JP3785566B2 - GaN compound semiconductor crystal manufacturing method - Google Patents
GaN compound semiconductor crystal manufacturing method Download PDFInfo
- Publication number
- JP3785566B2 JP3785566B2 JP2001078246A JP2001078246A JP3785566B2 JP 3785566 B2 JP3785566 B2 JP 3785566B2 JP 2001078246 A JP2001078246 A JP 2001078246A JP 2001078246 A JP2001078246 A JP 2001078246A JP 3785566 B2 JP3785566 B2 JP 3785566B2
- Authority
- JP
- Japan
- Prior art keywords
- gan
- compound semiconductor
- crystal
- plane
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、発光デバイス、電子デバイスなどの半導体デバイスの製造に用いられるＧａＮ系化合物半導体結晶の製造方法に関する。
【０００２】
【従来の技術】
ＧａＮ、ＩｎＧａＮ、ＡｌＧａＮ、ＩｎＧａＡｌＮ等のＧａＮ系化合物半導体（ＩｎｘＧａｙＡｌ１−ｘ−ｙＮ 但し０≦ｘ，ｙ；ｘ＋ｙ≦１）は、発光デバイスのみでなく、耐環境性に優れたデバイス、パワーデバイスなどの電子デバイス等の半導体デバイスの材料として期待され、またその他種々の分野で応用可能な材料として注目されている。
【０００３】
従来、ＧａＮ系化合物半導体のバルク結晶を成長させるのは困難であったため、上記電子デバイスには、例えばサファイア等の異種結晶上へのヘテロエピタキシーによってＧａＮ等の薄膜単結晶を形成した基板が用いられていた。
【０００４】
ところが、サファイア結晶とＧａＮ系化合物半導体結晶とは格子不整合性が大きいので、サファイア結晶上に成長させたＧａＮ系化合物半導体結晶の転位密度が大きくなり結晶欠陥が発生してしまうという問題があった。さらに、サファイアは熱伝導率が小さく放熱しにくいので、サファイア結晶上にＧａＮ系化合物半導体結晶を成長させた基板を消費電力の大きい電子デバイス等に用いると高温になりやすいという問題があった。
【０００５】
そこで、熱伝導率が大きくＧａＮ系化合物半導体結晶と格子整合する基板の必要性が一層高まり、ハイドライド気相成長法（以下、ＨＶＰＥと略する）を利用したＥＬＯ（Epitaxial lateral overgrowth）法等の研究が急速に進められた。ここでＥＬＯ法とは、例えばサファイア基板上に絶縁体マスクを形成し、該マスクの一部に開口部を設けて露出したサファイア基板面をエピタキシャル成長の種として結晶性の高いＧａＮ系化合物半導体結晶を成長させる方法である。この方法によれば、マスクに設けられた開口部からＧａＮ系化合物半導体結晶の成長が始まりマスク上に成長層が広がっていくので、結晶中の転位密度を小さく抑えることができ、結晶欠陥の少ないＧａＮ系化合物半導体結晶を得ることができる。
【０００６】
しかし、ＥＬＯ法により得られたＧａＮ系化合物半導体結晶ウェハは熱歪みが大きいため、ウェハ製造工程のポリッシングによりサファイア基板を離間させてＧａＮ系化合物半導体結晶ウェハを単体で得ようとするとＧａＮ系化合物半導体結晶ウェハが歪んでしまうという問題があった。
【０００７】
そこで本発明者等は、異種結晶基板の材料の一つとして希土類１３（３Ｂ）族ペロブスカイト結晶を用い、且つその｛０１１｝面または｛１０１｝面を成長面としてＧａＮ系化合物半導体をヘテロエピタキシーによって成長させる方法を提案した（ＷＯ９５／２７８１５号）。なお、ここでいう｛０１１｝面または｛１０１｝面とは、それぞれ（０１１）面、（１０１）面と等価な面の組を表す。
【０００８】
前記先願の成長技術によれば、例えば希土類１３（３Ｂ）族ペロブスカイトの一つであるＮｄＧａＯ３を基板として、その｛０１１｝面または｛１０１｝面にＧａＮを成長させる場合、格子不整合は１．２％程度であり格子不整合性をサファイアやその代替品として用いられるＳｉＣを基板とした場合よりも極めて小さくなる。よって、結晶中の転位密度が低くなるので結晶欠陥の少ないＧａＮ系化合物半導体結晶を成長させることができた。
【０００９】
【発明が解決しようとする課題】
