipe 124 for introducing the nitrogen-containing gas, but the pipe for discharging the gas from the reaction vessel 120 is Absent. For this reason, the alkali metal vapor evaporated from the solvent 132 does not leak to the outside from the reaction vessel 120, and fluctuations in the amount of the solvent 132 are suppressed. Further, by controlling the pressure of the nitrogen-containing gas in the reaction vessel 120, it becomes possible to introduce the amount of nitrogen-containing gas consumed by the growth of the group III nitride crystal from the second pipe 124. For this reason, the fluctuation | variation of the temperature of the solvent 132 is suppressed. Thus, since the fluctuation | variation of the temperature and liquid quantity of the solvent 132 is suppressed, a high quality group III nitride crystal can be grown stably.

また、本実施形態のＩＩＩ族窒化物結晶の成長装置においては、第１配管１２２は、第１部分１２２ｓとガス出口１２２ｅとの間の部分１２２ｂに所定の圧力Ｐｃにおいて窒素含有ガスを第１部分１２２ｓからガス出口１２２ｅまでの一方向のみに窒素含有ガスを流す差圧弁１２２ｗを有することが好ましい。かかる差圧弁１２２ｗにより、まず反応容器１２０に窒素含有ガスが導入される。次いで、反応容器１２０の内圧と耐圧容器１１０の内圧の差圧ΔＰが所定の圧力Ｐｃに達すると、差圧弁１２２ｗが開いて、耐圧容器１１０に窒素含有ガスが導入される。こうして、反応容器１２０および耐圧容器１１０への窒素含有ガスの供給および結晶成長の際に、反応容器１２０の内圧は耐圧容器１１０の内圧に比べて高く維持される。また、かかる差圧弁１２２ｗは、窒素含有ガスを第１配管１２２の第１部分１２２ｓからガス出口１２２ｅまでの一方向のみに流し、その反対方向には流さないため、耐圧容器１１０から反応容器１２０に窒素含有ガスが流入することはない。このため、反応容器１２０への不純物の流入が抑制され、品質の高いＩＩＩ族窒化物結晶を成長させることができる。   Further, in the group III nitride crystal growth apparatus of the present embodiment, the first pipe 122 supplies the nitrogen-containing gas to the portion 122b between the first portion 122s and the gas outlet 122e at the predetermined pressure Pc. It is preferable to have a differential pressure valve 122w that allows the nitrogen-containing gas to flow only in one direction from 122s to the gas outlet 122e. The nitrogen-containing gas is first introduced into the reaction vessel 120 by the differential pressure valve 122w. Next, when the pressure difference ΔP between the internal pressure of the reaction vessel 120 and the internal pressure of the pressure vessel 110 reaches a predetermined pressure Pc, the differential pressure valve 122w is opened, and a nitrogen-containing gas is introduced into the pressure vessel 110. Thus, the internal pressure of the reaction vessel 120 is maintained higher than the internal pressure of the pressure vessel 110 during the supply of nitrogen-containing gas to the reaction vessel 120 and the pressure vessel 110 and the crystal growth. Further, the differential pressure valve 122w allows the nitrogen-containing gas to flow only in one direction from the first portion 122s of the first pipe 122 to the gas outlet 122e and not in the opposite direction. Nitrogen-containing gas does not flow in. For this reason, the inflow of impurities into the reaction vessel 120 is suppressed, and a high-quality group III nitride crystal can be grown.

また、図３を参照して、本実施形態のＩＩＩ族窒化物結晶の成長装置においては、第２配管１２４の最小内部断面積Ｓｐに対する反応容器１２０（具体的には反応容器本体１２０ａ）の最小内部断面積Ｓｒの比Ｓｒ／Ｓｐは１０以上であることが好ましい。比Ｓｒ／Ｓｐを１０以上とすることにより反応容器１２０への窒素含有ガスの流入速度を十分に低くして、溶媒の蒸発量を抑制することにより溶媒の液量の変動を抑制することができる。かかる観点から、比Ｓｒ／Ｓｐは１００以上がより好ましい。ここで、配管または容器の最小内部断面積とは、配管または反応容器の内部空間において最小となる断面積をいうものとする。   Referring to FIG. 3, in the group III nitride crystal growth apparatus of the present embodiment, the minimum of reaction vessel 120 (specifically, reaction vessel main body 120 a) with respect to the minimum internal cross-sectional area Sp of second pipe 124. The ratio Sr / Sp of the internal cross-sectional area Sr is preferably 10 or more. By setting the ratio Sr / Sp to 10 or more, the flow rate of the nitrogen-containing gas into the reaction vessel 120 can be made sufficiently low, and the fluctuation of the solvent volume can be suppressed by suppressing the evaporation amount of the solvent. . From this viewpoint, the ratio Sr / Sp is more preferably 100 or more. Here, the minimum internal cross-sectional area of the pipe or the container refers to a cross-sectional area that is minimum in the internal space of the pipe or the reaction container.

また、図１を参照して、本実施形態のＩＩＩ族窒化物結晶の成長装置は、耐圧容器１１０からガスを排出する第３配管１１６と、第３配管１１６の途中に配置されている圧力調整器１１６ｐと、第１配管１２２の窒素含有ガス供給装置１８０と第１部分１２２ｓとの間の部分１２２ａに配置されているガス流量調整器１２２ｆと、をさらに備えることが好ましい。かかる圧力調整器１１６ｐにより耐圧容器１１０の内圧の制御が容易となり、ガス流量調整器１２２ｆにより反応容器１２０の内圧の制御が容易となる。また、圧力調整器１１６ｐおよびガス流量調整器１２２ｆとを連動させることにより、耐圧容器１１０の内圧および反応容器１２０の内圧の総合的な制御が容易となる。   Referring to FIG. 1, the group III nitride crystal growth apparatus of the present embodiment includes a third pipe 116 that discharges gas from the pressure vessel 110 and a pressure adjustment that is arranged in the middle of the third pipe 116. It is preferable to further include a vessel 116p and a gas flow rate regulator 122f disposed in a portion 122a between the nitrogen-containing gas supply device 180 and the first portion 122s of the first pipe 122. The pressure regulator 116p facilitates control of the internal pressure of the pressure vessel 110, and the gas flow rate regulator 122f facilitates control of the internal pressure of the reaction vessel 120. Further, by linking the pressure regulator 116p and the gas flow regulator 122f, comprehensive control of the internal pressure of the pressure vessel 110 and the internal pressure of the reaction vessel 120 is facilitated.

