JP2011068548A - GROUP 3B NITRIDE CRYSTAL IN WHICH Zn IS DOPED, MANUFACTURING METHOD THEREFOR, AND ELECTRONIC DEVICE - Google Patents
GROUP 3B NITRIDE CRYSTAL IN WHICH Zn IS DOPED, MANUFACTURING METHOD THEREFOR, AND ELECTRONIC DEVICE Download PDFInfo
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Abstract
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本発明は、Ｚｎがドープされた３Ｂ族窒化物結晶、その製法及び電子デバイスに関する。 The present invention relates to a group 3B nitride crystal doped with Zn, a method for producing the same, and an electronic device.
携帯電話の基地局用のパワーアンプに代表される高周波デバイスとしては、現在のところ砒化ガリウム（ＧａＡｓ）が用いられている。一方、窒化ガリウム（ＧａＮ）を用いた高周波デバイスは、ＧａＡｓを用いた高周波デバイスよりも、数多くの有利な特性を持っている。例えば、ＧａＮはバンドギャップがＧａＡｓと比べて広く絶縁破壊電界が大きいため、ＧａＮを用いた高周波デバイスはＧａＡｓを用いた高周波デバイスよりも高耐圧化が可能になる。その結果、高い電圧を印加して大電流を流すことが可能となり、高出力化に適している。一方、高周波デバイスに用いられるＧａＮは高抵抗であることが要求されるが、ノンドープＧａＮの比抵抗は０．１Ω・ｃｍ程度であるため、不純物ドープによる高抵抗のＧａＮの開発が進められている。 Currently, gallium arsenide (GaAs) is used as a high-frequency device typified by a power amplifier for a cellular phone base station. On the other hand, a high-frequency device using gallium nitride (GaN) has many advantageous characteristics as compared to a high-frequency device using GaAs. For example, since GaN has a wider band gap and a higher dielectric breakdown electric field than GaAs, a high-frequency device using GaN can have a higher breakdown voltage than a high-frequency device using GaAs. As a result, it is possible to apply a high voltage to flow a large current, which is suitable for high output. On the other hand, GaN used for high-frequency devices is required to have high resistance, but since the specific resistance of non-doped GaN is about 0.1 Ω · cm, development of high-resistance GaN by impurity doping is underway. .
例えば、特許文献１には、高抵抗ＧａＮ層として、ＺｎドープＧａＮ層が開示されている。具体的には、ＺｎドープＧａＮ層を比抵抗１Ωｃｍ以上１×１０5Ωｃｍ以下のＧａＮ層として利用することや、Ｚｎのドープ量を１×１０16ｃｍ-3以上１×１０19ｃｍ-3以下とするのが好ましいこと（単位は正しくはａｔｏｍｓ／ｃｍ-3と思われる）、Ｚｎのドープ量が１×１０16ｃｍ-3未満だと高抵抗にすることが困難なため好ましくなく１×１０19ｃｍ-3 を超えるとＧａＮの結晶性が悪化するおそれがあるため好ましくないこと等が開示されている。このようなＺｎドープＧａＮ層は、特許文献２に記載されているように、分子線エピタキシャル法（ＭＢＥ法）つまり気相法によって形成される。一方、特許文献３では、フラックス法において、ＺｎドープＧａＮ結晶の作製が試みられている。 For example, Patent Document 1 discloses a Zn-doped GaN layer as a high-resistance GaN layer. Specifically, the Zn-doped GaN layer is used as a GaN layer having a specific resistance of 1 Ωcm or more and 1 × 10 5 Ωcm or less, or the Zn doping amount is 1 × 10 16 cm -3 or more and 1 × 10 19 cm -3 or less. (The unit is supposed to be atoms / cm −3 correctly), and if the doping amount of Zn is less than 1 × 10 16 cm −3 , it is difficult to obtain a high resistance, which is not preferable. It is disclosed that if it exceeds 19 cm −3 , the crystallinity of GaN may be deteriorated, which is not preferable. Such a Zn-doped GaN layer is formed by a molecular beam epitaxial method (MBE method), that is, a vapor phase method, as described in Patent Document 2. On the other hand, Patent Document 3 attempts to produce a Zn-doped GaN crystal by a flux method.
しかしながら、気相法によって得られるＺｎドープＧａＮ層は、転位密度の低い高品質なものを得るのが難しいという問題があった。一方、特許文献３では、フラックス法によるＺｎドープＧａＮ結晶の作製が試みられているが、フラックス組成中のＺｎ添加量はごくわずかな量（フラックスに対し、０．００１〜０．１モル％）に限られていた。また、本発明者らが特許文献３の実施例４を追試したところ、上述のＺｎ添加量では、ＧａＮ結晶中のＺｎ取り込み量は３×１０16〜１×１０17ａｔｏｍｓ／ｃｍ3であり、ホール測定による比抵抗は０．５〜１．１Ω・ｃｍであった。この比抵抗は、Ｚｎ無添加で育成した場合の１０倍程度の抵抗値でしかない。ここで、特許文献３に記載のテスターや４探針法（特許文献３における「４端子法」は正しくは「４探針法」である）における抵抗測定では、接触抵抗の影響が大きく、その分離が困難であり、精確性に欠けるため、オーミック電極を取り付けたサンプルのホール測定を採用したところ、上述のように比抵抗が低いことが判明した。このため、Ｚｎ添加量を０．１モル％よりも増やしたところ、ガリウムが全く窒化しなくなり、結晶育成が困難となることが確認された。したがって、特許文献３では、再現良くＺｎ添加による高抵抗窒化ガリウム結晶の育成方法は確立されていなかったといえる。 However, the Zn-doped GaN layer obtained by the vapor phase method has a problem that it is difficult to obtain a high-quality layer having a low dislocation density. On the other hand, Patent Document 3 attempts to produce a Zn-doped GaN crystal by a flux method, but the Zn addition amount in the flux composition is very small (0.001 to 0.1 mol% with respect to the flux). It was limited to. In addition, when the present inventors re-examined Example 4 of Patent Document 3, with the above Zn addition amount, the Zn uptake amount in the GaN crystal is 3 × 10 16 to 1 × 10 17 atoms / cm 3 , The specific resistance by Hall measurement was 0.5 to 1.1 Ω · cm. This specific resistance is only about 10 times the resistance value when grown without adding Zn. Here, in the resistance measurement in the tester and the 4-probe method described in Patent Document 3 (“4-probe method” in Patent Document 3 is correctly “4-probe method”), the influence of contact resistance is large. Separation is difficult and lacks accuracy, and therefore, it was found that the specific resistance was low as described above when the hole measurement of the sample to which the ohmic electrode was attached was adopted. For this reason, when Zn addition amount was increased more than 0.1 mol%, it was confirmed that gallium was not nitrided at all and crystal growth became difficult. Therefore, it can be said that Patent Document 3 has not established a method for growing a high-resistance gallium nitride crystal by Zn addition with good reproducibility.