しかしながら、前記先願の成長方法では、ＧａＮ系化合物半導体結晶を成長させる際に基板との格子不整合による結晶欠陥の発生を抑えることができたが、得られたＧａＮ系化合物半導体結晶の結晶状態が多結晶になってしまうこともあった。すなわち、前記先願の成長方法では半導体デバイスに適したＧａＮ化合物半導体単結晶を歩留まりよく成長させることができない場合があるという問題があった。
【００１０】
本発明は、ＧａＮ系化合物半導体結晶と比較的よく格子整合する希土類１３（３Ｂ）族ペロブスカイトを基板として用いることにより、結晶欠陥が少ないＧａＮ系化合物半導体単結晶を歩留まりよく製造可能な方法を提供することを目的とする。
【００１１】
【課題を解決するための手段】
本発明は、上記目的を達成するためになされたものであり、１または２種類以上の希土類元素を含む希土類１３（３Ｂ）族ペロブスカイト結晶を基板としてＧａＮ系化合物半導体結晶を成長させる方法において、前記希土類１３（３Ｂ）族ペロブスカイト結晶基板の（０１１）面から１°から４°だけオフアングルさせた面を成長面とすることを特徴とするＧａＮ系化合物半導体結晶の製造方法である。
【００１２】
これにより、結晶欠陥が少ないＧａＮ系化合物半導体結晶を成長させることができるとともに、ＧａＮ系化合物半導体結晶の単結晶化率が向上するので、半導体デバイスに適したＧａＮ系化合物半導体単結晶を歩留まりよく製造することができる。
【００１３】
また、望ましくは前記オフアングルの方向を＜１００＞方向にするとよい。これにより、ＧａＮ系化合物半導体結晶の単結晶化率が特に高くなるので、ＧａＮ系化合物半導体単結晶を歩留まりよく製造することができる。
【００１４】
また、基板として用いられる上記希土類１３（３Ｂ）族ペロブスカイト結晶は、１３（３Ｂ）族元素のうちＡｌ，Ｇａ，Ｉｎの少なくとも１種類とＮｄとの化合物であるようにするとよい。例えば、希土類１３（３Ｂ）族ペロブスカイト結晶として、ＮｄＧａＯ３結晶を利用することができる。また、結晶成長方法としてはハイドライドＶＰＥが望ましい。
【００１５】
以下に、本発明を完成するに至った過程について説明する。
【００１６】
まず、本発明者等は前記先願で提案したＧａＮ系化合物半導体結晶の成長方法により得られたＧａＮ系化合物半導体結晶の中には、結晶状態が多結晶になっているものがあることに気付いた。つまり、前記成長法法ではＧａＮ系化合物半導体結晶を成長させる際に基板との格子不整合による結晶欠陥の発生を抑えることができたが、得られたＧａＮ系化合物半導体結晶の結晶状態が多結晶になる場合があるため、半導体デバイスの材料に適したＧａＮ化合物半導体結晶を製造する方法として実用化することは困難であることが判明した。
【００１７】
そこで、本発明者等は前記成長方法にはさらに改良する余地があると考え、前記成長方法により得られるＧａＮ系化合物半導体結晶の結晶状態を改善すべく希土類１３（３Ｂ）族ペロブスカイトの一つであるＮｄＧａＯ３基板の成長面に着目して鋭意研究を重ねた。具体的には、前記先願の成長方法ではＮｄＧａＯ３基板の（０１１）ジャスト面を成長面としていたのを、（０１１）面から所定の角度だけ傾斜したオフアングル面を成長面としてＧａＮ化合物半導体結晶を成長させる実験を行った。
【００１８】
まず、ＮｄＧａＯ３結晶のインゴットをスライスし、（０１１）ジャスト面および（０１１）面から＜１００＞方向に１°〜６°傾斜したオフアングル面が成長面となるようにした基板をそれぞれ複数枚用意した。そして、これらのＮｄＧａＯ３基板を洗浄してエッチングした後、ハイドライドＶＰＥ法によりＧａＮ化合物半導体結晶を成長させた。
【００１９】
その結果、（０１１）ジャスト面を成長面とした場合の単結晶化率は５０％、（０１１）面から１°傾斜したオフアングル面を成長面とした場合の単結晶化率は８０％、（０１１）面から２°傾斜したオフアングル面を成長面とした場合の単結晶化率は９０％、（０１１）面から３°傾斜したオフアングル面を成長面とした場合の単結晶化率は８０％、（０１１）面から４°傾斜したオフアングル面を成長面とした場合の単結晶化率は７０％、（０１１）面から５°傾斜したオフアングル面を成長面とした場合の単結晶化率は５０％、（０１１）面から６°傾斜したオフアングル面を成長面とした場合の単結晶化率は３０％となった（表１）。
【００２０】
【表１】
この実験より、ＮｄＧａＯ３基板の（０１１）ジャスト面を成長面とするよりも、（０１１）面から＜１００＞方向に１°〜４°傾斜したオフアングル面を成長面とした方が単結晶化率が向上することが分かった。
【００２２】
本発明は上記知見に基づいてなされたもので、この方法により半導体デバイスに適したＧａＮ化合物半導体単結晶を歩留まりよく成長させることができる。
【００２３】
なお、本発明は、ＮｄＧａＯ３基板にＧａＮ化合物半導体結晶を成長させる実験により見出されたものであるが、ＧａＮ化合物半導体結晶以外にも、ＩｎＧａＮ、ＡｌＧａＮ等のＧａＮ系化合物半導体結晶を成長させた場合も同様の効果が得られる。
