JP4586154B2 - Gallium arsenide single crystal manufacturing equipment - Google Patents

Gallium arsenide single crystal manufacturing equipment Download PDF

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JP4586154B2
JP4586154B2 JP2006172553A JP2006172553A JP4586154B2 JP 4586154 B2 JP4586154 B2 JP 4586154B2 JP 2006172553 A JP2006172553 A JP 2006172553A JP 2006172553 A JP2006172553 A JP 2006172553A JP 4586154 B2 JP4586154 B2 JP 4586154B2
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single crystal
sealant
carrier concentration
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良一 中村
俊明 大橋
隆一 鳥羽
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Dowa Electronics Materials Co Ltd
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Description

本発明はIII−Ｖ族化合物半導体単結晶の育成方法において、特にＢ2Ｏ3を液体封止剤とし、Ｓｉをドーパントとして用いるＧａＡｓ単結晶育成方法に関してドーパント濃度が所望範囲の濃度に精度よく制御された単結晶およびその単結晶育成技術に関する。 The present invention relates to a method for growing a III-V compound semiconductor single crystal, and in particular, for a GaAs single crystal growth method using B 2 O 3 as a liquid sealant and Si as a dopant, the dopant concentration is accurately controlled within a desired range. The present invention relates to a single crystal and a technique for growing the single crystal.

III−Ｖ族化合物半導体の単結晶は受発光素子、高速演算素子、マイクロ波素子等に利用されており、その用途により単結晶に種々の物質を添加して利用されている。   Single crystals of III-V compound semiconductors are used for light emitting / receiving elements, high-speed computing elements, microwave elements, and the like, and are used by adding various substances to the single crystal depending on the application.

ｎ型導電性ＧａＡｓ単結晶は一般にシリコン（Ｓｉ）がドーパントとして用いられ、結晶中の転位密度を小さくするため横型ボート法や縦型ボート法を用いて製造されている。特に縦型ボート法においては（１００）方位の結晶成長が育成可能であるばかりでなく、円形で大口径の結晶が得られる利点があり、縦型温度傾斜法（ＶＧＦ法）や縦型ブリッジマン法（ＶＢ法）による結晶成長が行われている。   In general, an n-type conductive GaAs single crystal uses silicon (Si) as a dopant, and is manufactured using a horizontal boat method or a vertical boat method in order to reduce the dislocation density in the crystal. In particular, the vertical boat method has the advantage that not only crystal growth in the (100) direction can be grown but also a circular and large-diameter crystal can be obtained. The vertical temperature gradient method (VGF method) and the vertical bridge man Crystal growth is performed by the method (VB method).

Ｖ族元素のＡｓは揮発成分であるため、結晶からの解離や分解を防ぐ目的等で封止剤として酸化ホウ素（Ｂ2Ｏ3）が用いられている。Ｂ2Ｏ3を液体封止剤として用いる場合、ドーパントであるＳｉがＢ2Ｏ3と反応して酸化シリコン（ＳｉＯ2またはＳｉＯ）を形成し結晶中のＳｉ濃度が制御しにくくなるため、本発明者らはＳｉ濃度を制御する方法として特公平３−５７０７９号で、予めＳｉ酸化物をドープしたＢ2Ｏ3を用いる発明を提供した。 As As of the group V element is a volatile component, boron oxide (B 2 O 3 ) is used as a sealing agent for the purpose of preventing dissociation and decomposition from the crystal. When B 2 O 3 is used as a liquid sealant, Si as a dopant reacts with B 2 O 3 to form silicon oxide (SiO 2 or SiO), making it difficult to control the Si concentration in the crystal. It in Kokoku No. 3-57079 as a method for controlling the Si concentration, provided the invention using B 2 O 3 doped with previously Si oxide.

この発明を用いれば、ＶＢ法またはＶＧＦ法等の縦型ボート法においても再現性よくＳｉ濃度つまりキャリア濃度が制御された単結晶を育成することができる。   By using this invention, it is possible to grow a single crystal in which the Si concentration, that is, the carrier concentration is controlled with good reproducibility even in the vertical boat method such as the VB method or the VGF method.