本発明はこのような課題を解決するためになされたものであり、高抵抗且つ低転位密度のＺｎドープ３Ｂ族窒化物結晶を提供することを主目的とする。 The present invention has been made to solve such problems, and has as its main object to provide a Zn-doped group 3B nitride crystal having a high resistance and a low dislocation density.
本発明者らは、系内に炭素を添加したＮａフラックス法でＺｎドープＧａＮを作製することを詳細に検討した結果、従来よりもＺｎを高濃度に添加した組成でも結晶育成が可能であることを見い出した。具体的には、気相法と同様、Ｚｎドープ量が多いと高抵抗になるが結晶性が悪くなることを確認する一方、気相法に比べて比抵抗を高くすることができることや転位密度を低く抑えることができる好適な条件があることを見いだし、本発明を完成するに至った。 As a result of a detailed study of producing Zn-doped GaN by the Na flux method in which carbon is added to the system, the present inventors are able to grow crystals even with a composition in which Zn is added at a higher concentration than before. I found out. Specifically, as in the vapor phase method, it is confirmed that the crystallinity deteriorates when the Zn doping amount is high, while the specific resistance can be increased as compared with the vapor phase method and the dislocation density. The present invention has been completed by finding that there are suitable conditions that can keep the temperature low.
すなわち、本発明のＺｎドープ３Ｂ族窒化物結晶は、室温における比抵抗が１×１０2Ω・ｃｍ以上１×１０9Ω・ｃｍ以下、３Ｂ族窒化物結晶中のＺｎ濃度が１．０×１０18ａｔｏｍｓ／ｃｍ3以上２．０×１０19ａｔｏｍｓ／ｃｍ3以下、エッチピット密度が１×１０6／ｃｍ2以下である。このＺｎドープ３Ｂ族窒化物結晶は、従来のフラックス法で製造されていたものに比べて、Ｚｎ濃度が高く、比抵抗の値が高く、かつ気相法で育成したものよりも転位密度が低い。このため、このＺｎドープ３Ｂ族窒化物結晶に高電圧を印加したとしても漏れ電流が発生することがない。なお、電子デバイス特性の観点から、比抵抗は１×１０6Ω・ｃｍ以上が好ましい。 That is, the Zn-doped group 3B nitride crystal of the present invention has a specific resistance at room temperature of 1 × 10 2 Ω · cm to 1 × 10 9 Ω · cm, and the Zn concentration in the 3B group nitride crystal is 1.0 ×. 10 18 atoms / cm 3 or more and 2.0 × 10 19 atoms / cm 3 or less, and the etch pit density is 1 × 10 6 / cm 2 or less. This Zn-doped group 3B nitride crystal has a higher Zn concentration, a higher specific resistance value, and a lower dislocation density than those grown by the vapor phase method, compared to those produced by the conventional flux method. . For this reason, even if a high voltage is applied to the Zn-doped group 3B nitride crystal, no leakage current is generated. From the viewpoint of electronic device characteristics, the specific resistance is preferably 1 × 10 6 Ω · cm or more.
ここで、３Ｂ族窒化物としては、窒化ホウ素（ＢＮ）、窒化アルミニウム（ＡｌＮ）、窒化ガリウム（ＧａＮ）、窒化インジウム（ＩｎＮ）、窒化タリウム（ＴｌＮ）などが挙げられるが、このうち窒化ガリウムが好ましい。 Here, examples of the group 3B nitride include boron nitride (BN), aluminum nitride (AlN), gallium nitride (GaN), indium nitride (InN), and thallium nitride (TlN). preferable.
本発明のＺｎドープ３Ｂ族窒化物結晶がＺｎドープ窒化ガリウム結晶の場合、波長３３０〜３８５ｎｍの光（例えば水銀ランプの光）を照射したときに４４０〜４７０ｎｍにピークを有するブロードな蛍光（青色の蛍光）を発する。Ｎａフラックス法により作製した窒化ガリウムの結晶は、一般にこの波長の光を照射すると青色の光を発する。これに対して、気相法により作製した窒化ガリウムの結晶は、同様の光を照射すると黄色の蛍光を発する。このため、この波長の光を照射したときに発する蛍光の色によって、Ｎａフラックス法による結晶か気相法による結晶かを区別することができる。 When the Zn-doped group 3B nitride crystal of the present invention is a Zn-doped gallium nitride crystal, broad fluorescence (blue-colored) having a peak at 440 to 470 nm when irradiated with light having a wavelength of 330 to 385 nm (for example, light from a mercury lamp). (Fluorescence). Gallium nitride crystals produced by the Na flux method generally emit blue light when irradiated with light of this wavelength. On the other hand, a gallium nitride crystal produced by a vapor phase method emits yellow fluorescence when irradiated with the same light. For this reason, it is possible to distinguish between crystals produced by the Na flux method and those produced by the vapor phase method, depending on the color of the fluorescence emitted when irradiated with light of this wavelength.