【００２４】
【発明の実施の形態】
以下、本発明の好適な実施の形態を、ＮｄＧａＯ３結晶を基板としてＧａＮ化合物半導体結晶を成長させる場合について説明する。
【００２５】
まず、ＮｄＧａＯ３のインゴットを（０１１）面から＜１００＞方向に２°傾斜したオフアングル面でスライスして基板とした。このとき、ＮｄＧａＯ３基板の大きさは５０mm径で、厚さは０．５ｍｍとした。
【００２６】
次に、鏡面研磨したＮｄＧａＯ３基板をアセトン中で５分間超音波洗浄を行い、続けてメタノールで５分間超音波洗浄を行った。その後、Ｎ２ガスでブローして液滴を吹き飛ばしてから自然乾燥させた。次に、洗浄したＮｄＧａＯ３基板を硫酸系エッチャント（燐酸：硫酸＝１：３、８０℃）で５分間エッチングした。
【００２７】
次に、このＮｄＧａＯ３基板をハイドライドＶＰＥ装置内の所定の部位に配置した後、Ｎ２ガスを導入しながら基板温度を６２０℃まで昇温し、ＧａメタルとＨＣｌガスから生成されたＧａＣｌと、ＮＨ３ガスとをＮ２キャリアガスを用いてＮｄＧａＯ３基板上に供給し、約１００ｎｍのＧａＮ保護層を形成した。ＮｄＧａＯ３は８００℃以上の高温でＮＨ３やＨ２と反応してネオジウム化合物を生成してしまうので、本実施形態ではキャリアガスとしてＮ２を用い、成長温度を６２０℃の低温で保護層を形成することによりネオジウム化合物が生成されないようにしている。
【００２８】
次に、基板温度を１０００℃に昇温し、ＧａメタルとＨＣｌガスから生成されたＧａＣｌと、ＮＨ３ガスとをＮ２キャリアガスを用いてＮｄＧａＯ３基板上に供給した。このとき、ＧａＣｌ分圧が４．０×１０−３ａｔｍ、ＮＨ３分圧が２．４×１０−１ａｔｍとなるようにそれぞれのガス導入量を制御しながら約４０μｍ／ｈの成長速度で３００分間ＧａＮ化合物半導体結晶を成長させた。
【００２９】
その後、冷却速度５．３℃／ｍｉｎで９０分間冷却して膜厚が約２００μｍのＧａＮ化合物半導体結晶を得た。
【００３０】
得られたＧａＮ化合物半導体結晶は、結晶欠陥が少なく結晶性に優れた単結晶であった。また、上述した方法によりＧａＮ化合物半導体結晶を作製した場合、ＧａＮ化合物半導体結晶の単結晶化率は９０％以上であり、半導体デバイスの材料として適したＧａＮ化合物半導体単結晶を歩留まりよく成長させることができた。
【００３１】
以上本発明者によってなされた発明を実施形態に基づき具体的に説明したが、本発明は上記実施の形態に限定されるものではない。例えば、＜１００＞方向に傾ける角度は２°に限定されず、１°〜４°の範囲とすることにより本実施形態と同様に単結晶化率を向上させることができる。
【００３２】
また、成長条件としては、ＧａＣｌ分圧が１．０×１０−３〜１．０×１０−２ａｔｍ、ＮＨ３分圧が１．０×１０−１〜４．０×１０−１ａｔｍ、成長速度が３０〜１００μｍ／ｈ、 成長温度が９３０〜１０５０℃、冷却速度が４〜１０℃／ｍｉｎであることが望ましい。
【００３３】
また、ＧａＮ化合物半導体結晶を成長させる場合に制限されず、例えば、ＩｎＧａＮ、ＡｌＧａＮ等のＧａＮ系化合物半導体結晶の成長方法に適用しても同様の効果を得ることができる。また、基板として用いられる希土類１３（３Ｂ）族ペロブスカイト結晶はＮｄＧａＯ３結晶に制限されず、Ａｌ，Ｇａ，Ｉｎの少なくとも１種類を含む希土類１３（３Ｂ）族ペロブスカイト結晶であればよいと考えられる。
【００３４】
【発明の効果】
本発明によれば、１または２種類以上の希土類元素を含む希土類１３（３Ｂ）族ペロブスカイト結晶を基板としてＧａＮ系化合物半導体結晶を成長させる方法において、前記希土類１３（３Ｂ）族ペロブスカイト結晶基板の（０１１）面から１°から４°だけオフアングルさせた面を成長面としたので、結晶欠陥が少ないＧａＮ系化合物半導体結晶を成長させることができるとともに、ＧａＮ系化合物半導体結晶の単結晶化率が向上するので、半導体デバイスに適したＧａＮ系化合物半導体単結晶を歩留まりよく製造することができるという効果を奏する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for manufacturing a GaN-based compound semiconductor crystal used for manufacturing a semiconductor device such as a light-emitting device or an electronic device.
[0002]
[Prior art]