図２は従来の単結晶育成装置の一例を示す概略縦断面図であって、るつぼ収納容器（サセプター）３内に設けたるつぼ４に種結晶５と化合物半導体原料を装入し、その上に封止剤（Ｂ2Ｏ3）８を置き、収納容器の回りをヒーター１７で加熱して原料ＧａＡｓを溶融し、温度制御により原料融液７から化合物半導体結晶６を育成させる。ヒーター１７の外周は断熱材１６で囲まれていて、総てこれらは気密容器１１内に収納され、前記るつぼ収納容器３は該気密容器１１に設けた気密シール２を通して下部ロッド１により支持され、かつ上下移動および回転が可能になっている。
特公平３−５７０７９号公報 FIG. 2 is a schematic longitudinal sectional view showing an example of a conventional single crystal growth apparatus, in which a seed crystal 5 and a compound semiconductor raw material are charged in a crucible 4 provided in a crucible storage container (susceptor) 3. A sealing agent (B 2 O 3 ) 8 is placed, the surroundings of the storage container are heated by a heater 17 to melt the raw material GaAs, and the compound semiconductor crystal 6 is grown from the raw material melt 7 by temperature control. The outer periphery of the heater 17 is surrounded by a heat insulating material 16, all of which are stored in an airtight container 11, and the crucible storage container 3 is supported by the lower rod 1 through an airtight seal 2 provided in the airtight container 11, In addition, it can move up and down and rotate.
Japanese Patent Publication No. 3-57079

しかしながら前述の発明を用いても、結晶中のキャリア濃度は結晶尾部になるに従い大きくなり、頭部と比較して３〜４倍程度となって結晶成長方向での不均一性が解消されず、歩留りを著しく悪くするという問題があった。   However, even using the above-mentioned invention, the carrier concentration in the crystal increases as it becomes the crystal tail, and is about 3 to 4 times that of the head, and the non-uniformity in the crystal growth direction is not eliminated, There was a problem of significantly reducing the yield.

さらに特に最近はキャリア濃度の範囲について狭める要望があり、特に上限値を低くする要望が強くなっている。   More recently, there has been a demand for narrowing the range of carrier concentration, and in particular, there has been a strong demand for lowering the upper limit value.

従って本発明の目的は、ＶＢ法やＶＧＦ法等の縦型ボート法を用いてＳｉドープ型ＧａＡｓ単結晶を製造する方法の改善により、ＳｉがＧａＡｓ単結晶中に再現性良くドープされた、またＳｉ濃度が均一であって単結晶の歩留りが高いＳｉドープｎ型ＧａＡｓ単結晶を提供することである。   Accordingly, an object of the present invention is to improve the method of manufacturing a Si-doped GaAs single crystal using a vertical boat method such as the VB method or the VGF method, so that Si is doped in the GaAs single crystal with good reproducibility. The object is to provide a Si-doped n-type GaAs single crystal having a uniform Si concentration and a high single crystal yield.

通常の単結晶製造を行った場合、キャリア濃度は図５に示すように横軸をインゴットの固化率、縦軸をキャリア濃度とすると結晶尾部に向けて濃度が高くなる右上がりの勾配となる。特に結晶尾部に近くなるとキャリア濃度は急増する傾向にある。固化率が０.１程度でキャリア濃度が１×１０18ｃｍ-3になるように結晶成長を行った場合、例えばキャリア濃度が上限４×１０18ｃｍ-3まででは固化率０.８までの歩留りとなるが、上限が２×１０18ｃｍ-3の場合は固化率０.６の歩留まりにしかならない。 When normal single crystal production is performed, the carrier concentration has an upward slope where the concentration increases toward the crystal tail when the horizontal axis indicates the solidification rate of the ingot and the vertical axis indicates the carrier concentration, as shown in FIG. In particular, the carrier concentration tends to increase rapidly near the crystal tail. When crystal growth is performed so that the solidification rate is about 0.1 and the carrier concentration is 1 × 10 18 cm −3 , for example, when the carrier concentration is up to 4 × 10 18 cm −3 , the solidification rate is up to 0.8. In terms of yield, when the upper limit is 2 × 10 18 cm −3 , the yield is only a solidification rate of 0.6.

この欠点を解消するため、本発明者はＳｉの挙動について検討を行った。   In order to eliminate this drawback, the present inventor examined the behavior of Si.

融液中に添加されたＳｉはＧａＡｓに溶解しているが、封止剤Ｂ2Ｏ3と接触しているため次式の反応により融液中から消費される。
３Ｓｉ(GaAs Melt 中)＋２Ｂ2Ｏ3＝３ＳｉＯ2(Ｂ2Ｏ3へ)＋４Ｂ(GaAs Meltへ)
上記反応は単結晶育成開始時にはほぼ平衡状態に達し、単結晶育成中はノーマルフリージングによる偏析現象によるＳｉのＧａＡｓ融液への濃縮がおこっているものと考えられる。 Si added to the melt is dissolved in GaAs, but since it is in contact with the sealant B 2 O 3 , it is consumed from the melt by the following reaction.
3Si (in GaAs Melt) + 2B 2 O 3 = 3SiO 2 (to B 2 O 3 ) + 4B (to GaAs Melt)
The above reaction reaches an almost equilibrium state at the start of single crystal growth, and it is considered that Si is concentrated in the GaAs melt due to segregation phenomenon due to normal freezing during single crystal growth.