また、図１を参照して、本実施形態のＩＩＩ族窒化物結晶の成長装置は、真空排気装置１９０と、第１配管１２２のガス流量調整器１２２ｆと第１部分１２２ｓとの間の第２部分１２２ｔから管内のガスを真空排気装置１９０で排気する第４配管１２６と、をさらに備えることが好ましい。かかる真空排気装置１９０および第４配管１２６を備えることにより、反応容器１２０および耐圧容器１１０に窒素含有ガスを供給する前に、第１配管１２２の管内のガスおよび不純物を排気することができ、不純物が少なく高品質のＩＩＩ族窒化物結晶が得られやすくなる。かかる第４配管の途中には真空排気を制御するためのバルブ１２６ｖが配置されている。なお、図１に、参考のために、第１配管１２２の窒素含有ガス供給装置１８０と第２部分１２２ｔとの間の部分１２２ａａと、第２部分１２２ｔと第１部分１２２ｓとの間の部分１２２ａｂとを示す。   Referring to FIG. 1, the group III nitride crystal growth apparatus of the present embodiment includes a vacuum exhaust device 190, a second gas flow regulator 122 f of the first pipe 122, and a second portion 122 s between the first portion 122 s. It is preferable to further include a fourth pipe 126 that exhausts the gas in the pipe from the portion 122t by the vacuum exhaust device 190. By providing the vacuum exhaust device 190 and the fourth pipe 126, the gas and impurities in the pipe of the first pipe 122 can be exhausted before supplying the nitrogen-containing gas to the reaction vessel 120 and the pressure vessel 110. Therefore, a high-quality group III nitride crystal is easily obtained. A valve 126v for controlling the vacuum exhaust is disposed in the middle of the fourth pipe. For reference, FIG. 1 shows a portion 122aa between the nitrogen-containing gas supply device 180 and the second portion 122t of the first pipe 122 and a portion 122ab between the second portion 122t and the first portion 122s. It shows.

（実施形態２）
図１を参照して、本発明にかかるＩＩＩ族窒化物結晶の成長方法は、実施形態１の結晶成長装置を用いたＩＩＩ族窒化物結晶の成長方法であって、反応容器１２０にＩＩＩ族金属とアルカリ金属とを含む溶媒１３２を収容する工程と、反応容器１２０に窒素含有ガスを供給してＩＩＩ族窒化物結晶４００を成長させる工程と、を備え、ＩＩＩ族窒化物結晶を成長させる工程において、ＩＩＩ族窒化物結晶４００の成長により消費された量の窒素含有ガスを供給する。 (Embodiment 2)
Referring to FIG. 1, the method for growing a group III nitride crystal according to the present invention is a method for growing a group III nitride crystal using the crystal growth apparatus according to the first embodiment. And a step of growing a group III nitride crystal by supplying a nitrogen-containing gas to the reaction vessel 120 and growing a group III nitride crystal 400. The amount of nitrogen-containing gas consumed by the growth of the group III nitride crystal 400 is supplied.

本実施形態のＩＩＩ族窒化物結晶の成長方法によれば、実施形態１の結晶成長装置を用いてＩＩＩ族窒化物結晶４００を成長させる際、ＩＩＩ族窒化物結晶の成長により消費された量の窒素含有ガスを供給することにより、反応容器１２０から窒素含有ガスを排気することなく必要最小限の窒素含有ガスの供給により結晶成長させるため、溶媒１３２の温度および液量の変動が抑制され、高品質のＩＩＩ族窒化物結晶４００を安定して成長させることができる。   According to the Group III nitride crystal growth method of the present embodiment, when the Group III nitride crystal 400 is grown using the crystal growth apparatus of Embodiment 1, the amount consumed by the Group III nitride crystal growth is increased. By supplying the nitrogen-containing gas, since the crystal growth is performed by supplying the minimum necessary nitrogen-containing gas without exhausting the nitrogen-containing gas from the reaction vessel 120, fluctuations in the temperature and the liquid amount of the solvent 132 are suppressed, and high Quality group III nitride crystal 400 can be stably grown.

図１を参照して、本実施形態のＩＩＩ族窒化物結晶の成長方法は、反応容器１２０にＩＩＩ族金属とアルカリ金属とを含む溶媒１３２を収容する工程を備える。アルカリ金属が水分と極めて反応しやすいため、ドライボックス中で溶媒１３２を反応容器１２０に収容することが好ましい。ここで、溶媒１３２に含まれるＩＩＩ族金属とアルカリ金属とのモル比は、（ＩＩＩ族金属）：（アルカリ金属）で９０：１０〜１０：９０が好ましく、５０：５０〜２０：８０がより好ましい。かかる範囲から外れると結晶成長速度が低くなる。   Referring to FIG. 1, the group III nitride crystal growth method of the present embodiment includes a step of storing a solvent 132 containing a group III metal and an alkali metal in a reaction vessel 120. Since the alkali metal easily reacts with moisture, it is preferable to store the solvent 132 in the reaction vessel 120 in a dry box. Here, the molar ratio of the group III metal and the alkali metal contained in the solvent 132 is preferably (group III metal) :( alkali metal), 90:10 to 10:90, more preferably 50:50 to 20:80. preferable. Outside this range, the crystal growth rate decreases.

また、大型のＩＩＩ族窒化物結晶を成長させやすい観点から、溶媒１３２とともに下地基板３００を反応容器１２０に収容することが好ましい。下地基板３００としては、特に制限はないが、成長させるＩＩＩ族窒化物結晶との格子定数の不整合が小さいサファイア基板、ＳｉＣ基板、ＩＩＩ族窒化物基板などが好ましく挙げられる。   Moreover, it is preferable to accommodate the base substrate 300 in the reaction vessel 120 together with the solvent 132 from the viewpoint of easy growth of a large group III nitride crystal. Although there is no restriction | limiting in particular as the base substrate 300, A sapphire substrate, a SiC substrate, a group III nitride board | substrate, etc. with a small mismatch of a lattice constant with the group III nitride crystal to grow is mentioned preferably.

溶媒１３２（好ましくは溶媒１３２および下地基板３００）を収容した反応容器１２０を、第２配管１２４のバルブ１２４ｖを閉じた状態で、ドライボックスから取り出して、第２配管１２４の端部を接続部１２４ｃを介して第１配管１２２の第１部分１２２ｓに接続する。   The reaction vessel 120 containing the solvent 132 (preferably the solvent 132 and the base substrate 300) is taken out from the dry box with the valve 124v of the second pipe 124 closed, and the end of the second pipe 124 is connected to the connecting portion 124c. It connects to the 1st part 122s of the 1st piping 122 via.

また、本実施形態のＩＩＩ族窒化物結晶の成長方法は、反応容器１２０に窒素含有ガスを供給してＩＩＩ族窒化物結晶４００を成長させる工程を備える。ＩＩＩ族窒化物結晶を成長させる工程は、たとえば、以下のように行なわれる。   In addition, the Group III nitride crystal growth method of the present embodiment includes a step of growing a Group III nitride crystal 400 by supplying a nitrogen-containing gas to the reaction vessel 120. The step of growing the group III nitride crystal is performed, for example, as follows.

まず、ＩＩＩ族窒化物結晶の製造装置が、真空排気装置１９０と、第１配管１２２内のガスを真空排気装置１９０で排気する第４配管１２６とを備える場合には、第１配管１２２内を真空排気して窒素含有ガス供給装置から第１配管１２２に窒素含有ガスを導入する窒素置換を１回以上行なうことが好ましい。かかる窒素置換を１回以上行なうことにより、第１配管１２２内の不純物を除去することができる。   First, when the group III nitride crystal production apparatus includes the vacuum exhaust device 190 and the fourth pipe 126 that exhausts the gas in the first pipe 122 by the vacuum exhaust apparatus 190, the inside of the first pipe 122 is It is preferable to perform nitrogen substitution for evacuating and introducing nitrogen-containing gas into the first pipe 122 from the nitrogen-containing gas supply device at least once. By performing such nitrogen substitution once or more, impurities in the first pipe 122 can be removed.

