JP5293428B2

JP5293428B2 - Crystal manufacturing method and crystal manufacturing apparatus

Info

Publication number: JP5293428B2
Application number: JP2009138884A
Authority: JP
Inventors: 武克山本; 尚峯本; 健畑山; 大蔵山崎
Original assignee: Ricoh Co Ltd
Current assignee: Ricoh Co Ltd
Priority date: 2009-06-10
Filing date: 2009-06-10
Publication date: 2013-09-18
Anticipated expiration: 2029-06-10
Also published as: JP2010285306A

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and an apparatus for producing a crystal where group III element nitride crystals such as a GaN single crystal formed by liquid phase growing are taken out of the inside of a raw material liquid in a short time. <P>SOLUTION: A crucible 1 is housed in a treating chamber 7 and a solid raw material treating liquid 8 is flown into the treating chamber 7 before or after the crucible 1 is housed in the treating chamber 7. A seed substrate 2 supported with a seed substrate support 3, a crystal substrate 10 generated on the seed substrate 2 and a solid raw material 4 covering the seed substrate 2 and the crystal substrate 10 are housed in the crucible 1 and then the crucible 1 is cut at a cutting part. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、結晶製造方法および結晶製造装置に関するものである。 The present invention relates to a crystal manufacturing method and a crystal manufacturing apparatus.

化合物半導体、そのなかでも窒化ガリウム（ＧａＮ）などのＩＩＩ族元素窒化物（以下、ＩＩＩ族窒化物、ＩＩＩ族窒化物半導体、またはＧａＮ系半導体という場合がある）は、青色や紫外光を発光する半導体素子の材料として注目されている。青色レーザダイオード(ＬＤ)は高密度光ディスクやディスプレイなどに応用され、青色発光ダイオード（ＬＥＤ）はディスプレイや照明などに応用されている。また、紫外線ＬＤはバイオテクノロジなどへの応用が期待され、紫外線ＬＥＤは蛍光灯の紫外線源として期待されている。 Compound semiconductors, among them Group III element nitrides such as gallium nitride (GaN) (hereinafter sometimes referred to as Group III nitrides, Group III nitride semiconductors, or GaN-based semiconductors) emit blue or ultraviolet light. It is attracting attention as a material for semiconductor elements. Blue laser diodes (LDs) are applied to high-density optical discs and displays, and blue light-emitting diodes (LEDs) are applied to displays and lighting. Further, ultraviolet LD is expected to be applied to biotechnology and the like, and ultraviolet LED is expected to be an ultraviolet source of fluorescent lamps.

ＬＤやＬＥＤ用のＩＩＩ族窒化物半導体（例えば、ＧａＮ）の基板は、通常、サファイア基板上に、気相エピタキシャル成長法を用いて、ＩＩＩ族窒化物単結晶をヘテロエピタキシャル成長させることによって形成されている。気相成長方法としては、有機金属化学気相成長法（ＭＯＣＶＤ法）、水素化物気相成長法（ＨＶＰＥ法）、分子線エピタキシー法（ＭＢＥ法）などがある。 A group III nitride semiconductor (for example, GaN) substrate for an LD or LED is usually formed by heteroepitaxially growing a group III nitride single crystal on a sapphire substrate using a vapor phase epitaxial growth method. . Examples of the vapor deposition method include a metal organic chemical vapor deposition method (MOCVD method), a hydride vapor deposition method (HVPE method), a molecular beam epitaxy method (MBE method), and the like.

一方、気相エピタキシャル成長ではなく、液相で結晶成長を行う方法も検討されてきた。ＧａＮやＡｌＮなどのＩＩＩ族窒化物単結晶の融点における窒素の平衡蒸気圧は１万気圧以上であるため、従来、窒化ガリウムを液相で育成させるためには１２００℃で８０００気圧（８０００×１．０１３２５×１０^５Ｐａ）の条件が必要とされてきた。これに対し、近年、Ｎａなどのアルカリ金属を用いることで、７５０℃、５０気圧（５０×１．０１３２５×１０^５Ｐａ）という比較的低温低圧でＧａＮを合成できることが明らかにされた。 On the other hand, a method of performing crystal growth in a liquid phase instead of vapor phase epitaxial growth has been studied. Since the equilibrium vapor pressure of nitrogen at the melting point of a group III nitride single crystal such as GaN or AlN is 10,000 atmospheres or more, conventionally, gallium nitride is grown at 1200 ° C. at 8000 atmospheres (8000 × 1) in the liquid phase. .01325 × 10 ⁵ Pa) has been required. On the other hand, in recent years, it has been clarified that GaN can be synthesized at a relatively low temperature and low pressure of 750 ° C. and 50 atm (50 × 1.01325 × 10 ⁵ Pa) by using an alkali metal such as Na.