GaN-based compound semiconductors such as GaN, InGaN, AlGaN, InGaAlN (In x Ga y Al 1-xy N where 0 ≦ x, y; x + y ≦ 1) are excellent not only in light-emitting devices but also in environmental resistance It is expected as a material for semiconductor devices such as electronic devices such as devices and power devices, and attracts attention as a material applicable in various other fields.
[0003]
Conventionally, since it has been difficult to grow a bulk crystal of a GaN-based compound semiconductor, a substrate in which a thin-film single crystal such as GaN is formed by heteroepitaxy on a heterogeneous crystal such as sapphire is used for the electronic device. It was.
[0004]
However, since sapphire crystal and GaN compound semiconductor crystal have large lattice mismatch, there is a problem in that dislocation density of GaN compound semiconductor crystal grown on sapphire crystal increases and crystal defects occur. . Furthermore, since sapphire has a low thermal conductivity and is difficult to dissipate heat, there is a problem that when a substrate on which a GaN-based compound semiconductor crystal is grown on a sapphire crystal is used for an electronic device with high power consumption, the temperature tends to increase.
[0005]
Therefore, the necessity of a substrate having a high thermal conductivity and lattice matching with the GaN compound semiconductor crystal is further increased, and research such as an ELO (Epitaxial lateral overgrowth) method using hydride vapor phase epitaxy (hereinafter referred to as HVPE) is performed. Was advanced rapidly. Here, the ELO method is, for example, that an insulator mask is formed on a sapphire substrate, an opening is provided in a part of the mask, and an exposed sapphire substrate surface is used as a seed for epitaxial growth to produce a highly crystalline GaN-based compound semiconductor crystal. It is a way to grow. According to this method, since the growth of the GaN-based compound semiconductor crystal starts from the opening provided in the mask and the growth layer spreads on the mask, the dislocation density in the crystal can be kept small, and there are few crystal defects. A GaN-based compound semiconductor crystal can be obtained.