もしも何らかの手段により単結晶育成中にも上記反応を右に進行させ続けることができるならばＧａＡｓ融液からのＳｉの損失も競合して起きることになる。この競合を制御すれば単結晶中のＳｉ濃度すなわちキャリア濃度を制御することができる。単結晶育成中でも上記反応を右に進めるためにはＢ2Ｏ3中のＳｉＯ2濃度を低減すれば可能である。これには結晶育成中にＳｉＯ2が含まれる量がより少ないＢ2Ｏ3を新たに添加すれば可能となる。すなわち、本発明は結晶成長時に融液に含まれるドーパント濃度を酸化（還元）反応により制御するものである。 If the above reaction can continue to proceed to the right even during single crystal growth by some means, loss of Si from the GaAs melt will also occur in competition. By controlling this competition, the Si concentration in the single crystal, that is, the carrier concentration can be controlled. In order to advance the above reaction to the right even during single crystal growth, it is possible to reduce the SiO 2 concentration in B 2 O 3 . This can be achieved by newly adding B 2 O 3 containing less SiO 2 during crystal growth. That is, the present invention controls the dopant concentration contained in the melt during crystal growth by an oxidation (reduction) reaction.

すなわち本発明は第１に、キャリア濃度が０.１×１０18ｃｍ-3〜３×１０18ｃｍ-3であり、かつ結晶尾部（固化率０.８）でのキャリア濃度が結晶肩部（固化率０.１）でのキャリア濃度の２倍以内であることを特徴とするＳｉドープガリウム砒素単結晶；第２に、結晶中のキャリア濃度が結晶肩部（固化率０.１）で０.１×１０18ｃｍ-3〜３×１０18ｃｍ-3の範囲にあり、かつ結晶尾部（固化率０.８）でのキャリア濃度は結晶肩部の２倍以内であり、さらにこの間の結晶位置（固化率０.１〜０.８）でもキャリア濃度が結晶肩部のキャリア濃度以上かつ結晶尾部のキャリア濃度以下である前記第１記載のＳｉドープガリウム砒素単結晶；第３に、液体封止剤を用いた縦型温度傾斜法または縦型ブリッジマン法によって製造されたＳｉドープガリウム砒素単結晶であって、キャリア濃度が０.１×１０18ｃｍ-3〜３×１０18ｃｍ-3であり、かつ結晶尾部（固化率０.８）でのキャリア濃度が結晶肩部（固化率０.１）でのキャリア濃度の２倍以内であることを特徴とするＳｉドープガリウム砒素単結晶を提供するものである。 That is, in the present invention, first, the carrier concentration is 0.1 × 10 18 cm −3 to 3 × 10 18 cm −3 , and the carrier concentration at the crystal tail (solidification rate 0.8) is the crystal shoulder ( Si-doped gallium arsenide single crystal characterized by being within twice the carrier concentration at a solidification rate of 0.1); second, the carrier concentration in the crystal is 0 at the crystal shoulder (solidification rate of 0.1) The carrier concentration in the range of 0.1 × 10 18 cm −3 to 3 × 10 18 cm −3 and the crystal tail (solidification rate 0.8) is within twice the crystal shoulder, and the crystal in the meantime The Si-doped gallium arsenide single crystal according to the first aspect, wherein the carrier concentration is not less than the carrier concentration at the crystal shoulder and not more than the carrier concentration at the crystal tail even at the position (solidification rate of 0.1 to 0.8); Si doping gas manufactured by vertical temperature gradient method using vertical stopper or vertical Bridgman method It is a single crystal of arsenic, the carrier concentration is 0.1 × 10 18 cm −3 to 3 × 10 18 cm −3 , and the carrier concentration at the crystal tail (solidification rate 0.8) is the crystal shoulder ( The present invention provides a Si-doped gallium arsenide single crystal characterized by being within twice the carrier concentration at a solidification rate of 0.1).

本発明の製造方法によればＢ2Ｏ3を液体封止剤とし、Ｓｉをドーパントとして用いる従来のＧａＡｓ単結晶の製造方法に対し、Ｓｉ濃度がより小さい第２の封止剤を併用することにより、さらにこれらを攪拌することにより結晶中のキャリア濃度を制御することが可能になるので、Ｓｉを単結晶中に再現性良くドープでき、またＳｉ濃度が均一であって単結晶の歩留りが高いＧａＡｓ単結晶およびその製造方法が提供できる。
これらの結果からＳｉ濃度のより小さい第２の封止剤を併用して用いること、さらにこれらを攪拌することにより結晶中のキャリア濃度を制御することが可能である。 According to the manufacturing method of the present invention, the second sealing agent having a lower Si concentration is used in combination with the conventional manufacturing method of GaAs single crystal using B 2 O 3 as a liquid sealing agent and Si as a dopant. By further stirring these, it becomes possible to control the carrier concentration in the crystal, so that Si can be doped into the single crystal with good reproducibility, and the Si concentration is uniform and the yield of the single crystal is high. A GaAs single crystal and a manufacturing method thereof can be provided.
From these results, it is possible to control the carrier concentration in the crystal by using a second sealant having a lower Si concentration in combination and further stirring them.