本発明の電子デバイスは、上述した本発明のＺｎドープ３Ｂ族窒化物結晶を利用したものである。この電子デバイスとしては、例えば、ハイブリッド自動車用のインバータに用いられるパワーデバイス（電界効果トランジスタ）や携帯電話の基地局用の高周波パワーアンプ（ＨＥＭＴ）などが挙げられる。また、本発明のＺｎドープ３Ｂ族窒化物結晶は、ＬＥＤ等の光デバイスにも利用することができる。 The electronic device of the present invention utilizes the above-described Zn-doped group 3B nitride crystal of the present invention. Examples of the electronic device include a power device (field effect transistor) used for an inverter for a hybrid vehicle and a high frequency power amplifier (HEMT) for a base station of a mobile phone. The Zn-doped group 3B nitride crystal of the present invention can also be used for optical devices such as LEDs.
本発明のＺｎドープ３Ｂ族窒化物結晶の製法は、種結晶基板を３Ｂ族金属、フラックス及び亜鉛を含む混合融液に浸漬して窒素ガスを含む加圧雰囲気下で加熱した状態で前記種結晶基板上にＺｎドープ３Ｂ族窒化物の結晶を成長させる方法であって、前記混合融液として炭素が添加されたものを用い、該混合融液中の亜鉛濃度を３Ｂ族金属に対して０．０４〜８ｍｏｌ％とするものである。この製法によれば、従来の気相法で製造されていたものに比べて、比抵抗の値が高く、転位密度が低いＺｎドープ３Ｂ族窒化物結晶が得られる。ここで、亜鉛濃度が下限値を下回る場合には、得られるＺｎドープ３Ｂ族窒化物結晶の比抵抗が十分高くならないため好ましくない。また、亜鉛濃度が上限値を上回る場合には、結晶性が低下するため好ましくない。亜鉛濃度は、０．２〜１．５モル％とするのが好ましく、０．５〜１．０モル％とするのがより好ましい。また、炭素は、フラックスに対して０．３〜１．０モル％添加するのが好ましい。炭素の濃度が下限値を下回る場合には、亜鉛によるガリウムの窒化阻害を抑制する効果が弱くなるため好ましくなく、上限値を上回る場合には、無極性面が発達し、亜鉛を添加された結晶育成が困難になるため好ましくない。 In the method for producing a Zn-doped group 3B nitride crystal of the present invention, the seed crystal is immersed in a mixed melt containing a group 3B metal, a flux and zinc and heated in a pressurized atmosphere containing nitrogen gas. A method for growing a Zn-doped group 3B nitride crystal on a substrate, wherein carbon is added as the mixed melt, and the zinc concentration in the mixed melt is set to 0. 3 with respect to the group 3B metal. It is set to 04 to 8 mol%. According to this manufacturing method, a Zn-doped group 3B nitride crystal having a high specific resistance value and a low dislocation density can be obtained as compared with those manufactured by a conventional vapor phase method. Here, when the zinc concentration is lower than the lower limit, the specific resistance of the obtained Zn-doped 3B group nitride crystal is not sufficiently high, which is not preferable. Moreover, since crystallinity falls when a zinc concentration exceeds an upper limit, it is unpreferable. The zinc concentration is preferably 0.2 to 1.5 mol%, and more preferably 0.5 to 1.0 mol%. Moreover, it is preferable to add carbon 0.3 to 1.0 mol% with respect to the flux. When the concentration of carbon is below the lower limit, the effect of suppressing inhibition of gallium nitridation by zinc is weakened, which is not preferable. When the concentration exceeds the upper limit, a nonpolar plane develops and crystals with added zinc are added. Since it becomes difficult to grow, it is not preferable.
なお、フラックス中に炭素を添加すること自体は、国際公開２００８／０５９９０１号パンフレットに記載がある。しかしながら、このパンフレットにおける炭素を添加する効果は、核発生を抑制することと、無極性面の成長が促進されることである。本発明における炭素を添加する効果は、亜鉛を用いた場合のガリウムの窒化阻害を抑制することであり、この点はこれまで知られていなかった。この効果が得られる理由は定かではないが、ナトリウム−ガリウム混合融液における、窒素分子の解離障壁（窒素分子が窒素原子２つに分かれるために必要なエネルギー）よりも、亜鉛−ナトリウム−ガリウム系における、窒素分子の解離障壁が高いのに対し、炭素−亜鉛−ナトリウム−ガリウム系における窒素分子の解離障壁はナトリウム−ガリウム系のそれと同程度となるためであると考えている。 Note that adding carbon to the flux itself is described in the pamphlet of International Publication No. 2008/059901. However, the effect of adding carbon in this pamphlet is to suppress nucleation and promote the growth of nonpolar surfaces. The effect of adding carbon in the present invention is to suppress inhibition of gallium nitridation when zinc is used, and this point has not been known so far. The reason why this effect is obtained is not clear, but the zinc-sodium-gallium system rather than the dissociation barrier of nitrogen molecules (energy required for the nitrogen molecules to be divided into two nitrogen atoms) in the sodium-gallium mixed melt. This is because the dissociation barrier of nitrogen molecules is high, whereas the dissociation barrier of nitrogen molecules in the carbon-zinc-sodium-gallium system is similar to that of the sodium-gallium system.
本発明のＺｎドープ３Ｂ族窒化物結晶を製造する好適な装置について、図面を用いて以下に説明する。図１は、結晶板製造装置１０の上部を水平に切断したときの断面図、図２は、図１のＡ−Ａ断面図、図３は、耐圧容器１２の全体構成を示す説明図（断面図）である。なお、図１及び図２では、便宜上、窒素ガスボンベ２２や真空ポンプ２６などの周辺機器は省略した。 A suitable apparatus for producing the Zn-doped group 3B nitride crystal of the present invention will be described below with reference to the drawings. 1 is a cross-sectional view when the upper part of the crystal plate manufacturing apparatus 10 is cut horizontally, FIG. 2 is a cross-sectional view taken along line AA of FIG. 1, and FIG. Figure). 1 and 2, peripheral devices such as the nitrogen gas cylinder 22 and the vacuum pump 26 are omitted for convenience.