最近では、アンモニアを含む窒素ガス雰囲気下においてＧａとＮａとの混合物を８００℃、５０気圧（５０×１．０１３２５×１０^５Ｐａ）で溶融させ、この融解液を用いて９６時間の育成時間で、最大結晶サイズが１．２ｍｍ程度の単結晶が得られている（例えば、特許文献１参照）。 Recently, a mixture of Ga and Na was melted at 800 ° C. and 50 atm (50 × 1.01325 × 10 ⁵ Pa) in a nitrogen gas atmosphere containing ammonia, and this melt was used for a growth time of 96 hours. A single crystal having a maximum crystal size of about 1.2 mm is obtained (for example, see Patent Document 1).

従来の液相成長によるＩＩＩ族元素窒化物結晶製造装置を図８に示す。説明のため、ＧａＮ結晶を作製する場合を例に取る。１４は原料ガスである窒素ガスを供給する原料ガス供給装置、１５は結晶育成を行うための密閉性の結晶成長容器、１６は原料ガス供給装置１４と結晶成長容器１５とを接続する接続配管、２４は加熱手段を具備した育成炉である。接続配管１６は、圧力調整器１７、ストップバルブ１８、リーク弁１９、切り離し部分２０を有している。育成炉２４は、断熱材２１とヒータ２２とを備える電気炉として構成されており、熱電対２３により温度管理され、全体を揺動可能である。 FIG. 8 shows a conventional group III element nitride crystal manufacturing apparatus using liquid phase growth. For the sake of explanation, the case of producing a GaN crystal is taken as an example. 14 is a raw material gas supply device for supplying nitrogen gas, which is a raw material gas, 15 is a hermetic crystal growth vessel for crystal growth, 16 is a connecting pipe for connecting the raw material gas supply device 14 and the crystal growth vessel 15, Reference numeral 24 denotes a growth furnace equipped with heating means. The connection pipe 16 includes a pressure regulator 17, a stop valve 18, a leak valve 19, and a disconnecting portion 20. The growth furnace 24 is configured as an electric furnace including a heat insulating material 21 and a heater 22, is temperature-controlled by a thermocouple 23, and can swing as a whole.

かかる構成の製造装置において、坩堝１内に、種基板２をセットする。この種基板２を、坩堝１の底面に平行な向きに配置する。また、原料である金属ガリウムとＮａとを所定の量だけ秤量し、坩堝１内にセットする。 In the manufacturing apparatus having such a configuration, the seed substrate 2 is set in the crucible 1. This seed substrate 2 is arranged in a direction parallel to the bottom surface of the crucible 1. Further, a predetermined amount of metal gallium and Na as raw materials are weighed and set in the crucible 1.

そして坩堝１を結晶成長容器１５に挿入し、さらにこの結晶成長容器１５を、育成炉２４内にセットし、接続パイプ１６を介して原料ガス供給装置に接続させて、育成温度８５０℃、窒素雰囲気圧力５０気圧（５０×１．０１３２５×１０^５Ｐａ）とし、Ｇａ／Ｎａ融解液（以下、原料液という）に窒素ガスを溶解させて、種基板２の上にＧａＮ単結晶の育成を行う。 Then, the crucible 1 is inserted into the crystal growth vessel 15, and this crystal growth vessel 15 is set in the growth furnace 24 and connected to the source gas supply device via the connection pipe 16, and the growth temperature is 850 ° C. and the nitrogen atmosphere. A pressure of 50 atm (50 × 1.01325 × 10 ⁵ Pa) is applied, nitrogen gas is dissolved in a Ga / Na melt (hereinafter referred to as a raw material solution), and a GaN single crystal is grown on the seed substrate 2.

作製されたＧａＮ単結晶は、固化した原料液とともに坩堝の中にあるので、この状態からＧａＮ単結晶を取り出さなければならない。 Since the produced GaN single crystal is in the crucible together with the solidified raw material solution, the GaN single crystal must be taken out from this state.

図９から図１０に、図８の製造装置で製造したＧａＮ単結晶の取り出し方法を示す。室温で坩堝１を結晶成長容器１５から取り出した状態では、原料液は固体状態の固体原料４となっており、そのままでは種基板２の上に成長させたＧａＮ単結晶を取り出すことが出来ない。そこで、図９に示すように固体原料処理液８が満たされている処理容器７に坩堝１を入れ、固体原料処理液８と固体原料４を化学反応させることにより固体原料４を上面より溶かしていく。ここで、原料としてＧａ／Ｎａ処理液を使用する場合は、固体原料処理液８としてエタノールを使用することにより、反応気体９として水素を発生させながら、固体原料４を溶かすことが可能となる。 9 to 10 show a method for extracting a GaN single crystal manufactured by the manufacturing apparatus of FIG. In a state where the crucible 1 is taken out from the crystal growth vessel 15 at room temperature, the raw material liquid is a solid raw material 4, and the GaN single crystal grown on the seed substrate 2 cannot be taken out as it is. Therefore, as shown in FIG. 9, the crucible 1 is placed in a processing vessel 7 filled with the solid raw material treatment liquid 8, and the solid raw material treatment liquid 8 and the solid raw material 4 are chemically reacted to dissolve the solid raw material 4 from the upper surface. Go. Here, when a Ga / Na treatment liquid is used as a raw material, it is possible to dissolve the solid raw material 4 while generating hydrogen as the reaction gas 9 by using ethanol as the solid raw material treatment liquid 8.