本発明では縦型温度傾斜法や縦型ブリッジマン法によりＳｉドープｎ型ＧａＡｓ単結晶を製造する場合、結晶原料融液としてＳｉを添加したＧａＡｓ融液と、液体封止剤としてＢ2Ｏ3を使用する。図１は本発明の単結晶を製造するための製造装置の断面図を模式的に示したものである。 In the present invention, when a Si-doped n-type GaAs single crystal is produced by a vertical temperature gradient method or a vertical Bridgman method, a GaAs melt added with Si as a crystal raw material melt and a B 2 O 3 as a liquid sealant. Is used. FIG. 1 schematically shows a cross-sectional view of a production apparatus for producing a single crystal of the present invention.

図１において封止剤８はＡｓの飛散や結晶成長開始時のＳｉ濃度を制御するための目的で投入（チャージ）したＢ2Ｏ3であり、第２の封止剤９は結晶育成途中でＳｉ濃度を制御するための目的で添加されるＢ2Ｏ3である。るつぼ収納容器３は下部ロッド１で保持されており、るつぼ４が回転可能となっている。 In FIG. 1, sealant 8 is B 2 O 3 charged (charged) for the purpose of controlling the scattering of As and the Si concentration at the start of crystal growth, and the second sealant 9 is in the middle of crystal growth. B 2 O 3 added for the purpose of controlling the Si concentration. The crucible storage container 3 is held by the lower rod 1, and the crucible 4 is rotatable.

るつぼ収納容器３上部には回転および上下移動可能でかつ攪拌板等や上部封止剤収納容器が取付け可能な上部ロッド１２が配置されており、るつぼ４内の融体の攪拌や封止剤を導入する配管としても利用可能となっている。   An upper rod 12 that can be rotated and moved up and down and to which a stirring plate or an upper sealant storage container can be attached is disposed at the upper part of the crucible storage container 3. It can also be used as a pipe to be introduced.

図３は第２の封止剤９を添加する形態を示したものであり、上部封止剤収納容器１５中の第２の封止剤９を溶解させてるつぼ４の上部あるいは溶体中に装入する。上部収納容器１５はヒーターで加熱して第２の封止剤を溶解させることでるつぼ４への装入が可能であり、ヒーターでの加熱を停止することでるつぼ４への装入は停止することも可能である。装入は攪拌しながら行っても良いし、攪拌を止めた状態で行っても良い。また装入開始や停止の時期や攪拌の有無についても最適の条件を選択すれば良い。   FIG. 3 shows a form in which the second sealant 9 is added. The second sealant 9 in the upper sealant container 15 is added to the upper part of the crucible 4 or in the solution. Enter. The upper storage container 15 can be charged into the crucible 4 by heating with a heater to dissolve the second sealant, and charging into the crucible 4 is stopped by stopping heating with the heater. It is also possible. The charging may be performed while stirring or may be performed while stirring is stopped. Moreover, what is necessary is just to select optimal conditions also about the timing of a charge start or stop, and the presence or absence of stirring.

図４は封止剤８の上部に第２の封止剤９をおいた状態を示すものである。この場合でも、攪拌については最適条件を選択すれば良い。   FIG. 4 shows a state in which the second sealant 9 is placed on the top of the sealant 8. Even in this case, the optimum condition may be selected for stirring.

また図示はしていないが、上部ロッドの形状は溶体が攪拌できればどのような形状であっても良い。また攪拌は図１に見られるように、上部ロッド１２や下部ロッド１を回転することで溶体を任意に攪拌することができる。
以下実施例により詳細に説明する。 Although not shown, the shape of the upper rod may be any shape as long as the solution can be stirred. In addition, as shown in FIG. 1, the solution can be arbitrarily stirred by rotating the upper rod 12 and the lower rod 1.
Examples will be described in detail below.