結晶板製造装置１０は、図１に示すように、耐圧容器１２と、この耐圧容器１２を揺動可能な揺動装置７０とを備えている。 As shown in FIG. 1, the crystal plate manufacturing apparatus 10 includes a pressure vessel 12 and a rocking device 70 that can rock the pressure vessel 12.
耐圧容器１２は、鍔の付いた容器本体１２ａと、同じく鍔の付いた容器蓋１２ｂとからなる。この耐圧容器１２は、図３に示すように、内部にヒータカバー１４で囲まれた加熱空間１６を有している。この加熱空間１６は、ヒータカバー１４の側面の上下方向に配置された上段ヒータ１８ａ、中段ヒータ１８ｂ及び下段ヒータ１８ｃのほか、ヒータカバー１４の底面に配置された底部ヒータ１８ｄによって内部温度が調節可能となっている。この加熱空間１６は、ヒータカバー１４の周囲を覆うヒータ断熱材２０によって断熱性が高められている。また、耐圧容器１２には、窒素ガスボンベ２２の窒素導入パイプ２４ａ，２４ｂが接続されると共に真空ポンプ２６の真空引き配管２８が接続されている。窒素導入パイプ２４ａは、耐圧容器１２、ヒータ断熱材２０、ヒータカバー１４及びコンテナ４２を貫通してコンテナ４２の内部に窒素ガスを導入可能となっている。窒素導入パイプ２４ｂは、耐圧容器１２を貫通して耐圧容器１２の内部に窒素ガスを導入可能となっている。窒素導入パイプ２４ａ，２４ｂのうち窒素ガスボンベ２２から耐圧容器１２に至るまでの部分はフレキシブルパイプで構成されている。また、窒素導入パイプ２４ａには流量を調節可能なマスフローコントローラ２５が取り付けられ、窒素導入パイプ２４ｂにはパイプの開閉が可能なバルブ２７が取り付けられている。真空引き配管２８は、耐圧容器１２を貫通し、耐圧容器１２とヒータ断熱材２０との隙間に開口している。ヒータカバー１４は、完全に密閉されているわけではないため、ヒータカバー１４の外側が真空状態になればその内側も真空状態になる。この真空引き配管２８はフレキシブルパイプで構成されている。耐圧容器１２には、更にバルブ４９の付いた窒素排気パイプ４８が取り付けられている。この窒素排気パイプ４８は、バルブ４９を開くことによりコンテナ４２の内部と外気とが連通するようになっている。この窒素排気パイプ４８のうち耐圧容器１２の外側部分は、フレキシブルパイプで構成されている。 The pressure vessel 12 includes a container body 12a with a jar and a container lid 12b with a jar. As shown in FIG. 3, the pressure vessel 12 has a heating space 16 surrounded by a heater cover 14. The internal temperature of the heating space 16 can be adjusted by the upper heater 18a, the middle heater 18b, and the lower heater 18c arranged in the vertical direction of the side surface of the heater cover 14 and the bottom heater 18d arranged on the bottom surface of the heater cover 14. It has become. The heating space 16 has enhanced heat insulation properties by a heater heat insulating material 20 that covers the periphery of the heater cover 14. Further, the pressure vessel 12 is connected to nitrogen introducing pipes 24 a and 24 b of the nitrogen gas cylinder 22 and to a vacuuming pipe 28 of a vacuum pump 26. The nitrogen introduction pipe 24 a can introduce nitrogen gas into the container 42 through the pressure vessel 12, the heater heat insulating material 20, the heater cover 14, and the container 42. The nitrogen introduction pipe 24 b can penetrate the pressure vessel 12 and introduce nitrogen gas into the pressure vessel 12. Of the nitrogen introduction pipes 24a and 24b, the part from the nitrogen gas cylinder 22 to the pressure vessel 12 is constituted by a flexible pipe. A mass flow controller 25 capable of adjusting the flow rate is attached to the nitrogen introduction pipe 24a, and a valve 27 capable of opening and closing the pipe is attached to the nitrogen introduction pipe 24b. The evacuation pipe 28 penetrates the pressure vessel 12 and opens in a gap between the pressure vessel 12 and the heater heat insulating material 20. Since the heater cover 14 is not completely sealed, if the outside of the heater cover 14 is in a vacuum state, the inside is also in a vacuum state. The evacuation pipe 28 is a flexible pipe. A nitrogen exhaust pipe 48 with a valve 49 is further attached to the pressure vessel 12. The nitrogen exhaust pipe 48 opens the valve 49 so that the inside of the container 42 communicates with the outside air. Of the nitrogen exhaust pipe 48, the outer portion of the pressure vessel 12 is formed of a flexible pipe.