また、原料液は坩堝１の底面と種基板２との間に入り込んでおり、薄い層状に固体原料４が存在している。図９に示すように、ＧａＮ単結晶より上側の固体原料４が処理されたあとは、種基板２の外周側から固体原料処理液９が回り込み、坩堝１の底面とＧａＮ単結晶２の間に存在する固体原料４を溶かしていく。そして、固体原料４が全て処理されるとＧａＮ単結晶２と坩堝１が分離され、ＧａＮ単結晶２を坩堝１から取り出すことが可能となる。 Further, the raw material liquid enters between the bottom surface of the crucible 1 and the seed substrate 2, and the solid raw material 4 exists in a thin layer shape. As shown in FIG. 9, after the solid raw material 4 above the GaN single crystal is processed, the solid raw material treatment liquid 9 circulates from the outer peripheral side of the seed substrate 2, and between the bottom surface of the crucible 1 and the GaN single crystal 2. The existing solid raw material 4 is melted. When all the solid raw materials 4 are processed, the GaN single crystal 2 and the crucible 1 are separated, and the GaN single crystal 2 can be taken out from the crucible 1.

特開２００２−２９３６９６号公報JP 2002-293696 A

しかしながら、前記従来の構成では、坩堝からＧａＮ単結晶を除去する際、固化した固体原料をエタノールなどの固体原料処理液で処理して取り除くため、坩堝の底部にＧａＮ単結晶があるために長時間を要していた。特に、種基板の下方底面に形成された種基板と坩堝底面との隙間に形成された固体原料は、種基板の下方底面全体が坩堝の内底面に当接した状態になっているので、固体原料処理液が接する固体原料の表面範囲がこの隙間の垂直方向の狭い範囲に限られるため、処理に時間がかかってしまう。さらには、坩堝の内底面に当接した固体原料の面積が大きいので、この範囲の固体原料を溶解するのに数日かかってしまっていて、生産性が悪いという問題があった。 However, in the conventional configuration, when the GaN single crystal is removed from the crucible, the solidified solid material is removed by treatment with a solid raw material treatment liquid such as ethanol. Needed. In particular, the solid raw material formed in the gap between the seed substrate formed on the bottom surface of the seed substrate and the bottom surface of the crucible is in a state where the entire bottom surface of the seed substrate is in contact with the inner bottom surface of the crucible. Since the surface range of the solid raw material in contact with the raw material treatment liquid is limited to a narrow range in the vertical direction of this gap, the processing takes time. Furthermore, since the area of the solid raw material in contact with the inner bottom surface of the crucible is large, it took several days to dissolve the solid raw material in this range, and there was a problem that productivity was poor.

本発明は、前記従来の課題を解決するもので、結晶を固体原料から短時間で取り出すことができる生産性が高い結晶製造方法およびその装置を提供することを目的とする。 SUMMARY OF THE INVENTION The present invention solves the above-described conventional problems, and an object thereof is to provide a crystal production method and an apparatus thereof with high productivity capable of taking out crystals from a solid raw material in a short time.

そしてこの目的を達成するために本発明は、処理容器内に坩堝を収納させ、この坩堝を処理容器内に入れる前、あるいは、入れた後に、前記処理容器内に固体原料処理液を流入させ、前記坩堝内には、種基板と、この種基板上に生成された結晶基板と、これらの種基板および結晶基板を覆った固体原料とが収納された状態とし、前記坩堝の底面を取り外した状態とした構成にした。 And in order to achieve this object, the present invention accommodates a crucible in a processing container, and before or after putting this crucible in the processing container, allows the solid raw material processing liquid to flow into the processing container, In the crucible, a seed substrate, a crystal substrate generated on the seed substrate, and a solid material covering the seed substrate and the crystal substrate are accommodated, and a bottom surface of the crucible is removed. The configuration was as follows.

これにより所期の目的を達成するものである。 This achieves the intended purpose.