［実施例１］図３はるつぼ４の上方に移動可能な攪拌板１０を備えた収納容器１５に第２の封止剤９を収納した状態を示したものであり、この図を用いて説明する。種結晶５上に化合物原料であるＧａＡｓ１３を３０００ｇ用意した。ドーパント１４としてのＳｉは化合物原料に対して０.０２７％となるように８１０ｍｇ用意した。封止剤８はＳｉ濃度換算で３重量％となるようにＳｉ酸化物を添加したＢ2 Ｏ3 ２４０ｇを用意した。第２の封止剤９はＢ2Ｏ3に対してＳｉ濃度換算でＳｉ酸化物を０.５重量％含有させたもの５０ｇを予め上部封止剤収納容器１５に用意した。 [Embodiment 1] FIG. 3 shows a state in which the second sealant 9 is stored in a storage container 15 having a stirring plate 10 movable above the crucible 4, and will be described with reference to this figure. To do. 3000 g of GaAs13 as a compound raw material was prepared on the seed crystal 5. 810 mg of Si as the dopant 14 was prepared so as to be 0.027% with respect to the compound raw material. As the sealant 8, 240 g of B 2 O 3 to which Si oxide was added so as to be 3% by weight in terms of Si concentration was prepared. 50 g of the second sealant 9 containing 0.5% by weight of Si oxide in terms of Si concentration with respect to B 2 O 3 was prepared in the upper sealant storage container 15 in advance.

これを通常の育成方法により溶解し固化を開始した。上部収納容器１５の第２の封止剤９は固化率０.４でるつぼ４に流入させ、攪拌板１０を用いて混合・攪拌を開始した。上部ロッド１２は５ｒｐｍで回転させたものと、回転させないものについて試験を行った。下部ロッドは回転させなかった。回転させたものについて固化率０.１でキャリア濃度は１×１０18ｃｍ-3であり、固化率０.８までキャリア濃度２×１０18ｃｍ-3以下の単結晶が得られた。回転させないものは固化率０.１でキャリア濃度は１×１０18ｃｍ-3であり、固化率０.６でキャリア濃度が２×１０18ｃｍ-3となった。図６に本実施例の上部ロッドを回転させて育成した結晶の固化率に対するキャリア濃度の変化を示した。 This was dissolved by a normal growth method and solidification was started. The second sealant 9 in the upper storage container 15 was allowed to flow into the crucible 4 at a solidification rate of 0.4, and mixing and stirring were started using the stirring plate 10. The upper rod 12 was tested for the one rotated at 5 rpm and the one not rotated. The lower rod was not rotated. With respect to the rotated one, the solidification rate was 0.1 and the carrier concentration was 1 × 10 18 cm −3 , and a single crystal having a carrier concentration of 2 × 10 18 cm −3 or less was obtained until the solidification rate was 0.8. Those that were not rotated had a solidification rate of 0.1 and a carrier concentration of 1 × 10 18 cm −3 , and a solidification rate of 0.6 and a carrier concentration of 2 × 10 18 cm −3 . FIG. 6 shows the change in the carrier concentration with respect to the solidification rate of the crystal grown by rotating the upper rod of this example.

［実施例２］第２の封止剤９はＢ2Ｏ3に対してＳｉを含まないもの５０ｇ用意し、実施例１と同様に試験を行った。回転させたものについて固化率０.１でキャリア濃度は１×１０18ｃｍ-3であり、固化率０.８までキャリア濃度１.８×１０18ｃｍ-3以下の単結晶が得られた。回転させないものは固化率０.１でキャリア濃度は１×１０18ｃｍ-3であり、固化率０.６でキャリア濃度が２×１０18ｃｍ-3となった。 [Example 2] 50 g of a second sealant 9 containing no Si with respect to B 2 O 3 was prepared and tested in the same manner as in Example 1. With respect to the rotated one, a solidification rate of 0.1 and a carrier concentration of 1 × 10 18 cm −3 were obtained, and a single crystal having a carrier concentration of 1.8 × 10 18 cm −3 or less was obtained up to a solidification rate of 0.8. Those that were not rotated had a solidification rate of 0.1 and a carrier concentration of 1 × 10 18 cm −3 , and a solidification rate of 0.6 and a carrier concentration of 2 × 10 18 cm −3 .

［実施例３］図４はるつぼ内に種結晶、化合物半導体原料、ドーパントと封止剤および第２の封止剤を収納し、上方に移動可能な攪拌板を設けた状態を示すものであり、この図を用いて説明する。化合物原料であるＧａＡｓ１３を３０００ｇ用意した。ドーパント１４としてＳｉは化合物原料に対して０.０２７％となるように８１０ｍｇ用意した。封止剤８はＳｉ濃度換算で３重量％となるように添加したＢ2Ｏ3 ２４０ｇを用意した。第２の封止剤９はＢ2Ｏ3に対してＳｉ濃度換算でＳｉ酸化物を０.５重量％含有させたもの５０ｇを予め上部封止剤８の上に用意した。 [Embodiment 3] FIG. 4 shows a state in which a seed crystal, a compound semiconductor raw material, a dopant, a sealant and a second sealant are housed in a crucible, and a stirring plate which can move upward is provided. This will be described with reference to FIG. 3000 g of GaAs13 which is a compound raw material was prepared. As dopant 14, 810 mg of Si was prepared so as to be 0.027% with respect to the compound raw material. As the sealant 8, 240 g of B 2 O 3 added so as to be 3% by weight in terms of Si concentration was prepared. 50 g of the second sealant 9 containing 0.5% by weight of Si oxide in terms of Si concentration with respect to B 2 O 3 was prepared on the upper sealant 8 in advance.