[0006]
However, since the GaN-based compound semiconductor crystal wafer obtained by the ELO method has a large thermal strain, when a single GaN-based compound semiconductor crystal wafer is obtained by separating the sapphire substrate by polishing in the wafer manufacturing process, the GaN-based compound semiconductor is obtained. There was a problem that the crystal wafer was distorted.
[0007]
Therefore, the present inventors use rare earth 13 (3B) group perovskite crystal as one of the materials of the different crystal substrate, and the GaN-based compound semiconductor by heteroepitaxy using the {011} plane or {101} plane as a growth plane. A method of growing was proposed (WO95 / 27815). Here, the {011} plane or {101} plane represents a set of planes equivalent to the (011) plane and the (101) plane, respectively.
[0008]
According to the growth technique of the prior application, for example, when NdGaO 3 which is one of rare earth 13 (3B) group perovskites is used as a substrate and GaN is grown on the {011} plane or the {101} plane, the lattice mismatch is It is about 1.2%, and the lattice mismatch is extremely smaller than that in the case of using sapphire or SiC used as a substitute for the substrate. Therefore, since the dislocation density in the crystal is low, a GaN-based compound semiconductor crystal with few crystal defects can be grown.
[0009]
[Problems to be solved by the invention]
However, the growth method of the prior application was able to suppress the occurrence of crystal defects due to lattice mismatch with the substrate when growing the GaN-based compound semiconductor crystal, but the crystal state of the obtained GaN-based compound semiconductor crystal Sometimes became polycrystalline. That is, the growth method of the prior application has a problem that a GaN compound semiconductor single crystal suitable for a semiconductor device may not be grown with a high yield.
[0010]
The present invention provides a method capable of producing a GaN-based compound semiconductor single crystal with few crystal defects with a high yield by using, as a substrate, a rare earth 13 (3B) group perovskite that lattice-matches with a GaN-based compound semiconductor crystal relatively well. For the purpose.
[0011]
[Means for Solving the Problems]
The present invention has been made to achieve the above object, and in the method for growing a GaN-based compound semiconductor crystal using a rare earth 13 (3B) group perovskite crystal containing one or more rare earth elements as a substrate, A method for producing a GaN-based compound semiconductor crystal, characterized in that a growth plane is a plane that is off-angled by 1 ° to 4 ° from a (011) plane of a rare earth 13 (3B) group perovskite crystal substrate.
[0012]
This makes it possible to grow GaN-based compound semiconductor crystals with few crystal defects and to improve the single crystallization rate of GaN-based compound semiconductor crystals, so that GaN-based compound semiconductor single crystals suitable for semiconductor devices can be manufactured with high yield. can do.
[0013]
Preferably, the off-angle direction is a <100> direction. Thereby, since the single crystallization rate of the GaN-based compound semiconductor crystal is particularly high, the GaN-based compound semiconductor single crystal can be manufactured with a high yield.
[0014]
The rare earth 13 (3B) group perovskite crystal used as the substrate may be a compound of Nd with at least one of Al, Ga, and In among the 13 (3B) group elements . For example, an NdGaO 3 crystal can be used as the rare earth 13 (3B) group perovskite crystal. As a crystal growth method, hydride VPE is desirable.
[0015]
The process that led to the completion of the present invention will be described below.
[0016]
First, the present inventors have noticed that some of the GaN-based compound semiconductor crystals obtained by the method for growing a GaN-based compound semiconductor crystal proposed in the previous application have a crystalline state. It was. That is, in the growth method, when the GaN compound semiconductor crystal was grown, the generation of crystal defects due to lattice mismatch with the substrate could be suppressed. However, the crystal state of the obtained GaN compound semiconductor crystal was polycrystalline. Therefore, it has been found difficult to put it into practical use as a method for producing a GaN compound semiconductor crystal suitable for a semiconductor device material.