次いで、第２配管１２４のバルブ１２４ｖを開けて、まず反応容器１２０に窒素含有ガスを導入して、反応容器１２０に窒素含有ガスを供給した。反応容器１２０の内圧と耐圧容器の内圧との差圧ΔＰが所定の圧力Ｐｃとなったときに、第１配管１２２のバルブ１２２ｖを開いて、耐圧容器１１０に窒素含有ガスを導入する。ここで、ＩＩＩ族窒化物結晶の製造装置の第１配管１２２が、第１部分１２２ｓとガス出口１２２ｅとの間の部分１２２ｂに、第１部分１２２ｓからガス出口までの一方向のみに窒素含有ガスを流す差圧弁１２２ｗを有する場合には、差圧弁１２２ｗが反応容器１２０の内圧と耐圧容器の内圧との差圧ΔＰが所定の圧力Ｐｃになったときに開くように設定しておくことが好ましい。この場合には、バルブ１２４ｖは、予め開けておく。   Next, the valve 124v of the second pipe 124 was opened, and a nitrogen-containing gas was first introduced into the reaction vessel 120, and the nitrogen-containing gas was supplied to the reaction vessel 120. When the pressure difference ΔP between the internal pressure of the reaction vessel 120 and the internal pressure of the pressure vessel becomes a predetermined pressure Pc, the valve 122v of the first pipe 122 is opened to introduce a nitrogen-containing gas into the pressure vessel 110. Here, the first piping 122 of the group III nitride crystal production apparatus has a nitrogen-containing gas only in one direction from the first portion 122s to the gas outlet in the portion 122b between the first portion 122s and the gas outlet 122e. Is preferably set so that the differential pressure valve 122w opens when the differential pressure ΔP between the internal pressure of the reaction vessel 120 and the internal pressure of the pressure-resistant vessel reaches a predetermined pressure Pc. . In this case, the valve 124v is opened beforehand.

このようにして、反応容器１２０に窒素含有ガスを供給して、反応容器１２０の内圧を所定の圧力とした後に、耐圧容器１１０に窒素含有ガスを供給するすることができる。このように反応容器１２０および耐圧容器１１０に窒素含有ガスを供給すると、耐圧容器１１０の窒素含有ガスが反応容器１２０に流入することがなく、耐圧容器１１０内の不純物が反応容器１２０に混入するのが抑制される。   In this manner, the nitrogen-containing gas can be supplied to the pressure vessel 110 after supplying the nitrogen-containing gas to the reaction vessel 120 and setting the internal pressure of the reaction vessel 120 to a predetermined pressure. When the nitrogen-containing gas is supplied to the reaction vessel 120 and the pressure vessel 110 in this way, the nitrogen-containing gas in the pressure vessel 110 does not flow into the reaction vessel 120, and impurities in the pressure vessel 110 are mixed into the reaction vessel 120. Is suppressed.

また、本実施形態のＩＩＩ族窒化物結晶の成長方法において、耐圧容器１１０の窒素含有ガスが反応容器１２０に流入することがなく、耐圧容器１１０内の不純物が反応容器１２０に混入するのが抑制される観点から、反応容器１２０の内圧は耐圧容器１１０の内圧に比べて高くすることが好ましい。ここで、反応容器１２０の内圧と耐圧容器の内圧との差圧ΔＰは、０．００１ＭＰａ以上０．１ＭＰａが好ましい。差圧ΔＰが０．００１ＭＰａより小さいとガスの圧力の精密制御に要するコストが大きくなり、０．１ＭＰａより大きいと加熱時に反応容器が変形して結晶を安定して成長させることができなくなる虞がある。   Further, in the group III nitride crystal growth method of the present embodiment, the nitrogen-containing gas in the pressure vessel 110 does not flow into the reaction vessel 120, and impurities in the pressure vessel 110 are prevented from being mixed into the reaction vessel 120. In view of this, the internal pressure of the reaction vessel 120 is preferably higher than the internal pressure of the pressure vessel 110. Here, the pressure difference ΔP between the internal pressure of the reaction vessel 120 and the internal pressure of the pressure vessel is preferably 0.001 MPa or more and 0.1 MPa. If the differential pressure ΔP is less than 0.001 MPa, the cost required for precise control of the gas pressure increases, and if it is greater than 0.1 MPa, the reaction vessel may be deformed during heating and crystals may not be able to grow stably. is there.

次いで、加熱器１１２により反応容器１２０を加熱して、反応容器１２０に収容された溶媒１３２を加熱する。溶媒１３２は、室温（たとえば、２５℃）では固体であるが、加熱により液化してＩＩＩ族金属とアルカリ金属とを含む融液となる。   Next, the reaction vessel 120 is heated by the heater 112 to heat the solvent 132 accommodated in the reaction vessel 120. The solvent 132 is solid at room temperature (for example, 25 ° C.), but is liquefied by heating to become a melt containing a group III metal and an alkali metal.

このように、反応容器１２０に窒素含有ガスを導入して加熱することにより、反応容器１２０に収容され、液化した溶媒１３２に窒素含有ガスが溶解した溶液が形成され、かかる溶液からＩＩＩ族窒化物結晶が析出して成長する。反応容器１２０に溶媒１３２および下地基板３００が配置された場合には、液化した溶媒１３２に窒素含有ガスが溶解した溶液が形成され、かかる溶液が下地基板に接触して、下地基板３００上にＩＩＩ族窒化物結晶４００が成長する。   Thus, by introducing and heating the nitrogen-containing gas into the reaction vessel 120, a solution containing the nitrogen-containing gas dissolved in the liquefied solvent 132 formed in the reaction vessel 120 is formed, and the group III nitride is formed from the solution. Crystals precipitate and grow. When the solvent 132 and the base substrate 300 are disposed in the reaction vessel 120, a solution in which a nitrogen-containing gas is dissolved is formed in the liquefied solvent 132, and the solution comes into contact with the base substrate and the III is formed on the base substrate 300. Group nitride crystal 400 grows.

本実施形態のＩＩＩ族窒化物結晶の成長方法は、ＩＩＩ族窒化物結晶を成長させる工程において、ＩＩＩ族窒化物結晶４００の成長により消費した量と同じ量の窒素含有ガスを供給する。ＩＩＩ族窒化物結晶４００を成長させる際、このように窒素含有ガスを供給することにより、反応容器１２０から窒素含有ガスを排気することなく必要最小限の窒素含有ガスの供給により結晶成長させるため、溶媒１３２の温度および液量の変動が抑制され、高品質のＩＩＩ族窒化物結晶４００を安定して成長させることができる。   In the method for growing a group III nitride crystal of the present embodiment, the same amount of nitrogen-containing gas as that consumed by the growth of the group III nitride crystal 400 is supplied in the step of growing the group III nitride crystal. When the group III nitride crystal 400 is grown, by supplying the nitrogen-containing gas in this way, the crystal is grown by supplying the minimum necessary nitrogen-containing gas without exhausting the nitrogen-containing gas from the reaction vessel 120. Variations in the temperature and liquid volume of the solvent 132 are suppressed, and the high-quality group III nitride crystal 400 can be stably grown.