耐圧容器１２の内部には、嵩上げ台３０の上にコンテナ４２が配置されている。コンテナ４２は、有底筒状でインコネル製のコンテナ本体４２ａと、このコンテナ本体４２ａの上部開口を閉鎖するインコネル製のコンテナ蓋４２ｂとを備えている。コンテナ蓋４２ｂには、窒素導入パイプ２４ａと共に、導入した窒素がコンテナ４２の内部空間からオーバーフローする分を排出するための窒素排気パイプ４８も併設されている。コンテナ４２の内部には、有底筒状の本体と蓋とを備えた中間容器６０が収容され、この中間容器６０の内部には、有底筒状の本体と蓋とを備えたアルミナ製の育成容器５０が配置されている。育成容器５０には、育成原料（例えばナトリウム／ガリウム／亜鉛／炭素）の混合融液が入っており、その混合融液中に円板状でアルミナ製の種結晶基板トレー５２が配置されている。この種結晶基板トレー５２は、一端がトレー台５６に接し、他端が育成容器５０の底面に接している。また、種結晶基板トレー５２は、中央部分に円板状の種結晶基板５４をはめ込むための凹みを有している。種結晶基板５４は、サファイア基板の表面にＧａＮの薄膜が気相法により形成されたものを用いてもよいし、ＧａＮの基板を用いてもよい。 A container 42 is disposed on the raising platform 30 inside the pressure vessel 12. The container 42 includes a bottomed cylindrical Inconel container main body 42a and an Inconel container lid 42b that closes the upper opening of the container main body 42a. In addition to the nitrogen introduction pipe 24 a, the container lid 42 b is also provided with a nitrogen exhaust pipe 48 for discharging the introduced nitrogen from the internal space of the container 42. An intermediate container 60 having a bottomed cylindrical main body and a lid is accommodated in the container 42, and the intermediate container 60 is made of alumina having a bottomed cylindrical main body and a lid. A growth container 50 is arranged. The growth container 50 contains a mixed melt of growth raw materials (for example, sodium / gallium / zinc / carbon), and a seed crystal substrate tray 52 made of alumina in a disk shape is disposed in the mixed melt. . The seed crystal substrate tray 52 has one end in contact with the tray base 56 and the other end in contact with the bottom surface of the growth vessel 50. The seed crystal substrate tray 52 has a recess for fitting a disc-shaped seed crystal substrate 54 at the center. The seed crystal substrate 54 may be a sapphire substrate having a GaN thin film formed by a vapor phase method, or a GaN substrate.
揺動装置７０は、図１及び図２に示すように、耐圧容器１２を載置する基台７２と、この基台７２の周囲に立設された４本の柱７３の上方にそれぞれ取り付けられたブラケット７４と、各ブラケット７４と基台７２との間に接続された伸縮機構７６とを備えている。基台７２は、平面視したときの形状が略四角形である板状部材であり、中央に耐圧容器１２を載置可能となっている。ブラケット７４は、サーボモータを有するアクチュエータ７８を水平軸により揺動可能に支持している。伸縮機構７６は、下方にシリンダ７７が取り付けられたアクチュエータ７８と、シリンダ７７に取り付けられボールネジを介して上下方向に伸縮可能な可動シャフト８０と、この可動シャフト８０の下端に取り付けられたユニバーサルジョイント８２と、基台７２に固定されユニバーサルジョイント８２を支持する支持シャフト８４とを備えている。そして、図２において、互いに向かい合う一対の伸縮機構７６，７６（左側及び右側の伸縮機構７６，７６）の一方の可動シャフト８０（右側の可動シャフト８０）を伸ばし他方の可動シャフト８０（左側の可動シャフト８０）を縮めることにより、基台７２は図４のように斜めに傾斜する。このとき、各支持シャフト８４は基台７２に固定されているが、支持シャフト８４と可動シャフト８０との間には全方位の角度に対応するユニバーサルジョイント８２が介在しており、また、アクチュエータ７８はブラケット７４に揺動可能に取り付けられているため、支障なく基台７２を斜めに傾斜させることができる。そして、４つのアクチュエータ７８を図示しないシーケンサにより制御すれば、基台７２を水平面に対して所定角度だけ傾斜させた状態で回転させることができる。これにより、基台７２に載置された耐圧容器１２内の育成容器５０中の混合融液を回転させたり、混合融液に上下方向の対流を起こさせたりすることができる。 As shown in FIGS. 1 and 2, the oscillating device 70 is attached above a base 72 on which the pressure-resistant container 12 is placed and four columns 73 erected around the base 72. Brackets 74, and an expansion / contraction mechanism 76 connected between each bracket 74 and the base 72. The base 72 is a plate-like member having a substantially square shape when viewed in plan, and the pressure-resistant container 12 can be placed in the center. The bracket 74 supports an actuator 78 having a servo motor so as to be swingable about a horizontal axis. The expansion / contraction mechanism 76 includes an actuator 78 having a cylinder 77 attached below, a movable shaft 80 that is attached to the cylinder 77 and can be expanded and contracted in the vertical direction via a ball screw, and a universal joint 82 that is attached to the lower end of the movable shaft 80. And a support shaft 84 that is fixed to the base 72 and supports the universal joint 82. In FIG. 2, one movable shaft 80 (right movable shaft 80) of a pair of expansion mechanisms 76, 76 (left and right expansion mechanisms 76, 76) facing each other is extended and the other movable shaft 80 (left movable). By contracting the shaft 80), the base 72 is inclined obliquely as shown in FIG. At this time, each support shaft 84 is fixed to the base 72, but a universal joint 82 corresponding to angles in all directions is interposed between the support shaft 84 and the movable shaft 80, and an actuator 78 is provided. Is swingably attached to the bracket 74, so that the base 72 can be inclined obliquely without any trouble. If the four actuators 78 are controlled by a sequencer (not shown), the base 72 can be rotated with a predetermined angle with respect to the horizontal plane. Thereby, the mixed melt in the growth container 50 in the pressure-resistant container 12 placed on the base 72 can be rotated, or vertical convection can be caused in the mixed melt.