[0017]
Therefore, the present inventors consider that there is room for further improvement in the growth method, and one of the rare earth 13 (3B) group perovskites to improve the crystal state of the GaN-based compound semiconductor crystal obtained by the growth method. Research has been conducted focusing on the growth surface of a certain NdGaO 3 substrate. Specifically, in the growth method of the previous application, the (011) just surface of the NdGaO 3 substrate was used as the growth surface, but the off-angle surface inclined by a predetermined angle from the (011) surface was used as the growth surface. Experiments were conducted to grow crystals.
[0018]
First, an NdGaO 3 crystal ingot is sliced, and a plurality of substrates each having a (011) just plane and an off-angle plane inclined from 1 ° to 6 ° in the <100> direction from the (011) plane as growth planes are provided. Prepared. Then, these NdGaO 3 substrates were cleaned and etched, and then a GaN compound semiconductor crystal was grown by a hydride VPE method.
[0019]
As a result, the single crystallization rate is 50% when the (011) just plane is the growth plane, and the single crystallization ratio is 80% when the off-angle plane inclined by 1 ° from the (011) plane is the growth plane. The single crystallization rate is 90% when the off-angle plane inclined by 2 ° from the (011) plane is used as the growth plane, and the single crystallization rate when the off-angle plane inclined by 3 ° from the (011) plane is used as the growth plane. Is 80%, the single crystallization rate is 70% when the off-angle plane inclined by 4 ° from the (011) plane is the growth plane, and the off-angle plane inclined by 5 ° from the (011) plane is the growth plane. The single crystallization rate was 50%, and the single crystallization rate was 30% when an off-angle plane inclined by 6 ° from the (011) plane was used as the growth surface (Table 1).
[0020]
[Table 1]
From this experiment, it was found that an off-angle plane inclined by 1 ° to 4 ° in the <100> direction from the (011) plane was used as the growth plane, rather than the (011) just plane of the NdGaO 3 substrate as the growth plane. It was found that the conversion rate was improved.
[0022]
The present invention has been made on the basis of the above knowledge, and by this method, a GaN compound semiconductor single crystal suitable for a semiconductor device can be grown with high yield.
[0023]
The present invention is the one found by experiment to grow a GaN compound semiconductor crystal NdGaO 3 substrate, other than the GaN compound semiconductor crystal was grown InGaN, GaN-based compound semiconductor crystal of AlGaN, etc. In this case, the same effect can be obtained.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, a preferred embodiment of the present invention will be described in the case of growing a GaN compound semiconductor crystal using an NdGaO 3 crystal as a substrate.
[0025]
First, an ingot of NdGaO 3 was sliced at an off-angle plane inclined by 2 ° in the <100> direction from the (011) plane to obtain a substrate. At this time, the NdGaO 3 substrate had a diameter of 50 mm and a thickness of 0.5 mm.
[0026]
Next, the mirror-polished NdGaO 3 substrate was subjected to ultrasonic cleaning in acetone for 5 minutes, followed by ultrasonic cleaning with methanol for 5 minutes. After that, it was blown with N 2 gas to blow off the droplets and then naturally dried. Next, the cleaned NdGaO 3 substrate was etched with a sulfuric acid-based etchant (phosphoric acid: sulfuric acid = 1: 3, 80 ° C.) for 5 minutes.
[0027]
Next, after this NdGaO 3 substrate is placed at a predetermined site in the hydride VPE apparatus, the substrate temperature is raised to 620 ° C. while introducing N 2 gas, and GaCl generated from Ga metal and HCl gas, NH 3 gas was supplied onto the NdGaO 3 substrate using N 2 carrier gas to form a GaN protective layer of about 100 nm. Since NdGaO 3 reacts with NH 3 or H 2 at a high temperature of 800 ° C. or higher to generate a neodymium compound, N 2 is used as a carrier gas in this embodiment, and the protective layer is formed at a low growth temperature of 620 ° C. The formation prevents a neodymium compound from being generated.
[0028]
Next, the substrate temperature was raised to 1000 ° C., and GaCl generated from Ga metal and HCl gas and NH 3 gas were supplied onto the NdGaO 3 substrate using N 2 carrier gas. At this time, at a growth rate of about 40 μm / h while controlling the amount of gas introduced so that the GaCl partial pressure is 4.0 × 10 −3 atm and the NH 3 partial pressure is 2.4 × 10 −1 atm. A GaN compound semiconductor crystal was grown for 300 minutes.