すなわち、本実施形態のＩＩＩ族窒化物結晶の成長方法においては、窒素含有ガス供給装置１８０から供給された窒素含有ガスにより、反応容器１２０の内圧および耐圧容器１１０の内圧が制御されている。   That is, in the group III nitride crystal growth method of this embodiment, the internal pressure of the reaction vessel 120 and the internal pressure of the pressure vessel 110 are controlled by the nitrogen-containing gas supplied from the nitrogen-containing gas supply device 180.

かかる反応容器１２０および耐圧容器１１０の内圧の制御には、特に制限はないが、ＩＩＩ族窒化物結晶の成長装置が、耐圧容器１１０からガスを排出する第３配管１１６と、第３配管の途中の部分に配置された圧力調整器１１６ｐと、第１配管１２２の窒素含有ガス供給装置１８０と第１部分１２２ｓの間の部分１２２２ａに配置されたガス流量調整器１２２ｆと、さらに備える場合には、圧力調整器１１６ｐとガス流量調整器１２２ｆとを用いることが好ましい。圧力調整器１１６ｐとガス流量調整器１２２ｆとを用いることにより、かかる反応容器１２０および耐圧容器１１０の内圧の制御が容易になる。   Control of the internal pressures of the reaction vessel 120 and the pressure vessel 110 is not particularly limited, but the group III nitride crystal growth apparatus discharges the gas from the pressure vessel 110 and the middle of the third pipe. When the pressure regulator 116p disposed in the portion of the first pipe 122 and the gas flow regulator 122f disposed in the portion 1222a between the nitrogen-containing gas supply device 180 of the first pipe 122 and the first portion 122s are further provided, It is preferable to use the pressure regulator 116p and the gas flow regulator 122f. By using the pressure regulator 116p and the gas flow regulator 122f, control of the internal pressure of the reaction vessel 120 and the pressure vessel 110 is facilitated.

このように、反応容器１２０の内圧が耐圧容器１１０の内圧に比べて高くなるように制御することにより、耐圧容器１１０の不純物が反応容器１２０に流入することが抑制され、高品質のＩＩＩ族窒化物結晶を容易に成長させることができる。   Thus, by controlling the internal pressure of the reaction vessel 120 to be higher than the internal pressure of the pressure vessel 110, the impurities in the pressure vessel 110 are suppressed from flowing into the reaction vessel 120, and high-quality group III nitriding is performed. A physical crystal can be easily grown.

（予備検討：第２の配管および反応容器の最小内部断面積の比較）
図１および図３を参照して、溶媒１３２の蒸発の抑制効果を高めるために好適な第２の配管１２４の最小内部断面積Ｓｐに対する反応容器１２０（具体的には反応器本体１２０ａ）の最小内部断面積Ｓｒの比Ｓｒ／Ｓｐを調べた。具体的には、表１に示すような最小内径Ｄｐおよび最小内部断面積Ｓｐを有する第２配管１２４と最小内径Ｄｒおよび最小内部断面積Ｓｒを有する反応容器１２０（具体的には反応容器本体１２０ａ）を用いて、上記最小内部断面積×高さ８０ｍｍの反応容器１２０内に収容された４５ｇの溶媒１３２（Ｇａ−Ｎａ融液、ここでＧａとＮａのモル比は３対７）に、８８０℃の雰囲気温度下で４ＭＰａの窒素ガスを９６時間接触させたときの溶媒１３２（Ｇａ−Ｎａ融液）の蒸発量を算出した。結果を表１に示す。 (Preliminary study: Comparison of the minimum internal cross-sectional area of the second piping and reaction vessel)
Referring to FIGS. 1 and 3, the minimum of reaction vessel 120 (specifically, reactor main body 120a) with respect to the minimum internal cross-sectional area Sp of second pipe 124 suitable for enhancing the effect of suppressing the evaporation of solvent 132. The ratio Sr / Sp of the internal cross-sectional area Sr was examined. Specifically, as shown in Table 1, the second pipe 124 having the minimum inner diameter Dp and the minimum internal cross-sectional area Sp, and the reaction vessel 120 having the minimum inner diameter Dr and the minimum internal cross-sectional area Sr (specifically, the reaction vessel main body 120a). ) To the 45 g of the solvent 132 (Ga—Na melt, where the molar ratio of Ga to Na is 3 to 7) contained in the reaction vessel 120 having the minimum internal cross-sectional area × height of 80 mm. The amount of evaporation of the solvent 132 (Ga—Na melt) when 4 MPa of nitrogen gas was contacted for 96 hours under an ambient temperature of ° C. was calculated. The results are shown in Table 1.

Figure 0005032406
Figure 0005032406

表１を参照して、Ａの場合は比Ｓｒ／Ｓｐが４であり溶媒の蒸発量が５５質量％であった。Ｂの場合は比Ｓｒ／Ｓｐが１６であり溶媒の蒸発量が９質量％であった。Ｃの場合は比Ｓｒ／Ｓｐが２５６であり溶媒の蒸発量が０質量％であった。Ｄの場合は比Ｓｒ／Ｓｐが１６００であり溶媒の蒸発量が０質量％であった。これらの結果から、比Ｓｒ／Ｓｐは、１０以上が好ましく、１００以上がより好ましいことがわかる。   Referring to Table 1, in the case of A, the ratio Sr / Sp was 4, and the evaporation amount of the solvent was 55% by mass. In the case of B, the ratio Sr / Sp was 16, and the evaporation amount of the solvent was 9% by mass. In the case of C, the ratio Sr / Sp was 256, and the evaporation amount of the solvent was 0% by mass. In the case of D, the ratio Sr / Sp was 1600, and the evaporation amount of the solvent was 0% by mass. From these results, it can be seen that the ratio Sr / Sp is preferably 10 or more, and more preferably 100 or more.

（実施例１）
１．ＧａＮ結晶（ＩＩＩ族窒化物結晶）の成長装置
図１に示すような結晶成長装置を作製した。本結晶成長装置の詳細は実施形態１で説明したとおりである。ここで、上記予備検討の結果を考慮して、最小内径Ｄｒが８０ｍｍで最小内部断面積Ｓｒが５０２４ｍｍ2の反応容器１２０と、最小内径Ｄｐが５ｍｍで最小内部断面積Ｓｐが１９．６ｍｍ2の第２配管１２２を用いた。また、第１、第３および第４配管についても、第２配管と同じ最小内径および最小内部断面積を有する配管を用いた。 Example 1
1. GaN crystal (group III nitride crystal) growth apparatus A crystal growth apparatus as shown in FIG. 1 was produced. The details of this crystal growth apparatus are as described in the first embodiment. Here, in consideration of the result of the preliminary examination, the reaction vessel 120 having the minimum inner diameter Dr of 80 mm and the minimum inner sectional area Sr of 5024 mm 2 , the minimum inner diameter Dp of 5 mm and the minimum inner sectional area Sp of 19.6 mm 2 is used. The second piping 122 was used. For the first, third, and fourth pipes, pipes having the same minimum inner diameter and minimum internal cross-sectional area as the second pipe were used.

２．ＧａＮ結晶（ＩＩＩ族窒化物結晶）の成長
次に、ＧａＮ基板（下地基板３００）と金属Ｇａおよび金属Ｎａ（溶媒１３２）とを収容した反応容器１２０に接続されている第２配管１２４のバルブ１２４ｖを閉じて、反応容器１２０をドライボックスから取り出し、第２配管１２４を接続部１２４ｃを介して第１配管１２２の第１部分１２２ｓに接続した。 2. Growth of GaN Crystal (Group III Nitride Crystal) Next, the valve 124v of the second pipe 124 connected to the reaction vessel 120 containing the GaN substrate (underlying substrate 300), metal Ga and metal Na (solvent 132). Was closed, the reaction vessel 120 was taken out of the dry box, and the second pipe 124 was connected to the first portion 122s of the first pipe 122 via the connection portion 124c.