このようにして構成された本実施形態の結晶板製造装置１０の使用例について説明する。この結晶板製造装置１０は、フラックス法によりＺｎドープ３Ｂ族窒化物結晶を製造するのに用いられる。以下には、Ｚｎドープ３Ｂ族窒化物結晶としてＺｎドープＧａＮ結晶を製造する場合を例に挙げて説明する。この場合、種結晶基板５４としては、ＧａＮテンプレート、３Ｂ族金属としては金属ガリウム、フラックスとしては金属ナトリウムを用意する。まず、育成容器５０内で種結晶基板５４を金属ガリウム、金属ナトリウム、金属亜鉛及び炭素を含む混合融液に浸漬する。続いて、真空ポンプ２６により、耐圧容器１２内部を１０-2Ｐａ台まで真空引きし、内部に残留する水分、酸素を低減する。その後、所定の圧力まで窒素ガスを導入し、加熱空間１６が所定の結晶成長温度になるように各ヒータ１８ａ〜１８ｄを制御しながら混合融液に窒素ガスを供給し続ける。その後、アクチュエータ７８を制御して基台を水平面に対して所定角度（例えば５〜１５°）傾斜させた状態で時計回りや反時計回りに所定周期（例えば３０〜３００秒）で切り替えながら所定の速度（例えば１〜１０ｒｐｍの速度）で回転させることにより、育成容器５０の内容物を強制的に攪拌する。こうすることにより、種結晶基板５４に対して混合融液を絶えず移動させることができる。この際、種結晶基板５４の最も結晶成長の速い面を上向きとするのが好ましい。こうすれば、常に気液界面で窒素が溶け込んだ原料を種結晶に供給することになり、高品質な３Ｂ族金属窒化物を得やすい。この状態を維持することにより、混合融液中で種結晶基板５４上にＺｎドープＧａＮの結晶が成長する。なお、混合融液に炭素を適量加えると、亜鉛によるガリウム原料の窒化阻害が抑制される。育成容器５０内の混合融液中で成長したＺｎドープＧａＮ結晶板は、冷却後、容器に有機溶剤（例えばイソプロパノールやエタノールなどの低級アルコール）を加えて該有機溶剤にフラックスなどの不要物を溶かすことにより回収することができる。 A usage example of the crystal plate manufacturing apparatus 10 of the present embodiment configured as described above will be described. This crystal plate manufacturing apparatus 10 is used to manufacture a Zn-doped group 3B nitride crystal by a flux method. Hereinafter, a case where a Zn-doped GaN crystal is manufactured as a Zn-doped group 3B nitride crystal will be described as an example. In this case, as the seed crystal substrate 54, a GaN template is prepared as a 3B group metal, metal gallium, and a flux as metal sodium. First, the seed crystal substrate 54 is immersed in a mixed melt containing metal gallium, metal sodium, metal zinc, and carbon in the growth vessel 50. Subsequently, the inside of the pressure vessel 12 is evacuated to a level of 10 −2 Pa by the vacuum pump 26 to reduce moisture and oxygen remaining inside. Thereafter, nitrogen gas is introduced to a predetermined pressure, and the nitrogen gas is continuously supplied to the mixed melt while controlling the heaters 18a to 18d so that the heating space 16 reaches a predetermined crystal growth temperature. Thereafter, the actuator 78 is controlled so that the base is inclined at a predetermined angle (for example, 5 to 15 °) with respect to the horizontal plane, and is switched in a predetermined cycle (for example, 30 to 300 seconds) in a clockwise direction or a counterclockwise direction. By rotating at a speed (for example, a speed of 1 to 10 rpm), the contents of the growth container 50 are forcibly stirred. By doing so, the mixed melt can be continuously moved with respect to the seed crystal substrate 54. At this time, it is preferable that the surface of the seed crystal substrate 54 having the fastest crystal growth is faced upward. In this way, a raw material in which nitrogen is dissolved at the gas-liquid interface is always supplied to the seed crystal, and it is easy to obtain a high-quality group 3B metal nitride. By maintaining this state, a Zn-doped GaN crystal grows on the seed crystal substrate 54 in the mixed melt. When an appropriate amount of carbon is added to the mixed melt, inhibition of nitriding of the gallium raw material by zinc is suppressed. After cooling the Zn-doped GaN crystal plate grown in the mixed melt in the growth vessel 50, an organic solvent (for example, a lower alcohol such as isopropanol or ethanol) is added to the vessel to dissolve unnecessary substances such as flux in the organic solvent. Can be recovered.
上述したようにＺｎドープＧａＮ結晶板を製造する場合、結晶成長温度は８００〜９５０℃に設定するのが好ましく、８５０〜９００℃に設定するのがより好ましい。加熱空間１６の温度を均一にするには、上段ヒータ１８ａ、中段ヒータ１８ｂ、下段ヒータ１８ｃ、底部ヒータ１８ｄの順に温度が高くなるように設定したり、上段ヒータ１８ａと中段ヒータ１８ｂを同じ温度Ｔ１に設定し、下段ヒータ１８ｃと底部ヒータ１８ｄをその温度Ｔ１よりも高い温度Ｔ２に設定したりするのが好ましい。また、窒素ガスの圧力は、２〜５ＭＰａに設定するのが好ましく、２．５〜４ＭＰａに設定するのがより好ましい。窒素ガスの圧力を調整するには、まず、真空ポンプ２６を駆動して真空引き配管２８を介して耐圧容器１２の内部圧力を高真空状態（例えば１Ｐａ以下とか０．１Ｐａ以下）とし、その後、真空引き配管２８を図示しないバルブによって閉鎖し、窒素ガスボンベ２２から窒素導入パイプ２４ａを介して加熱空間１６に窒素ガスを供給することにより行う。ＧａＮ結晶が成長している間、炉内の構造物から不純物が拡散することによりコンテナ４２の内部の雰囲気が汚染されることを防ぐために、結晶成長中は加熱空間１６に窒素ガスをマスフローコントローラ２５により所定流量となるように供給し続ける。この間、窒素導入パイプ２４ｂはバルブ２７により閉鎖する。なお、オーバーフローした窒素ガスは窒素排気パイプ４８を介して大気へ放出される。 As described above, when a Zn-doped GaN crystal plate is manufactured, the crystal growth temperature is preferably set to 800 to 950 ° C, and more preferably set to 850 to 900 ° C. In order to make the temperature of the heating space 16 uniform, the upper heater 18a, the middle heater 18b, the lower heater 18c, and the bottom heater 18d are set to increase in temperature in order, or the upper heater 18a and the middle heater 18b are set to the same temperature T1. Preferably, the lower heater 18c and the bottom heater 18d are set to a temperature T2 higher than the temperature T1. Moreover, it is preferable to set the pressure of nitrogen gas to 2-5 MPa, and it is more preferable to set to 2.5-4 MPa. In order to adjust the pressure of the nitrogen gas, first, the vacuum pump 26 is driven and the internal pressure of the pressure vessel 12 is set to a high vacuum state (for example, 1 Pa or less or 0.1 Pa or less) through the evacuation pipe 28, The evacuation pipe 28 is closed by a valve (not shown), and nitrogen gas is supplied from the nitrogen gas cylinder 22 to the heating space 16 through the nitrogen introduction pipe 24a. While the GaN crystal is growing, nitrogen gas is supplied to the heating space 16 during the crystal growth in order to prevent impurities inside the furnace from diffusing impurities from contaminating the atmosphere inside the container 42. The supply is continued at a predetermined flow rate. During this time, the nitrogen introduction pipe 24 b is closed by the valve 27. The overflowed nitrogen gas is discharged to the atmosphere through the nitrogen exhaust pipe 48.