[0029]
Thereafter, it was cooled at a cooling rate of 5.3 ° C./min for 90 minutes to obtain a GaN compound semiconductor crystal having a film thickness of about 200 μm.
[0030]
The obtained GaN compound semiconductor crystal was a single crystal with few crystal defects and excellent crystallinity. Further, when a GaN compound semiconductor crystal is manufactured by the above-described method, the crystallization rate of the GaN compound semiconductor crystal is 90% or more, and a GaN compound semiconductor single crystal suitable as a semiconductor device material can be grown with a high yield. did it.
[0031]
Although the invention made by the present inventor has been specifically described based on the embodiment, the present invention is not limited to the above embodiment. For example, the angle inclined in the <100> direction is not limited to 2 °, and the single crystallization rate can be improved in the same manner as in this embodiment by setting the angle in the range of 1 ° to 4 °.
[0032]
As growth conditions, the GaCl partial pressure is 1.0 × 10 −3 to 1.0 × 10 −2 atm, the NH 3 partial pressure is 1.0 × 10 −1 to 4.0 × 10 −1 atm, It is desirable that the growth rate is 30 to 100 μm / h, the growth temperature is 930 to 1050 ° C., and the cooling rate is 4 to 10 ° C./min.
[0033]
Further, the present invention is not limited to the case of growing a GaN compound semiconductor crystal, and the same effect can be obtained even when applied to a growth method of a GaN compound semiconductor crystal such as InGaN or AlGaN. The rare earth 13 (3B) group perovskite crystal used as the substrate is not limited to the NdGaO 3 crystal, but may be any rare earth 13 (3B) group perovskite crystal including at least one of Al, Ga, and In.
[0034]
【The invention's effect】
According to the present invention, in a method of growing a GaN-based compound semiconductor crystal using a rare earth 13 (3B) group perovskite crystal containing one or more kinds of rare earth elements as a substrate, the rare earth 13 (3B) group perovskite crystal substrate ( 011) Since the growth plane is the plane off-angled by 1 ° to 4 ° from the plane, a GaN-based compound semiconductor crystal with few crystal defects can be grown, and the crystallization rate of the GaN-based compound semiconductor crystal can be increased. As a result, the GaN-based compound semiconductor single crystal suitable for the semiconductor device can be produced with a high yield.
Claims (2)
前記希土類１３（３Ｂ）族ペロブスカイト結晶基板の（０１１）面から＜１００＞方向に１°から４°だけオフアングルさせた面を成長面とすることを特徴とするＧａＮ系化合物半導体結晶の製造方法。In a method of growing a GaN-based compound semiconductor crystal using a rare earth 13 (3B) group perovskite crystal containing one or more kinds of rare earth elements as a substrate,
A method for producing a GaN-based compound semiconductor crystal, characterized in that a growth plane is a plane that is off-angled by 1 ° to 4 ° in the <100> direction from the (011) plane of the rare earth 13 (3B) group perovskite crystal substrate. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001078246A JP3785566B2 (en) | 2001-03-19 | 2001-03-19 | GaN compound semiconductor crystal manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001078246A JP3785566B2 (en) | 2001-03-19 | 2001-03-19 | GaN compound semiconductor crystal manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002274997A JP2002274997A (en) | 2002-09-25 |
| JP3785566B2 true JP3785566B2 (en) | 2006-06-14 |
Family
ID=18934887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001078246A Expired - Fee Related JP3785566B2 (en) | 2001-03-19 | 2001-03-19 | GaN compound semiconductor crystal manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3785566B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY141883A (en) | 2001-06-06 | 2010-07-16 | Ammono Sp Zoo | Process and apparatus for obtaining bulk mono-crystalline gallium-containing nitride |
| CN1300901C (en) | 2001-10-26 | 2007-02-14 | 波兰商艾蒙诺公司 | Light emitting element structure using nitride bulk single crystal layer |
| US20060138431A1 (en) | 2002-05-17 | 2006-06-29 | Robert Dwilinski | Light emitting device structure having nitride bulk single crystal layer |
| PL225427B1 (en) * | 2002-05-17 | 2017-04-28 | Ammono Spółka Z Ograniczoną Odpowiedzialnością | Light emitting element structure having nitride bulk single crystal layer |
| PL224993B1 (en) | 2002-12-11 | 2017-02-28 | Ammono Spółka Z Ograniczoną Odpowiedzialnością | Process for obtaining bulk monocrystalline gallium-containing nitride |