次に、第４配管１２６のバルブ１２６ｖを開いて第１配管１２２内を真空排気した（真空度は１Ｔｏｒｒ（１３３Ｐａ）程度）。次いで、第４配管１２６のバルブ１２６ｖを閉めて窒素含有ガス供給装置１８０から第１配管１２２に純度９９．９９質量％以上の窒素ガスを導入した。かかる第１配管１２２の真空排気および窒素ガス置換は３回行なった。   Next, the valve 126v of the fourth pipe 126 was opened, and the inside of the first pipe 122 was evacuated (the degree of vacuum was about 1 Torr (133 Pa)). Next, the valve 126v of the fourth pipe 126 was closed, and nitrogen gas having a purity of 99.99 mass% or more was introduced from the nitrogen-containing gas supply device 180 into the first pipe 122. The first pipe 122 was evacuated and replaced with nitrogen gas three times.

次に、第２配管１２４のバルブ１２４ｖを開いて、窒素含有ガス供給装置１８０から第１配管１２２のガス流量調整器１２２ｆおよび第１部分１２２ｓおよび第２配管１２４を通って、反応容器１２０に窒素ガス（窒素含有ガス）を導入した。このとき、第１配管１２２の第１部分１２２ｓとガス出口１２２ｅとの間の部分１２２ｂに配置された差圧弁１２２ｗは、０．００３ＭＰａの差圧ΔＰにより第１部分１２２ｓからガス出口１２２ｅの一方向のみに窒素ガスが流れるように設定した。また、第１配管１２２のガス出口１２２ｅ付近に配置されているバルブ１２２ｖは開いておいた。反応容器１２０の内圧が耐圧容器１１０の内圧に比べて０．００３ＭＰａ以上高くなると、第１配管１２２の第１部分１２２ｓとガス出口１２２ｅとの間の部分１２２ｂを通って窒素ガスが耐圧容器１１０に導入された。   Next, the valve 124v of the second pipe 124 is opened, and the nitrogen-containing gas supply device 180 passes through the gas flow rate regulator 122f, the first portion 122s of the first pipe 122, and the second pipe 124 to supply nitrogen to the reaction vessel 120. Gas (nitrogen-containing gas) was introduced. At this time, the differential pressure valve 122w disposed in the portion 122b between the first portion 122s of the first pipe 122 and the gas outlet 122e is unidirectional from the first portion 122s to the gas outlet 122e by the differential pressure ΔP of 0.003 MPa. Only nitrogen gas was set to flow. In addition, the valve 122v disposed in the vicinity of the gas outlet 122e of the first pipe 122 was open. When the internal pressure of the reaction vessel 120 becomes higher than the internal pressure of the pressure vessel 110 by 0.003 MPa or more, nitrogen gas enters the pressure vessel 110 through the portion 122b between the first portion 122s of the first pipe 122 and the gas outlet 122e. Was introduced.

こうして、反応容器１２０の内圧と耐圧容器１１０の内圧との差圧ΔＰを０．００３ＭＰａに維持しながら、反応容器１２０および耐圧容器１１０に窒素ガスを供給して、反応容器１２０の内圧を４ＭＰａとし、耐圧容器１１０の内圧を３．９９７ＭＰａとした。   In this way, while maintaining the differential pressure ΔP between the internal pressure of the reaction vessel 120 and the internal pressure of the pressure vessel 110 at 0.003 MPa, nitrogen gas is supplied to the reaction vessel 120 and the pressure vessel 110 to set the internal pressure of the reaction vessel 120 to 4 MPa. The internal pressure of the pressure vessel 110 was 3.997 MPa.

次に、加熱器１１２により反応容器１２０を加熱して、２時間で８８０℃に昇温させた。   Next, the reaction vessel 120 was heated by the heater 112, and the temperature was raised to 880 ° C. in 2 hours.

次に、ガス流量調整器１２２ｆの窒素ガス流量を１００ｓｃｃｍとして、反応容器の内圧を４ＭＰａとし温度８８０℃で９６時間保持して、ＧａＮ基板上にＧａＮ結晶を成長させた。   Next, the nitrogen gas flow rate of the gas flow rate regulator 122f was 100 sccm, the internal pressure of the reaction vessel was 4 MPa, and the temperature was maintained at 880 ° C. for 96 hours to grow GaN crystals on the GaN substrate.

次に、反応容器の温度を８８０℃から３０℃に降温させ、反応容器１２０の内圧と耐圧容器１１０の内圧との差圧ΔＰを維持しながら減圧した。反応容器１２０の内圧が０．００３ＭＰａになると、耐圧容器１１０の内圧は大気圧となり、、その後反応容器１２０の内圧を大気圧まで減圧した。   Next, the temperature of the reaction vessel was lowered from 880 ° C. to 30 ° C., and the pressure was reduced while maintaining the differential pressure ΔP between the internal pressure of the reaction vessel 120 and the internal pressure of the pressure resistant vessel 110. When the internal pressure of the reaction vessel 120 reached 0.003 MPa, the internal pressure of the pressure vessel 110 became atmospheric pressure, and then the internal pressure of the reaction vessel 120 was reduced to atmospheric pressure.

次に、反応容器１２０の坩堝１３０内の溶媒１３２からＧａＮ基板（下地基板３００）上に成長したＧａＮ結晶（ＩＩＩ族窒化物結晶４００）を取り出した。   Next, the GaN crystal (Group III nitride crystal 400) grown on the GaN substrate (underlying substrate 300) was taken out from the solvent 132 in the crucible 130 of the reaction vessel 120.

こうして得られたＧａＮ結晶について、成長厚さ、キャリア濃度および転位密度を測定した。ここで、成長厚さの測定は、成長後の結晶の厚さから下地基板の厚さを差し引いて算出した。結晶および下地基板の厚さはデジマチックインジケータ（株式会社ミツトヨ製）を用いて測定した。キャリア濃度の測定は、ホール測定法により行なった。また、転位密度の測定は、カソードルミネッセンス（ＣＬ）法で行なった。   The growth thickness, carrier concentration, and dislocation density of the GaN crystal thus obtained were measured. Here, the growth thickness was calculated by subtracting the thickness of the base substrate from the thickness of the crystal after growth. The thickness of the crystal and the base substrate was measured using a Digimatic indicator (manufactured by Mitutoyo Corporation). The carrier concentration was measured by the Hall measurement method. The dislocation density was measured by the cathodoluminescence (CL) method.

上記の同一の工程および条件で、ＧａＮ結晶の成長を１０回実施し、成長させた１０個のＧａＮ結晶について、成長厚さ、キャリア密度および転位密度を測定したところ、それぞれ１．９〜２．２ｍｍ、３．７×１０16〜５．０×１０16ｃｍ-3および３．５×１０5〜４５×１０5ｃｍ-2であった。これらの結果を表２にまとめた。 Under the same process and conditions described above, GaN crystals were grown 10 times, and the growth thickness, carrier density, and dislocation density were measured for the 10 grown GaN crystals. 2 mm, was 3.7 × 10 16 ~5.0 × 10 16 cm -3 and 3.5 × 10 5 ~45 × 10 5 cm -2. These results are summarized in Table 2.