これを通常の育成方法により溶解し固化を開始した。固化率０.３で攪拌を開始した。上部ロッドは２ｒｐｍで回転させたものと、回転させないものについて試験を行った。下部ロッドは回転させなかった。回転させたものについて固化率０.１でキャリア濃度は１×１０18ｃｍ-3であり、固化率０.８までキャリア濃度２×１０18ｃｍ-3以下の単結晶が得られた。回転させないものは固化率０.１でキャリア濃度は１×１０18ｃｍ-3であり、固化率０.６でキャリア濃度が２×１０18ｃｍ-3となった。 This was dissolved by a normal growth method and solidification was started. Stirring was started at a solidification rate of 0.3. The upper rod was tested with and without rotating at 2 rpm. The lower rod was not rotated. With respect to the rotated one, the solidification rate was 0.1 and the carrier concentration was 1 × 10 18 cm −3 , and a single crystal having a carrier concentration of 2 × 10 18 cm −3 or less was obtained until the solidification rate was 0.8. Those that were not rotated had a solidification rate of 0.1 and a carrier concentration of 1 × 10 18 cm −3 , and a solidification rate of 0.6 and a carrier concentration of 2 × 10 18 cm −3 .

［実施例４］第２の封止剤９はＢ2Ｏ3に対してＳｉを含まないもの５０ｇ用意し、実施例３と同様に試験を行った。回転させたものについて固化率０.１でキャリア濃度は１×１０18ｃｍ-3であり、固化率０.８までキャリア濃度１.８×１０18ｃｍ-3以下の単結晶が得られた。回転させないものは固化率０.１でキャリア濃度は１×１０18ｃｍ-3であり、固化率０.６でキャリア濃度が２×１０18ｃｍ-3以上となった。 [Example 4] 50 g of the second sealant 9 containing no Si with respect to B 2 O 3 was prepared and tested in the same manner as in Example 3. With respect to the rotated one, a solidification rate of 0.1 and a carrier concentration of 1 × 10 18 cm −3 were obtained, and a single crystal having a carrier concentration of 1.8 × 10 18 cm −3 or less was obtained up to a solidification rate of 0.8. Those that were not rotated had a solidification rate of 0.1 and a carrier concentration of 1 × 10 18 cm −3 , and a solidification rate of 0.6 and a carrier concentration of 2 × 10 18 cm −3 or more.

［実施例５］実施例１と同様に化合物原料であるＧａＡｓ１３を３０００ｇ用意した。ドーパント１４としてＳｉは化合物原料に対して０.０２７％となるように８１０ｍｇ用意した。封止剤８はＳｉ濃度換算で３重量％となるようにＳｉ酸化物を添加したＢ2Ｏ3 ２４０ｇを用意した。第２の封止剤９はＢ2Ｏ3に対してＳｉ濃度換算でＳｉ酸化物を０.５重量％含有させたもの５０ｇを上部封止剤収納容器１５に予め用意しておいた。 [Example 5] In the same manner as in Example 1, 3000 g of GaAs13 as a compound raw material was prepared. As dopant 14, 810 mg of Si was prepared so as to be 0.027% with respect to the compound raw material. As the sealant 8, 240 g of B 2 O 3 to which Si oxide was added so as to be 3% by weight in terms of Si concentration was prepared. 50 g of the second sealant 9 containing 0.5% by weight of Si oxide in terms of Si concentration with respect to B 2 O 3 was prepared in the upper sealant storage container 15 in advance.

これを通常の育成方法により溶解し固化を開始した。固化率０.４で上部収納容器１５中の第２の封止剤９を溶解させてるつぼの溶体上に流下させた。上部ロッド１２は回転を停止させ、下部ロッド１を２ｒｐｍで回転させたものと、回転させないものについて試験を行った。回転させたものについて固化率０.１でキャリア濃度は１×１０18ｃｍ-3であり、固化率０.８までキャリア濃度２×１０18ｃｍ-3以下の単結晶が得られた。回転させないものは固化率０.１でキャリア濃度は１×１０18ｃｍ-3であり、固化率０.６でキャリア濃度が２×１０18ｃｍ-3以上となった。 This was dissolved by a normal growth method and solidification was started. The second sealant 9 in the upper storage container 15 was allowed to flow down onto the crucible solution in which the solidification rate was 0.4. The upper rod 12 was stopped from rotating, and the test was performed on the case where the lower rod 1 was rotated at 2 rpm and the case where the lower rod 1 was not rotated. With respect to the rotated one, a solidification rate of 0.1 and a carrier concentration of 1 × 10 18 cm −3 were obtained, and a single crystal having a carrier concentration of 2 × 10 18 cm −3 or less was obtained up to a solidification rate of 0.8. Those that were not rotated had a solidification rate of 0.1 and a carrier concentration of 1 × 10 18 cm −3 , and a solidification rate of 0.6 and a carrier concentration of 2 × 10 18 cm −3 or more.