以上のように本発明は、処理容器内に坩堝を収納させ、この坩堝を処理容器内に入れる前、あるいは、入れた後に、前記処理容器内に固体原料処理液を流入させ、前記坩堝内には、種基板と、この種基板上に生成された結晶基板と、これらの種基板および結晶基板を覆った固体原料とが収納された状態とし、前記坩堝の底面を取り外した状態としたものであるので、生産性を高くすることができるものである。 As described above, according to the present invention, the crucible is accommodated in the processing container, and before or after the crucible is placed in the processing container, the solid raw material processing liquid is allowed to flow into the processing container, and the crucible is placed in the crucible. Is a state in which a seed substrate, a crystal substrate generated on the seed substrate, and a solid material covering the seed substrate and the crystal substrate are stored, and a bottom surface of the crucible is removed. Therefore, productivity can be increased.

すなわち、坩堝の底面が取り外されているので、坩堝の底部からも固体原料処理液を導入できるので、固体原料処理液が固体原料に接する範囲が広くなり、固体原料を速く溶解させることができる。 That is, since the bottom of the crucible is removed, the solid raw material treatment liquid can be introduced also from the bottom of the crucible, so the range in which the solid raw material treatment liquid is in contact with the solid raw material is widened, and the solid raw material can be dissolved quickly.

しかも、最も時間がかかる種基板と坩堝底面の間に存在する固体原料を、初期から溶解可能であるので、数時間で種基板を取り出すことが出来るようになり、生産性を高くすることができるのである。 Moreover, since the solid raw material existing between the seed substrate and the bottom of the crucible, which takes the longest time, can be dissolved from the beginning, the seed substrate can be taken out in a few hours, and the productivity can be increased. It is.

実施の形態１の結晶製造装置を用いた初期の固体原料処理工程図Initial solid raw material treatment process using the crystal production apparatus of the first embodiment 実施の形態１の結晶製造装置の一部の組図Partial assembly diagram of crystal manufacturing apparatus according to Embodiment 1 実施の形態１の物結晶製造装置の一部の断面図Sectional drawing of a part of physical crystal manufacturing apparatus of Embodiment 1 実施の形態１の坩堝固定台の斜面・断面図Slope / cross-sectional view of crucible fixing base of Embodiment 1 実施の形態１の結晶製造装置を用いた後期の固体原料処理工程図Late solid raw material treatment process using the crystal production apparatus of the first embodiment 実施の形態２の結晶製造装置の一部の断面図Partial sectional view of the crystal manufacturing apparatus of the second embodiment 実施の形態３の結晶製造装置の断面図Sectional drawing of the crystal manufacturing apparatus of Embodiment 3 一般的なIII族窒化物単結晶製造方法を行う装置の概略構成断面図Schematic configuration cross-sectional view of an apparatus for performing a general group III nitride single crystal manufacturing method 従来の初期の固体原料処理工程図Conventional initial solid raw material treatment process diagram 従来の後期の固体原料処理工程図Conventional late-stage solid material treatment process diagram

以下に本発明の物結晶製造方法および装置の実施の形態を図面とともに詳細に説明する。 Embodiments of the method and apparatus for producing a product crystal of the present invention will be described below in detail with reference to the drawings.

（実施の形態１）
図２に、本発明の実施の形態における結晶製造製造装置の一部を示す。図２に示すように、アルミナ等の耐熱材料で作成されたカップ状の坩堝１と、同様に耐熱材料で作成された支持体３と、表面に窒化物結晶を成長させる種基板２で構成されている。坩堝１の坩堝内底面１２に種基板支持体３を設置し、種基板支持体３によって種基板２を所定の高さに保持している。 (Embodiment 1)
FIG. 2 shows a part of the crystal manufacturing and manufacturing apparatus according to the embodiment of the present invention. As shown in FIG. 2, it is composed of a cup-shaped crucible 1 made of a heat-resistant material such as alumina, a support 3 similarly made of a heat-resistant material, and a seed substrate 2 on which a nitride crystal is grown. ing. The seed substrate support 3 is installed on the crucible inner bottom surface 12 of the crucible 1, and the seed substrate 2 is held at a predetermined height by the seed substrate support 3.

次に、結晶の製造方法を説明する。まず、図２に示す坩堝１に原料である結晶元素材料（例えば、ガリウム、アルミニウム、インジウム）とアルカリ金属（例えば、リチウム、ナトリウム、カリウム）またはアルカリ土類金属（例えば、カルシウム、ストロンチウム、バリウム、ラジウム、ベリリウム、マグネシウム）を供給する。これらアルカリ金属およびアルカリ土類金属は、１種類を単独で用いてもよいし、２種類以上を併用してもよい。III族元素材料およびアルカリ金属の秤量や取り扱いは、アルカリ金属の酸化や水分吸着を回避するために、窒素ガスやアルゴンガスやネオンガスなどで置換されたグローブボックス中で行うことが好ましい。 Next, a method for producing a crystal will be described. First, a crystal element material (for example, gallium, aluminum, indium) and an alkali metal (for example, lithium, sodium, potassium) or an alkaline earth metal (for example, calcium, strontium, barium, Supply radium, beryllium, magnesium). These alkali metals and alkaline earth metals may be used alone or in combination of two or more. It is preferable to weigh and handle the group III element material and the alkali metal in a glove box substituted with nitrogen gas, argon gas, neon gas or the like in order to avoid alkali metal oxidation or moisture adsorption.