（比較例１）
１．ＧａＮ結晶（ＩＩＩ族窒化物結晶）の成長装置
図２に示すような典型的な結晶成長装置を用いた。本結晶成長装置は、金属Ｇａ（ＩＩＩ族金属）と金属Ｎａ（アルカリ金属）とを含む溶媒２３２を入れる坩堝２３０を収容する反応容器２２０と、反応容器２２０の周囲に配設された加熱器２１２と、加熱器２１２の周囲に配設された断熱材２１４と、反応容器２２０および加熱器２１２および断熱材２１４を収容する耐圧容器２１０と、反応容器２２０および耐圧容器２１０に窒素ガス（窒素含有ガス）を供給する窒素含有ガス供給装置２８０とを備える。ここで、反応容器２２０は反応容器本体２２０ａと反応容器蓋２２０ｂとで形成されている。また、耐圧容器２１０は耐圧容器本体２１０ａと耐圧容器蓋２１０ｂとで形成されている。 (Comparative Example 1)
1. GaN crystal (group III nitride crystal) growth apparatus A typical crystal growth apparatus as shown in FIG. 2 was used. This crystal growth apparatus includes a reaction vessel 220 containing a crucible 230 containing a solvent 232 containing metal Ga (Group III metal) and metal Na (alkali metal), and a heater 212 arranged around the reaction vessel 220. A heat insulating material 214 disposed around the heater 212, a pressure vessel 210 containing the reaction vessel 220 and the heater 212 and the heat insulating material 214, and a nitrogen gas (nitrogen-containing gas) in the reaction vessel 220 and the pressure vessel 210. A nitrogen-containing gas supply device 280. Here, the reaction vessel 220 is formed of a reaction vessel main body 220a and a reaction vessel lid 220b. The pressure vessel 210 is formed of a pressure vessel body 210a and a pressure vessel lid 210b.

また、本結晶成長装置は、窒素含有ガス供給装置２８０から反応容器２２０に窒素ガス（窒素含有ガス）を導入する配管２２３と、反応容器２２０から耐圧容器２１０に窒素ガスを導入する配管２２５と、耐圧容器２１０から窒素ガスを排出する配管２１６とを備える。ここで、配管２２３には窒素含有ガス供給装置２８０側から反応容器２２０側にかけて順にガス流量調整器２２３ｆ、接続部２２３ｃおよびバルブ２２３ｖが配置されている。また、配管２２５の途中の部分にはバルブ２２５ｖが配置されている。また、配管２１６の途中の部分には圧力調整器２１６ｐが配置されている。   Further, the present crystal growth apparatus includes a pipe 223 for introducing nitrogen gas (nitrogen-containing gas) from the nitrogen-containing gas supply device 280 to the reaction vessel 220, a pipe 225 for introducing nitrogen gas from the reaction vessel 220 to the pressure vessel 210, And a pipe 216 for discharging nitrogen gas from the pressure vessel 210. Here, in the pipe 223, a gas flow rate regulator 223f, a connection part 223c, and a valve 223v are sequentially arranged from the nitrogen-containing gas supply device 280 side to the reaction vessel 220 side. In addition, a valve 225v is arranged in the middle of the pipe 225. In addition, a pressure regulator 216p is disposed in the middle of the pipe 216.

また、上記予備検討の結果を考慮して、最小内径Ｄｒが８０ｍｍで最小内部断面積Ｓｒが５０２４ｍｍ2の反応容器２２０と、最小内径Ｄｐが５ｍｍで最小内部断面積Ｓｐが１９．６ｍｍ2の配管２１６，２２３および２２５を用いた。 Further, in view of the results of the preliminary study, the minimum inner diameter Dr is the minimum internal cross-sectional area Sr at 80mm and the reaction vessel 220 of 5024Mm 2, the minimum internal cross-sectional area Sp minimum inner diameter Dp is in 5mm of 19.6 mm 2 pipe 216, 223 and 225 were used.

２．ＧａＮ結晶（ＩＩＩ族窒化物結晶）の成長
次に、ＧａＮ基板（下地基板３００）と金属Ｇａおよび金属Ｎａ（溶媒２３２）とを収容した反応容器２２０に接続されている配管２２３および配管２２５のそれぞれのバルブ２２３ｖおよび２２５ｖを閉じて、反応容器２２０をドライボックスから取り出し、配管２２３を接続部２２３ｃを介してガス流量調整器２２３ｆおよび窒素含有ガス供給装置２８０に接続した。 2. Growth of GaN Crystal (Group III Nitride Crystal) Next, piping 223 and piping 225 connected to a reaction vessel 220 containing a GaN substrate (underlying substrate 300), metal Ga and metal Na (solvent 232), respectively. The valves 223v and 225v were closed, the reaction vessel 220 was taken out of the dry box, and the pipe 223 was connected to the gas flow rate regulator 223f and the nitrogen-containing gas supply device 280 via the connection part 223c.

次に、配管２２３のバルブ２２３ｖを開いて、窒素含有ガス供給装置２８０から配管２２３のガス流量調整器２２３ｆおよび接続部２２３ｃを通って、反応容器２２０に窒素含有ガスを導入した。反応容器２２０の内圧が０．０５ＭＰａ以上になったとき、配管２２５のバルブ２２５ｖを開けて、反応容器２２０から耐圧容器２１０に窒素ガス（窒素含有ガス）を導入した。このようにして、反応容器２２０および耐圧容器２１０の内圧をいずれも４ＭＰａとした。   Next, the valve 223v of the pipe 223 was opened, and the nitrogen-containing gas was introduced into the reaction vessel 220 from the nitrogen-containing gas supply device 280 through the gas flow rate regulator 223f and the connection part 223c of the pipe 223. When the internal pressure of the reaction vessel 220 became 0.05 MPa or more, the valve 225v of the pipe 225 was opened, and nitrogen gas (nitrogen-containing gas) was introduced from the reaction vessel 220 to the pressure vessel 210. In this way, the internal pressures of the reaction vessel 220 and the pressure vessel 210 were both 4 MPa.

次に、加熱器２１２により反応容器２２０を加熱して、２時間で８８０℃に昇温させた。   Next, the reaction vessel 220 was heated by the heater 212, and the temperature was raised to 880 ° C. in 2 hours.

次に、ガス流量調整器２２３ｆの窒素ガス流量を１００ｓｃｃｍとして、反応容器の内圧を４ＭＰａとし温度８８０℃で９６時間保持して、ＧａＮ基板上にＧａＮ結晶を成長させた。   Next, the nitrogen gas flow rate of the gas flow rate regulator 223f was set to 100 sccm, the internal pressure of the reaction vessel was set to 4 MPa, and the temperature was maintained at 880 ° C. for 96 hours to grow a GaN crystal on the GaN substrate.

次に、反応容器の温度を８８０℃から３０℃に降温させ、反応容器２２０および耐圧容器２１０の内圧を減圧した。   Next, the temperature of the reaction vessel was lowered from 880 ° C. to 30 ° C., and the internal pressures of the reaction vessel 220 and the pressure vessel 210 were reduced.