以上詳述したように、本実施形態の結晶板製造装置１０によれば、比抵抗の値が高く転位密度の低いＺｎドープＧａＮ結晶板を得ることができる。また、育成容器５０内の内容物を強制的に撹拌するため、Ｚｎが均一に分散しやすく、ＺｎドープＧａＮ結晶が均質になりやすい。更に、上、中、下段ヒータ１８ａ〜１８ｃに加えて底部ヒータ１８ｄを配置したため、加熱空間１６のうち温度が不均一になりやすい底面付近も含めて全体を均一な温度に維持することができる。 As described above in detail, according to the crystal plate manufacturing apparatus 10 of the present embodiment, a Zn-doped GaN crystal plate having a high specific resistance value and a low dislocation density can be obtained. Moreover, since the contents in the growth vessel 50 are forcibly stirred, Zn is easily dispersed uniformly, and the Zn-doped GaN crystal is likely to be homogeneous. Furthermore, since the bottom heater 18d is arranged in addition to the upper, middle, and lower heaters 18a to 18c, the entire heating space 16 can be maintained at a uniform temperature including the vicinity of the bottom surface where the temperature tends to be non-uniform.
なお、本発明は上述した実施形態に何ら限定されることはなく、本発明の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。 It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that the present invention can be implemented in various modes as long as it belongs to the technical scope of the present invention.
例えば、上述した実施形態では、揺動装置７０により基台７２に載置された耐圧容器１２内の育成容器５０中の融液を回転させたり対流させたりするようにしたが、揺動装置７０の代わりに基台７２を回転させる回転機構を採用して融液を回転させたり対流させたりするようにしてもよい。 For example, in the above-described embodiment, the melt in the growth vessel 50 in the pressure-resistant vessel 12 placed on the base 72 is rotated or convected by the swing device 70. Instead of this, a rotating mechanism that rotates the base 72 may be employed to rotate or convect the melt.
［実施例１］
まず、直径２インチ、厚さ０．４３ｍｍのｃ面サファイア基板の表面に、５５０℃にてＧａＮ低温バッファ層を７０ｎｍ成膜し、その後、厚さ１０μｍのＧａＮ薄膜を１０５０℃にて気相により成膜し、種結晶基板５４として利用可能なＧａＮテンプレートを得た。次いで、このＧａＮテンプレート基板上に、フラックス法によってＺｎドープＧａＮ単結晶を育成した。以下、図１〜図４を参照して具体的に説明する。まず、アルゴン雰囲気のグローブボックス内で、内径φ７０ｍｍの育成容器５０としてのアルミナ坩堝の中にトレー台５６を置き、種結晶基板トレー５２をトレー台５６に立て掛けて角度が１０°になるよう育成容器５０の底面中央に斜めに置き、その種結晶基板トレー５２の中央に種結晶基板５４として先ほどのＧａＮテンプレートを配置した。そして、金属ナトリウム３４ｇ、金属ガリウム３８ｇ、炭素９０ｍｇ、亜鉛１７５ｍｇを育成容器５０内に充填した。このときのＮａに対するＧａの割合は２７ｍｏｌ％、Ｎａに対する亜鉛の割合は０．１８ｍｏｌ％、Ｇａに対する亜鉛の割合は０．４９ｍｏｌ％、Ｎａに対する炭素の割合は０．５ｍｏｌ％であった。亜鉛の原料は、直径１ｍｍのワイヤー状のものを３ｍｍ程度の大きさに切断したものを適量用いた。この育成容器５０を中間容器６０に入れ、この中間容器６０をコンテナ本体４２ａに入れてコンテナ蓋４２ｂを閉じたあと、コンテナ４２を耐圧容器１２の容器本体１２ａに入れ、容器蓋１２ｂを閉めて基台７２の上に設置した。続いて、耐圧容器１２の内部圧力を高真空状態とした後、真空引き配管２８の図示しないバルブを閉じた。続いて、窒素ガスボンベ２２から窒素導入パイプ２４ａ，２４ｂを介して耐圧容器１２内及びコンテナ４２内に窒素ガスを供給し、窒素ガス圧力を１３．２ＭＰａに調整した。また、コンテナ４２の内部温度が８７０℃になるように各ヒータ１８ａ〜１８ｄの温度制御を行った。なお、温度が８７０℃、窒素ガス圧力が１３．２ＭＰａになるまで２時間かけて昇温加圧した。その後、４つのアクチュエータ７８をそれぞれシーケンサを用いて制御することにより、耐圧容器１２を水平方向に対して１０°に傾けた状態で時計回りと反時計回りとを６０秒周期で交互に切り替えることで、育成容器５０内の溶液を攪拌しながら１００時間保持することにより結晶成長させた。なお、耐圧容器１２の回転速度は５ｒｐｍとした。その後、３０時間かけて室温まで徐冷した。その後、耐圧容器１２から育成容器５０を取り出し、エタノールを用いて、フラックスを除去し、種結晶基板５４上に成長したＺｎドープＧａＮ結晶板を回収した。このＺｎドープＧａＮ結晶板は、大きさはφ２インチであり、厚さは約１．０ｍｍであり、焦げ茶色を呈していた（図５の透過顕微鏡像及び図６の全体像を参照）。このＺｎドープＧａＮ結晶板を研磨し、ホール測定により室温における比抵抗を測定したところ、測定上限オーバーであった。このときの測定上限が１０4Ω・ｃｍであったことから、それ以上の高抵抗であることがわかった。次に、サンプルの表裏にオーミック電極を形成し、２端子法により、室温における比抵抗を測定したところ、１０4Ω・ｃｍであった。また、ＳＩＭＳ分析によるＧａＮ結晶中のＺｎ濃度は４×１０18ａｔｏｍｓ／ｃｍ3であった。また、基板中央のＸＲＣ半値幅は（０００２）反射が１２０秒（ａｒｃｓｅｃ、以下同じ）、（１０−１２）反射が１２０秒であり、リン酸：硫酸＝３：１の混合液を用いて２５０℃、１４０分エッチングしたときのエッチピット密度（ＥＰＤ）は５×１０5／ｃｍ2であった。ＥＰＤの具体的な測定手順は、まず、微分干渉顕微鏡にて、４００倍のレンズにて１２０×１５０ミクロンの視野を無作為に選び、５枚撮影した。次に、撮影した画像データから、１００ミクロン角の領域で、ピットが何個あるかを数えた。例えば、ピットが１０個あれば、ＥＰＤは１×１０5／ｃｍ2となる。画像の枚数が多いほど精度の高い値となるが、ここでは５枚の画像データの平均値をもってＥＰＤとした。なお、ＺｎドープＧａＮ結晶中には炭素はほとんど取り込まれず、ＳＩＭＳ分析で検出下限以下（約０．１ｐｐｍ以下）であった。
[Example 1]