次に、図８に示す結晶成長容器１５に坩堝１挿入し、密閉状態でグローブボックスから取り出し、結晶成長容器１５を育成炉２４内に固定する。その後、結晶成長容器１５と接続管１６を接続し、ストップバルブ１８を開放して、原料ガス供給装置１４から結晶成長容器１５に原料ガスを注入する。 Next, the crucible 1 is inserted into the crystal growth vessel 15 shown in FIG. 8, taken out from the glove box in a sealed state, and the crystal growth vessel 15 is fixed in the growth furnace 24. Thereafter, the crystal growth vessel 15 and the connecting pipe 16 are connected, the stop valve 18 is opened, and the source gas is injected from the source gas supply device 14 into the crystal growth vessel 15.

そして、熱電対２３や圧力調整器１７によって、育成炉２４の温度および育成雰囲気の圧力を制御しながら加圧・加熱を行う。なお、結晶を生成するための原料の溶融および育成の条件は、原料である結晶材料やアルカリ金属の成分、および原料ガスの成分およびその圧力に依存するが、例えば、温度は７００℃〜１１００℃、好ましくは７００℃〜９００℃の低温が用いられる。圧力は２０気圧（２０×１．０１３２５×１０５Ｐａ）以上、好ましくは３０気圧（５×１．０１３２５×１０５Ｐａ）〜１００気圧（１００×１．０１３２５×１０５Ｐａ）が用いられる。 Then, pressurization / heating is performed by controlling the temperature of the growth furnace 24 and the pressure of the growth atmosphere by the thermocouple 23 and the pressure regulator 17. The conditions for melting and growing the raw material for generating crystals depend on the raw crystal material and the alkali metal component, the raw material gas component and the pressure thereof. For example, the temperature is 700 ° C. to 1100 ° C. Preferably, a low temperature of 700 ° C. to 900 ° C. is used. The pressure is 20 atmospheres (20 × 1.01325 × 105 Pa) or more, preferably 30 atmospheres (5 × 1.01325 × 105 Pa) to 100 atmospheres (100 × 1.01325 × 105 Pa).

このように、育成温度に昇温することにより、坩堝１内で、結晶元素材料／アルカリ金属の融解液、つまり原料液が形成され、この原料液中に原料ガスが溶け込み、結晶元素材料と原料ガスとが反応して、種基板２の上にIII族元素窒化物単結晶が育成される。 In this way, by raising the temperature to the growth temperature, a crystal element material / alkali metal melt, that is, a raw material liquid is formed in the crucible 1, and the raw material gas is dissolved in the raw material liquid. The group reacts with the gas to grow a group III element nitride single crystal on the seed substrate 2.

所定の時間が経過して結晶基板の育成が終了した後に、育成炉２４を常圧・常温に戻し、結晶成長容器１５と接続管１１を取り外し、育成炉２４から結晶成長容器１５を取り出す。さらに、結晶成長容器２４から坩堝１を取り出す。 After the growth of the crystal substrate is completed after a predetermined time has elapsed, the growth furnace 24 is returned to normal pressure and room temperature, the crystal growth vessel 15 and the connecting tube 11 are removed, and the crystal growth vessel 15 is taken out from the growth furnace 24. Further, the crucible 1 is taken out from the crystal growth vessel 24.