次に、反応容器２２０の坩堝２３０内の溶媒２３２からＧａＮ基板（下地基板３００）上に成長したＧａＮ結晶（ＩＩＩ族窒化物結晶４００）を取り出した。   Next, the GaN crystal (Group III nitride crystal 400) grown on the GaN substrate (underlying substrate 300) was taken out from the solvent 232 in the crucible 230 of the reaction vessel 220.

こうして得られたＧａＮ結晶について、成長厚さ、キャリア濃度および転位密度を測定した。   The growth thickness, carrier concentration, and dislocation density of the GaN crystal thus obtained were measured.

上記の同一の工程および条件で、ＧａＮ結晶の成長を１０回実施し、成長させた１０個のＧａＮ結晶について、成長厚さ、キャリア密度および転位密度を測定したところ、それぞれ１．２〜２．７ｍｍ、１．７×１０16〜７．０×１０16ｃｍ-3および３．７×１０5〜３２０×１０5ｃｍ-2であった。これらの結果を表２にまとめた。 Under the same process and conditions described above, GaN crystals were grown 10 times, and the growth thickness, carrier density, and dislocation density were measured for 10 grown GaN crystals. 7 mm, 1.7 × 10 16 to 7.0 × 10 16 cm −3 and 3.7 × 10 5 to 320 × 10 5 cm −2 . These results are summarized in Table 2.

Figure 0005032406
Figure 0005032406

表２を参照して、比較例１と実施例１とを対比すると、ＧａＮ結晶の成長厚さ、キャリア濃度および転位密度のいずれにおいてもそれらの数値のバラツキの範囲が小さくなった。このことから、実施例１は比較例１に比べて、高品質のＧａＮ結晶を安定して成長したことがわかる。   Referring to Table 2, when Comparative Example 1 and Example 1 were compared, the range of variation of those values was small in any of the growth thickness, carrier concentration, and dislocation density of the GaN crystal. From this, it can be seen that the high-quality GaN crystal was stably grown in Example 1 as compared with Comparative Example 1.

ここで、比較例１の結晶成長装置には反応容器２２０に窒素含有ガスを導入する配管（配管２２３）および排出する配管（配管２２５）が設けられているのに対し、実施例１の結晶成長装置には反応容器１２０に窒素含有ガスを導入する配管（第２配管１２４）のみが設けられ窒素含有ガスを排出する配管は設けられていない。このため、溶媒の温度および液量の変動が抑制され、安定した結晶成長が可能になったものと考えられる。   Here, the crystal growth apparatus of Comparative Example 1 is provided with a pipe (pipe 223) for introducing a nitrogen-containing gas into the reaction vessel 220 and a pipe (pipe 225) for discharging it, while the crystal growth of Example 1 is performed. In the apparatus, only a pipe (second pipe 124) for introducing a nitrogen-containing gas into the reaction vessel 120 is provided, and no pipe for discharging the nitrogen-containing gas is provided. For this reason, it is considered that fluctuations in the temperature and liquid volume of the solvent are suppressed, and stable crystal growth is possible.

また、比較例１の結晶成長容器には反応容器２２０と耐圧容器２１０と繋ぐ配管（配管２２５）に差圧弁が設けられていないのに対し、実施例１の結晶成長容器には反応容器１２０と耐圧容器１１０と繋ぐ配管（第１配管１２２の第１部分１２２ｓとガス出口１２２ｅとの間の部分１２２ｂ）に差圧弁１２２ｗが設けられている。このため、実施例１においては、耐圧容器の内圧に比べて反応容器の内圧を大きくすることができ、耐圧容器内の不純物が反応容器に流入するのが抑制され、高品質の結晶が得られたものと考えられる。   The crystal growth vessel of Comparative Example 1 is not provided with a differential pressure valve in the pipe (pipe 225) connecting the reaction vessel 220 and the pressure vessel 210, whereas the crystal growth vessel of Example 1 has the reaction vessel 120 and A differential pressure valve 122w is provided in a pipe (a part 122b between the first part 122s of the first pipe 122 and the gas outlet 122e) connected to the pressure vessel 110. For this reason, in Example 1, the internal pressure of the reaction vessel can be increased as compared with the internal pressure of the pressure vessel, and impurities in the pressure vessel are prevented from flowing into the reaction vessel, and high-quality crystals are obtained. It is thought that.

また、比較例１の結晶成長容器には窒素含有ガスを反応容器に供給する配管（配管２２３）内を真空排気する真空排気装置が設けられいないのに対し、実施例１の結晶成長装置には窒素含有ガスを反応容器に供給する配管（第１配管１２２の窒素含有ガス供給装置１８０と第１部分１２２ｓとの間の部分）内を真空排気する真空排気装置１９０が設けられている。このため、実施例１においては、窒素含有ガスを供給する配管内の不純物が反応容器に流入するのが抑制され、高品質の結晶が得られたものと考えられる。   The crystal growth vessel of Comparative Example 1 is not provided with a vacuum exhaust device for evacuating the inside of the pipe (pipe 223) for supplying a nitrogen-containing gas to the reaction vessel, whereas the crystal growth device of Example 1 A vacuum exhaust device 190 is provided for evacuating the inside of the pipe for supplying the nitrogen-containing gas to the reaction vessel (the portion of the first pipe 122 between the nitrogen-containing gas supply device 180 and the first portion 122s). For this reason, in Example 1, it is thought that the impurity in the piping which supplies nitrogen-containing gas flows into the reaction vessel, and high quality crystals are obtained.

今回開示された実施の形態および実施例はすべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は、上記した説明でなくて特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内のすべての変更が含まれることが意図される。   It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

本発明にかかるＩＩＩ族窒化物結晶の成長装置の一例を示す概略図である。It is the schematic which shows an example of the growth apparatus of the group III nitride crystal concerning this invention. 典型的なＩＩＩ族窒化物結晶の製造装置の一例を示す概略図である。It is the schematic which shows an example of the manufacturing apparatus of a typical group III nitride crystal. 図１のＩＩＩ族窒化物結晶の成長装置の一部分を示す概略断面図である。ここで、（ａ）は第２配管のガス流れ方向に垂直な面における概略断面図を示し、（ｂ）は第２配管および反応容器のガス流れ方向に平行な面における概略断面図を示し、（ｃ）は反応容器のガス流れ方向に垂直な面における概略断面図である。FIG. 3 is a schematic cross-sectional view showing a part of the group III nitride crystal growth apparatus of FIG. 1. Here, (a) shows a schematic cross-sectional view in a plane perpendicular to the gas flow direction of the second pipe, (b) shows a schematic cross-sectional view in a plane parallel to the gas flow direction of the second pipe and the reaction vessel, (C) is a schematic sectional drawing in the surface perpendicular | vertical to the gas flow direction of reaction container.