| US7410539B2 (en) | 2002-12-11 | 2008-08-12 | Ammono Sp. Z O.O. | Template type substrate and a method of preparing the same |
| WO2005121415A1 (en) | 2004-06-11 | 2005-12-22 | Ammono Sp. Z O.O. | Bulk mono-crystalline gallium-containing nitride and its application |
| PL371405A1 (en) | 2004-11-26 | 2006-05-29 | Ammono Sp.Z O.O. | Method for manufacture of volumetric monocrystals by their growth on crystal nucleus |
| DE102005021099A1 (en) | 2005-05-06 | 2006-12-07 | Universität Ulm | GaN layers |
| JP5529420B2 (en) | 2009-02-09 | 2014-06-25 | 住友電気工業株式会社 | Epitaxial wafer, method for producing gallium nitride semiconductor device, gallium nitride semiconductor device, and gallium oxide wafer |
-
2001
- 2001-03-19 JP JP2001078246A patent/JP3785566B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002274997A (en) | 2002-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4581490B2 (en) | III-V group nitride semiconductor free-standing substrate manufacturing method and III-V group nitride semiconductor manufacturing method | |
| JP4150527B2 (en) | Crystal production method | |
| JP2002343728A (en) | Gallium nitride crystalline substrate and method for manufacturing the same | |
| JP2007519591A5 (en) | ||
| JP2009071279A (en) | Substrate for growing gallium nitride and method for preparing substrate for growing gallium nitride | |
| TW200933705A (en) | Group III nitride semiconductor and a manufacturing method thereof | |
| JP3785566B2 (en) | GaN compound semiconductor crystal manufacturing method | |
| JP2002299253A (en) | Production method for semiconductor wafer and semiconductor device | |
| JP2002305155A (en) | CRYSTAL GROWING APPARATUS FOR GaN-BASED COMPOUND SEMICONDUCTOR CRYSTAL | |
| JP3758537B2 (en) | Method for producing group III nitride compound semiconductor | |
| JP2011093803A (en) | Method for manufacturing gallium nitride-based compound semiconductor single crystal | |
| US6875272B2 (en) | Method for preparing GaN based compound semiconductor crystal | |
| JP4236121B2 (en) | Manufacturing method of semiconductor substrate | |
| JP4236122B2 (en) | Manufacturing method of semiconductor substrate | |
| JP4355232B2 (en) | GaN compound semiconductor crystal manufacturing method and GaN compound semiconductor crystal | |
| JP4673514B2 (en) | GaN compound semiconductor crystal manufacturing method | |
| JP2013209270A (en) | Production method for nitride semiconductor crystal of group 13 metal of periodic table, and nitride semiconductor crystal of group 13 metal of periodic table obtained by the production method | |
| JP2003218043A (en) | METHOD OF MANUFACTURING GaN-BASED COMPOUND SEMICONDUCTOR CRYSTAL | |
| JP2002211999A (en) | Method of producing crystal growth substrate of group iii nitride-based compound semiconductor | |
| KR100839224B1 (en) | Method for manufacturing thick film of gan | |
| JP2000012901A (en) | Manufacture of gallium nitride-based compound semiconductor single crystal | |
| JP2000247790A (en) | Substrate for semiconductor element, semiconductor element and production of nitrogen compound single crystal substrate | |
| CN116504607A (en) | Epitaxial layer of gallium nitride on silicon and preparation method of HEMT device | |
| JP2008162886A (en) | Method for manufacturing substrate | |
| JP2003073195A (en) | Method for producing gallium nitride crystal and gallium nitride crystal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20051110 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20051122 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060120 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060307 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060308 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090331 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090331 Year of fee payment: 3 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090331 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090331 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100331 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100331 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110331 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110331 Year of fee payment: 5 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110331 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120331 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120331 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130331 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130331 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140331 Year of fee payment: 8 |
|
| LAPS | Cancellation because of no payment of annual fees |