ここで図３に示す、結晶成長後の坩堝１内の原料液中には結晶元素材料は５〜３０％程度しか残存せず、殆どがアルカリ金属である。また、原料液は常温では固体原料４として存在し、結晶基板が一体に形成された種基板２や種基板支持体３を覆っている。この坩堝１を切断部５の位置で、旋盤やワイヤーカットなどの装置を用いて輪切りにして、坩堝１の坩堝内底面１２を取り外す。このとき、切断部５の位置に分離溝１１を形成しておくと、切断時間が短くなるとともに、切断時に坩堝１に加わる応力が小さくなり、種基板２に過剰な応力が加わって破損することが無い。また、外部から目視で切断部５を確認できるので、誤って種基板２を切断することが無い。分離溝１０をＶ形状にすると、溝形成が容易であるとともに、目視しやすい利点があるため有効であるが、Ｖ形状に限定するものではなく、凹形状やＵ形状でも良い。 Here, only about 5 to 30% of the crystal element material remains in the raw material liquid in the crucible 1 after crystal growth shown in FIG. 3, and most of the element is alkali metal. The raw material liquid exists as a solid raw material 4 at room temperature, and covers the seed substrate 2 and the seed substrate support 3 on which the crystal substrate is integrally formed. The crucible 1 is cut into a round shape using a lathe or a wire cutting device at the position of the cutting portion 5, and the crucible inner bottom surface 12 of the crucible 1 is removed. At this time, if the separation groove 11 is formed at the position of the cutting portion 5, the cutting time is shortened, the stress applied to the crucible 1 during cutting is reduced, and the seed substrate 2 is damaged due to excessive stress. There is no. Moreover, since the cutting part 5 can be visually confirmed from the outside, the seed substrate 2 is not cut by mistake. If the separation groove 10 is formed in a V shape, it is effective because it is easy to form the groove and has an advantage of being easily visible, but it is not limited to the V shape, and may be a concave shape or a U shape.

次に、図１に示すように結晶基板１０が一体に形成された種基板２を取り出すために固体原料４の処理を行う。切断した坩堝１を処理容器７に設置した坩堝固定台６に固定し、水酸基（-OH）を含む任意の固体原料処理液８、たとえばエタノール、メタノール、イソプロピルアルコールなどのアルコール類や水などを注入する。固体原料４を固体原料処理液８に浸漬させることで、処理液中に溶解する金属アルコキシド（水を用いる場合は金属水酸化物）と反応気体９である水素を生成させて、固体原料４を処理する。坩堝１を切断しているため、固体原料４の上面だけでなく、切断部５（下面側）も固体原料処理液８と接するため、処理時間の短縮が可能となる。 Next, as shown in FIG. 1, the solid material 4 is processed in order to take out the seed substrate 2 on which the crystal substrate 10 is integrally formed. The cut crucible 1 is fixed to a crucible fixing base 6 installed in a processing vessel 7, and an arbitrary solid raw material treatment liquid 8 containing a hydroxyl group (-OH), for example, alcohols such as ethanol, methanol, isopropyl alcohol, or water is injected. To do. By immersing the solid raw material 4 in the solid raw material treatment liquid 8, a metal alkoxide (a metal hydroxide if water is used) and hydrogen as a reaction gas 9 are generated in the treatment liquid, and the solid raw material 4 is obtained. To process. Since the crucible 1 is cut, not only the upper surface of the solid raw material 4 but also the cutting part 5 (lower surface side) is in contact with the solid raw material treatment liquid 8, so that the processing time can be shortened.

ここで、図４に示すように、坩堝固定台６は複数の支持脚６ａと坩堝を支持する支持部６ｂを有する。この坩堝固定台６の支持部６ｂで坩堝１の外周下面側を支持している。この坩堝固定台６は、複数の支持脚６ａの間に空間が設けられているので、固体原料処理液８を切断部５に供給する事が可能となっている。なお、種基板支持体支持部６ｃを設ける事により、固体原料４が全て溶解した後に種基板支持体３や種基板２及び結晶基板１０が処理液７の底面に落下するのを防ぐ事が可能となり、結晶基板１０が損傷するのを防ぐ事ができる。なお、図４では１部品で坩堝固定台６を形成しているが、複数部品で形成しても良い。 Here, as shown in FIG. 4, the crucible fixing base 6 has a plurality of support legs 6a and a support portion 6b for supporting the crucible. The support 6 b of the crucible fixing base 6 supports the outer peripheral lower surface side of the crucible 1. Since this crucible fixing base 6 is provided with a space between the plurality of support legs 6 a, the solid raw material treatment liquid 8 can be supplied to the cutting part 5. In addition, it is possible to prevent the seed substrate support 3, the seed substrate 2, and the crystal substrate 10 from falling on the bottom surface of the processing liquid 7 after the solid raw material 4 is completely dissolved by providing the seed substrate support support 6 c. Thus, the crystal substrate 10 can be prevented from being damaged. In FIG. 4, the crucible fixing base 6 is formed by one component, but may be formed by a plurality of components.

固体原料４の処理が進むと、図５に示すように種基板２と種基板支持台３の間の隙間に固体原料４が残るが、図１０に示す従来例に比べて、隙間に残る固体原料４が少ない。また、種基板２の外周側からだけでなく種基板支持台３の無い周側からも固体原料処理液８が浸漬するので、処理時間の更なる短縮が可能となる。 As the processing of the solid raw material 4 proceeds, the solid raw material 4 remains in the gap between the seed substrate 2 and the seed substrate support 3 as shown in FIG. 5, but the solid remaining in the gap as compared with the conventional example shown in FIG. There are few raw materials 4. Further, since the solid raw material treatment liquid 8 is immersed not only from the outer peripheral side of the seed substrate 2 but also from the peripheral side where the seed substrate support 3 is not present, the processing time can be further shortened.