符号の説明Explanation of symbols

１１０，２１０ 耐圧容器、１１０ａ，２１０ａ 耐圧容器本体、１１０ｂ，２１０ｂ 耐圧容器蓋、１１２，２１２ 加熱器、１１４，２１４ 断熱材、１１６ 第３配管、１１６ｐ，２１６ｐ 圧力調整器、１２０，２２０ 反応容器、１２０ａ，２２０ａ 反応容器本体、１２０ｂ，２２０ｂ 反応容器蓋、１２２ 第１配管、１２２ａ，１２２ａａ，１２２ａｂ，１２２ｂ 部分、１２２ｅ ガス出口、１２２ｆ，２２３ｆ ガス流量調整器、１２２ｓ 第１部分、１２２ｔ 第２部分、１２２ｖ，１２４ｖ，１２６ｖ，２２３ｖ，２２５ｖ バルブ、１２２ｗ 差圧弁、１２４ 第２配管、１２４ｃ，２２３ｃ 接続部、１２６ 第４配管、１３０，２３０ 坩堝、１３２，２３２ 溶媒，１８０，２８０ 窒素含有ガス供給装置、１９０ 真空排気装置、２１６，２２３，２２５ 配管、３００ 下地基板、４００ ＩＩＩ族窒化物結晶。   110, 210 pressure vessel, 110a, 210a pressure vessel body, 110b, 210b pressure vessel lid, 112, 212 heater, 114, 214 insulation, 116 third piping, 116p, 216p pressure regulator, 120, 220 reaction vessel, 120a, 220a reaction vessel main body, 120b, 220b reaction vessel lid, 122 first piping, 122a, 122aa, 122ab, 122b part, 122e gas outlet, 122f, 223f gas flow regulator, 122s first part, 122t second part, 122v, 124v, 126v, 223v, 225v valve, 122w differential pressure valve, 124 second piping, 124c, 223c connection portion, 126 fourth piping, 130, 230 crucible, 132, 232 solvent, 180, 280 nitrogen-containing gas supply device, 190 Vacuum exhaust Device, 216,223,225 pipe, 300 a base substrate, 400 III-nitride crystal.

Claims (5)

ＩＩＩ族金属とアルカリ金属とを含む溶媒を収容する反応容器と、前記反応容器を収容する耐圧容器と、前記反応容器および前記耐圧容器に窒素含有ガスを供給する窒素含有ガス供給装置と、前記窒素含有ガス供給装置から前記耐圧容器に窒素含有ガスを導入する第１配管と、前記第１配管の途中の第１部分から前記反応容器に前記窒素含有ガスを導入する第２配管と、を備える成長装置を用いたＩＩＩ族窒化物結晶の成長方法であって、
前記反応容器に前記ＩＩＩ族金属と前記アルカリ金属とを含む前記溶媒を収容する工程と、前記反応容器に前記窒素含有ガスを供給してＩＩＩ族窒化物結晶を成長させる工程と、を備え、
前記ＩＩＩ族窒化物結晶を成長させる工程において、前記ＩＩＩ族窒化物結晶の成長により消費された量の前記窒素含有ガスを供給するＩＩＩ族窒化物結晶の成長方法。 A reaction vessel containing a solvent containing a Group III metal and an alkali metal, a pressure vessel containing the reaction vessel, a nitrogen-containing gas supply device for supplying a nitrogen-containing gas to the reaction vessel and the pressure vessel, and the nitrogen A growth comprising: a first pipe for introducing a nitrogen-containing gas from the contained gas supply device into the pressure vessel; and a second pipe for introducing the nitrogen-containing gas into the reaction container from a first part in the middle of the first pipe. A method for growing a group III nitride crystal using an apparatus,
Wherein provided between the group III metal in the reaction vessel and the step of housing said solvent comprising said alkali metal, and growing a group III nitride crystal by supplying the nitrogen-containing gas to said reaction vessel, and
A method for growing a group III nitride crystal, wherein in the step of growing the group III nitride crystal, an amount of the nitrogen-containing gas consumed by the growth of the group III nitride crystal is supplied. 前記反応容器に前記窒素含有ガスを供給して前記反応容器を所定の内圧とした後に、前記耐圧容器に前記窒素含有ガスを供給する請求項１に記載のＩＩＩ族窒化物結晶の成長方法。 Wherein the reaction vessel by supplying the nitrogen-containing gas to the reaction vessel after a predetermined internal pressure, the growing method of a group III nitride crystal according to claim 1 for supplying the nitrogen-containing gas into the pressure vessel. 前記反応容器の内圧は前記耐圧容器の内圧に比べて高い請求項２に記載のＩＩＩ族窒化物結晶の成長方法。 The method for growing a group III nitride crystal according to claim 2 , wherein the internal pressure of the reaction vessel is higher than the internal pressure of the pressure vessel. 前記窒素含有ガスにより、前記反応容器の内圧および前記耐圧容器の内圧が制御されている請求項１に記載のＩＩＩ族窒化物結晶の成長方法。 The method for growing a group III nitride crystal according to claim 1 , wherein an internal pressure of the reaction vessel and an internal pressure of the pressure vessel are controlled by the nitrogen-containing gas. ＩＩＩ族金属とアルカリ金属とを含む溶媒を収容する反応容器と、前記反応容器を収容する耐圧容器と、前記反応容器および前記耐圧容器に窒素含有ガスを供給する窒素含有ガス供給装置と、前記窒素含有ガス供給装置から前記耐圧容器に窒素含有ガスを導入する第１配管と、前記第１配管の途中の第１部分から前記反応容器に前記窒素含有ガスを導入する第２配管と、前記耐圧容器からガスを排出する第３配管と、前記第３配管の途中の部分に配置された圧力調整器と、前記第１配管の前記窒素含有ガス供給装置と前記第１部分との間の部分に配置されたガス流量調整器と、を備える成長装置を用いたＩＩＩ族窒化物結晶の成長方法であって、
前記反応容器に前記ＩＩＩ族金属と前記アルカリ金属とを含む前記溶媒を収容する工程と、前記反応容器に前記窒素含有ガスを供給してＩＩＩ族窒化物結晶を成長させる工程と、を備え、
前記ＩＩＩ族窒化物結晶を成長させる工程において、前記ＩＩＩ族窒化物結晶の成長により消費された量の前記窒素含有ガスを供給し、
前記窒素含有ガスにより、前記圧力調整器と、前記ガス流量調整器とを用いて、前記反応容器の内圧および前記耐圧容器の内圧が制御されているＩＩＩ族窒化物結晶の成長方法。 A reaction vessel containing a solvent containing a Group III metal and an alkali metal, a pressure vessel containing the reaction vessel, a nitrogen-containing gas supply device for supplying a nitrogen-containing gas to the reaction vessel and the pressure vessel, and the nitrogen A first pipe for introducing a nitrogen-containing gas from the contained gas supply device into the pressure vessel, a second pipe for introducing the nitrogen-containing gas into the reaction vessel from a first portion in the middle of the first pipe, and the pressure vessel A third pipe for discharging gas from the gas, a pressure regulator arranged in the middle part of the third pipe, and a part of the first pipe between the nitrogen-containing gas supply device and the first part. A method for growing a group III nitride crystal using a growth apparatus comprising:
Wherein provided between the group III metal in the reaction vessel and the step of housing said solvent comprising said alkali metal, and growing a group III nitride crystal by supplying the nitrogen-containing gas to said reaction vessel, and
In the step of growing the group III nitride crystal, supplying the nitrogen-containing gas in an amount consumed by the growth of the group III nitride crystal;
A method for growing a group III nitride crystal in which the internal pressure of the reaction vessel and the internal pressure of the pressure vessel are controlled by the nitrogen-containing gas using the pressure regulator and the gas flow rate regulator.
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