［実施例６］第２の封止剤９はＢ2Ｏ3に対してＳｉを含まないもの５０ｇ用意し、実施例５と同様に試験を行った。回転させたものについて固化率０.１でキャリア濃度は１×１０18ｃｍ-3であり、固化率０.８までキャリア濃度２×１０18ｃｍ-3以下の単結晶が得られた。回転させないものは固化率０.１でキャリア濃度は１×１０18ｃｍ-3であり、固化率０.６でキャリア濃度が２×１０18ｃｍ-3以上となった。 [Example 6] 50 g of the second sealant 9 containing no Si with respect to B 2 O 3 was prepared and tested in the same manner as in Example 5. With respect to the rotated one, the solidification rate was 0.1 and the carrier concentration was 1 × 10 18 cm −3 , and a single crystal having a carrier concentration of 2 × 10 18 cm −3 or less was obtained until the solidification rate was 0.8. Those that were not rotated had a solidification rate of 0.1 and a carrier concentration of 1 × 10 18 cm −3 , and a solidification rate of 0.6 and a carrier concentration of 2 × 10 18 cm −3 or more.

［比較例］化合物原料であるＧａＡｓ１３を３０００ｇ用意した。ドーパント１４としてＳｉは化合物原料に対して０.０２７％となるように８１０ｍｇ用意した。封止剤８はＳｉ濃度換算で３重量％となるようにＳｉ酸化物を添加したＢ2Ｏ3 ２９０ｇを用意した。第２の封止剤９は用いなかった。 [Comparative Example] 3000 g of GaAs13 as a compound raw material was prepared. As dopant 14, 810 mg of Si was prepared so as to be 0.027% with respect to the compound raw material. As the sealant 8, 290 g of B 2 O 3 to which Si oxide was added so as to be 3% by weight in terms of Si concentration was prepared. The second sealant 9 was not used.

これを通常の育成方法により溶解し固化を開始した。固化率０.１でキャリア濃度は１×１０18ｃｍ-3であり、固化率０.６でキャリア濃度が２×１０18ｃｍ-3以上の単結晶となった。 This was dissolved by a normal growth method and solidification was started. The carrier concentration was 1 × 10 18 cm −3 at a solidification rate of 0.1, and a single crystal having a solidification rate of 0.6 and a carrier concentration of 2 × 10 18 cm −3 or more was obtained.

本発明での単結晶製造装置の一例を示す概略縦断面図である。It is a schematic longitudinal cross-sectional view which shows an example of the single-crystal manufacturing apparatus in this invention. 従来の単結晶製造装置の一例を示す概略縦断面図である。It is a schematic longitudinal cross-sectional view which shows an example of the conventional single crystal manufacturing apparatus. 本発明の実施例において、るつぼ内に化合物半導体原料、種結晶、ドーパントＳｉ、Ｓｉ酸化物を予めドープした封止剤を収納し、さらに上部に移動可能な攪拌板を具備した収納容器に第２の封止剤を収納した状態を示す模式断面図である。In an embodiment of the present invention, the container containing the compound semiconductor raw material, seed crystal, dopant Si, Si oxide pre-doped sealing agent in the crucible, and further equipped with a stirring plate that can be moved to the upper part is provided in the second container. It is a schematic cross section which shows the state which accommodated the sealing agent. 本発明の実施例において、るつぼ内に化合物半導体原料、種結晶、ドーパントＳｉ、Ｓｉ酸化物を予めドープした封止剤および第２の封止剤を収納し、さらに上部に移動可能な攪拌板を装備した状態を示す模式断面図である。In an embodiment of the present invention, a compound semiconductor raw material, a seed crystal, a dopant Si, a sealant pre-doped with Si oxide and a second sealant are housed in a crucible, and a stirring plate that can move further upward is provided. It is a schematic cross section which shows the state equipped. 従来のＳｉドープガリウム砒素単結晶中の成長方向のキャリア濃度分布の一例を示すグラフである。It is a graph which shows an example of the carrier concentration distribution of the growth direction in the conventional Si dope gallium arsenide single crystal. 本発明を用いたＳｉドープガリウム砒素単結晶中の成長方向のキャリア濃度分布の一例を示すグラフである。It is a graph which shows an example of the carrier concentration distribution of the growth direction in the Si dope gallium arsenide single crystal using this invention.