固体原料４の処理が完全に終了すると、結晶基板１０が一体に形成された種基板２と坩堝１及び種基板支持台４は分離されているので、結晶基板１０及び種基板２を坩堝１から取り出すことが可能となる。 When the processing of the solid raw material 4 is completed, the seed substrate 2, the crucible 1, and the seed substrate support 4 on which the crystal substrate 10 is integrally formed are separated, so that the crystal substrate 10 and the seed substrate 2 are removed from the crucible 1. It can be taken out.

内径９０mmの坩堝１に直径５０mmの種基板２を入れて、原料としてガリウムとナトリウムを使用してＧａＮ単結晶を育成し、固体原料４の上面と結晶基板１０上面の距離が１０mmである固体原料４をエタノール処理する実験を行った。従来例では種基板２や結晶基板１０の周りの固体原料４を処理する時間（図９から図１０になる時間）が４時間、坩堝１の底面１５と種基板２との隙間に存在する固体原料４を処理するのに５０時間ほどかかる。それに対し本実施例では、種基板２周りの固体原料４を処理する時間（図１から図５になる時間）が３時間、坩堝１の底面１５と種基板支持台３との隙間に存在する固体原料４を処理するのに５時間程度で可能となり、大幅な時間短縮が可能となった。 A seed substrate 2 having a diameter of 50 mm is placed in a crucible 1 having an inner diameter of 90 mm, a GaN single crystal is grown using gallium and sodium as raw materials, and the distance between the upper surface of the solid material 4 and the upper surface of the crystal substrate 10 is 10 mm. An experiment was conducted in which 4 was treated with ethanol. In the conventional example, the time for processing the solid raw material 4 around the seed substrate 2 and the crystal substrate 10 (the time from FIG. 9 to FIG. 10) is 4 hours, and the solid existing in the gap between the bottom surface 15 of the crucible 1 and the seed substrate 2. It takes about 50 hours to process the raw material 4. In contrast, in this embodiment, the time for processing the solid raw material 4 around the seed substrate 2 (the time from FIG. 1 to FIG. 5) is 3 hours, which is present in the gap between the bottom surface 15 of the crucible 1 and the seed substrate support 3. It took about 5 hours to process the solid raw material 4, and the time could be greatly reduced.

（実施の形態２）
本発明の実施の形態２の結晶製造装置を、図６に示す。図６において、実施の形態１の構成と異なる所は、種基板支持部１３を坩堝１の坩堝内底面１２を加工して、坩堝１と一体で形成された点である。このように、種基板支持部１３を坩堝１と一体形成しても、実施の形態１と同様の効果が得られ、結晶基板１０や種基板２を短時間で取り出す事ができる。さらには、坩堝と一体形成されているので、部品点数を減少でき、生産性を高くする事ができる。 (Embodiment 2)
A crystal manufacturing apparatus according to Embodiment 2 of the present invention is shown in FIG. In FIG. 6, the difference from the configuration of the first embodiment is that the seed substrate support portion 13 is formed integrally with the crucible 1 by processing the bottom surface 12 in the crucible 1. Thus, even if the seed substrate support portion 13 is formed integrally with the crucible 1, the same effect as in the first embodiment can be obtained, and the crystal substrate 10 and the seed substrate 2 can be taken out in a short time. Furthermore, since it is integrally formed with the crucible, the number of parts can be reduced and the productivity can be increased.

なお、実施の形態１の図３の種基板支持体３は円筒形状、実施の形態２の図６種基板支持部１３は円盤形状としたが、種基板支持台３を円盤形状、種基板支持部１３を円筒形状としても良い。さらに、円形状ではなく四角などの他の外・内形状にすることも可能である。 Although the seed substrate support 3 in FIG. 3 of the first embodiment has a cylindrical shape and the seed substrate support 13 in FIG. 6 of the second embodiment has a disk shape, the seed substrate support base 3 has a disk shape and a seed substrate support. The part 13 may be cylindrical. Furthermore, it is possible to use other outer / inner shapes such as a square instead of a circular shape.

（実施の形態３）
本発明の実施の形態３の結晶製造装置を、図７に示す。図７において、実施の形態1の構成と異なるところは坩堝１を処理容器７の内底面に対して、傾斜させている点である。このように傾斜させる事により、実施の形態１のように坩堝固定台６に複数の支持脚を設けなくても、固体原料処理液８を切断部５に供給する事が可能となっている。さらに、固体原料処理液８を切断部５の全面に供給可能であるので、処理速度の短縮をさらに図る事ができ、結晶基板１０や種基板２を原料液の中から短時間で取り出すことができる。 (Embodiment 3)
A crystal manufacturing apparatus according to Embodiment 3 of the present invention is shown in FIG. In FIG. 7, the difference from the configuration of the first embodiment is that the crucible 1 is inclined with respect to the inner bottom surface of the processing vessel 7. By inclining in this way, the solid raw material processing liquid 8 can be supplied to the cutting unit 5 without providing a plurality of support legs on the crucible fixing base 6 as in the first embodiment. Furthermore, since the solid raw material treatment liquid 8 can be supplied to the entire surface of the cutting section 5, the processing speed can be further reduced, and the crystal substrate 10 and the seed substrate 2 can be taken out of the raw material liquid in a short time. it can.

本発明にかかる結晶製造方法及び装置は、液相成長にて形成したＧａＮ単結晶などのＩＩＩ族元素窒化物結晶を原料液の中から短時間で取り出すことに効果を有し、青色レーザーダイオードや青色発光ダイオードなどに使用される半導体素子の基板製造に有用である。 The crystal manufacturing method and apparatus according to the present invention have an effect of taking out a group III element nitride crystal such as a GaN single crystal formed by liquid phase growth from a raw material solution in a short time, It is useful for manufacturing a substrate of a semiconductor element used for a blue light emitting diode or the like.

１坩堝
２種基板
３種基板支持体
４固体原料
５切断部
６坩堝固定台
６ａ支持脚
６ｂ支持部
６ｃ種基板支持体支持部
７処理容器
８固体原料処理液
９反応気体
１０結晶基板
１１分離溝
１２坩堝内底面
１３種基板支持部
１４原料ガス供給装置
１５結晶成長容器
１６接続管
１７圧力調整器
１８ストップバルブ
１９リーク弁
２０切り離し部
２１断熱材
２２ヒータ
２３熱伝対
２４育成炉 DESCRIPTION OF SYMBOLS 1 Crucible 2 Seed substrate 3 Seed substrate support 4 Solid raw material 5 Cutting part 6 Crucible fixing stand 6a Support leg 6b Support part 6c Seed substrate support support part 7 Processing container 8 Solid raw material process liquid 9 Reactive gas 10 Crystal substrate 11 Separation groove 12 bottom surface of crucible 13 seed substrate support unit 14 raw material gas supply device 15 crystal growth vessel 16 connection pipe 17 pressure regulator 18 stop valve 19 leak valve 20 separation unit 21 heat insulating material 22 heater 23 thermocouple 24 growth furnace

Claims

As a post-process for growing a crystal, a method for producing a crystal in which the crystal is extracted from a solid raw material,
A crucible is housed in a processing container, and before or after the crucible is placed in the processing container, a solid raw material processing solution is allowed to flow into the processing container, and a seed substrate and the seed are contained in the crucible. A crystal manufacturing method in which a crystal substrate generated on a substrate, a seed substrate and a solid material covering the crystal substrate are stored, and a bottom surface of the crucible is removed.

A crucible fixing base that supports the crucible with respect to the inner bottom surface of the processing container is provided, the crucible fixing base has a plurality of crucible fixing base support legs arranged at predetermined intervals, and each crucible fixing base support leg The crystal manufacturing method according to claim 1, wherein the outer peripheral lower surface side of the crucible is supported by a support portion.

The crystal manufacturing method according to claim 1, further comprising: a support body that holds the seed substrate at a predetermined height with respect to an inner bottom surface of the processing container, wherein the outer peripheral lower surface side of the seed substrate is supported by the support body. .

The crystal manufacturing method according to claim 1, wherein the crucible includes a tilting unit that tilts the crucible with respect to an inner bottom surface of the processing container.

The crystal manufacturing according to any one of claims 1 to 4, wherein a separation groove that is parallel to the bottom surface is provided on a side surface of the crucible, and the bottom surface of the crucible is removed by cutting along the separation groove. Method.

The crystal manufacturing method according to claim 5, wherein the separation groove is formed so as to be continuously connected to a side surface of the crucible.

The crystal manufacturing method according to claim 5, wherein a cross section of the separation groove is V-shaped.

The method for producing a crystal according to claim 3, wherein the height from the inner bottom surface of the crucible to the support portion of the support leg is higher than the thickness of the seed substrate.

The crystal manufacturing method according to claim 1, wherein the seed substrate is a gallium nitride substrate.

A crystal substrate manufacturing apparatus for use in the method for manufacturing a crystal substrate according to claim 1, wherein the processing vessel table, an inflow means for allowing the solid raw material processing liquid to flow into the processing vessel, and the crucible And a take-out means for taking out the crystal substrate and the seed substrate from the processing container after the solid raw material is dissolved in the solid raw material treatment liquid.