符号の説明Explanation of symbols

１ 下部ロッド
２ 気密シール
３ るつぼ収納容器（サセプタ）
４ るつぼ
５ 種結晶
６ 化合物半導体結晶
７ 原料融液
８ 封止剤
９ 第２の封止剤
１０ 攪拌板
１１ 気密容器
１２ 上部ロッド
１３ 化合物原料ＧａＡｓ
１４ ドーパント
１５ 上部封止剤収納容器
１６ 断熱材
１７ ヒーター 1 Lower rod 2 Airtight seal 3 Crucible container (susceptor)
4 Crucible 5 Seed crystal 6 Compound semiconductor crystal 7 Raw material melt 8 Sealant 9 Second sealant 10 Stirring plate 11 Airtight container 12 Upper rod 13 Compound raw material GaAs
14 Dopant 15 Upper Sealant Storage Container 16 Heat Insulating Material 17 Heater

Claims (2)

液体封止剤を使用した縦型温度傾斜法または縦型ブリッジマン法によるＳｉドープガリウム砒素単結晶の製造装置であって、内面底部に種結晶収納部が形成され該種結晶の上にガリウム砒素原料、ドーパントＳｉ、Ｓｉ酸化物を含有させた封止剤を収納し上方が開放されたるつぼと、該るつぼの上方に配置され該封止剤よりも小さいＳｉ濃度でＳｉ酸化物を含有させた第２封止剤を収納し下部に開口と撹拌板を上部に上部ロッドを有して上下移動及び回転可能な上部封止剤収納容器と、を備えたＳｉドープガリウム砒素単結晶の製造装置。 An apparatus for producing a Si-doped gallium arsenide single crystal using a vertical temperature gradient method or a vertical Bridgman method using a liquid sealant, wherein a seed crystal storage portion is formed at the bottom of the inner surface, and the gallium arsenide is formed on the seed crystal A crucible containing a raw material, dopant Si, Si oxide and containing a crucible opened at the top, and Si oxide contained at a lower Si concentration than the sealant disposed above the crucible. An apparatus for producing a Si-doped gallium arsenide single crystal , comprising: an upper sealant storage container that houses a second sealant, and has an opening and a stirring plate at a lower part and an upper rod at an upper part, and is movable up and down and rotatable . 前記るつぼを収納する容器が下部ロッドで保持され回転及び上下移動可能な容器である、請求項１記載のＳｉドープガリウム砒素単結晶の製造装置。 The apparatus for producing a Si-doped gallium arsenide single crystal according to claim 1 , wherein the container for housing the crucible is a container that is held by a lower rod and is rotatable and vertically movable .
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5262200A (en) * 1975-11-17 1977-05-23 Sumitomo Electric Ind Ltd Single crystal of gallium arsenide without dislocation
JPS63166799A (en) * 1986-12-27 1988-07-09 Dowa Mining Co Ltd Production of si doped n-type gallium arsenide single crystal
JPH03153600A (en) * 1989-11-10 1991-07-01 Hitachi Cable Ltd Production of single crystal of iii-v compound semiconductor
JPH06219900A (en) * 1993-01-28 1994-08-09 Dowa Mining Co Ltd Production of si-doped n-type gallium arsenide single crystal
JPH0848592A (en) * 1994-08-10 1996-02-20 Sumitomo Electric Ind Ltd Production of compound semiconductor crystal
JPH08151290A (en) * 1994-09-28 1996-06-11 Sumitomo Electric Ind Ltd Method for growing single crystal of compound semiconductor
JPH10259100A (en) * 1997-03-18 1998-09-29 Japan Energy Corp Production of garium-arsenic single crystal

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS649898A (en) * 1987-07-02 1989-01-13 Nippon Mining Co Production of silicon-containing gaas single crystal

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5262200A (en) * 1975-11-17 1977-05-23 Sumitomo Electric Ind Ltd Single crystal of gallium arsenide without dislocation
JPS63166799A (en) * 1986-12-27 1988-07-09 Dowa Mining Co Ltd Production of si doped n-type gallium arsenide single crystal
JPH03153600A (en) * 1989-11-10 1991-07-01 Hitachi Cable Ltd Production of single crystal of iii-v compound semiconductor
JPH06219900A (en) * 1993-01-28 1994-08-09 Dowa Mining Co Ltd Production of si-doped n-type gallium arsenide single crystal
JPH0848592A (en) * 1994-08-10 1996-02-20 Sumitomo Electric Ind Ltd Production of compound semiconductor crystal
JPH08151290A (en) * 1994-09-28 1996-06-11 Sumitomo Electric Ind Ltd Method for growing single crystal of compound semiconductor
JPH10259100A (en) * 1997-03-18 1998-09-29 Japan Energy Corp Production of garium-arsenic single crystal

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