First, a 70 nm GaN low-temperature buffer layer is formed on the surface of a c-plane sapphire substrate having a diameter of 2 inches and a thickness of 0.43 mm at 550 ° C., and then a GaN thin film having a thickness of 10 μm is formed by vapor phase at 1050 ° C. Film formation was performed to obtain a GaN template that can be used as a seed crystal substrate 54. Next, a Zn-doped GaN single crystal was grown on the GaN template substrate by a flux method. Hereinafter, a specific description will be given with reference to FIGS. First, in a glove box in an argon atmosphere, a tray base 56 is placed in an alumina crucible as a growth container 50 having an inner diameter of 70 mm, and the seed crystal substrate tray 52 is leaned against the tray base 56 so that the angle becomes 10 °. The GaN template is placed as a seed crystal substrate 54 in the center of the seed crystal substrate tray 52 at an angle at the center of the bottom surface of the 50. Then, 34 g of metallic sodium, 38 g of metallic gallium, 90 mg of carbon, and 175 mg of zinc were filled in the growth vessel 50. At this time, the ratio of Ga to Na was 27 mol%, the ratio of zinc to Na was 0.18 mol%, the ratio of zinc to Ga was 0.49 mol%, and the ratio of carbon to Na was 0.5 mol%. As the zinc raw material, an appropriate amount of a wire-like one having a diameter of 1 mm cut into a size of about 3 mm was used. The growth container 50 is placed in the intermediate container 60, the intermediate container 60 is placed in the container main body 42a and the container lid 42b is closed. It was installed on a table 72. Subsequently, after the internal pressure of the pressure vessel 12 was changed to a high vacuum state, a valve (not shown) of the evacuation pipe 28 was closed. Subsequently, nitrogen gas was supplied from the nitrogen gas cylinder 22 into the pressure vessel 12 and the container 42 through the nitrogen introduction pipes 24a and 24b, and the nitrogen gas pressure was adjusted to 13.2 MPa. Moreover, temperature control of each heater 18a-18d was performed so that the internal temperature of the container 42 might be 870 degreeC. In addition, it heated up and pressurized over 2 hours until temperature became 870 degreeC and nitrogen gas pressure became 13.2 MPa. Thereafter, by controlling the four actuators 78 using a sequencer, the clockwise and counterclockwise directions are alternately switched in a cycle of 60 seconds with the pressure vessel 12 tilted by 10 ° with respect to the horizontal direction. Then, the solution in the growth vessel 50 was held for 100 hours with stirring to grow crystals. The rotational speed of the pressure vessel 12 was 5 rpm. Then, it was gradually cooled to room temperature over 30 hours. Thereafter, the growth vessel 50 was taken out from the pressure vessel 12, the flux was removed using ethanol, and the Zn-doped GaN crystal plate grown on the seed crystal substrate 54 was recovered. This Zn-doped GaN crystal plate had a diameter of 2 inches, a thickness of about 1.0 mm, and a dark brown color (see the transmission microscope image in FIG. 5 and the overall image in FIG. 6). When this Zn-doped GaN crystal plate was polished and the specific resistance at room temperature was measured by hole measurement, the measurement upper limit was exceeded. Since the upper limit of measurement at this time was 10 4 Ω · cm, it was found that the resistance was higher than that. Next, ohmic electrodes were formed on the front and back of the sample, and the specific resistance at room temperature was measured by the two-terminal method, which was 10 4 Ω · cm. Further, the Zn concentration in the GaN crystal by SIMS analysis was 4 × 10 18 atoms / cm 3 . The XRC half width at the center of the substrate is (0002) reflection for 120 seconds (arcsec, the same applies hereinafter), (10-12) reflection for 120 seconds, and 250 using a mixed solution of phosphoric acid: sulfuric acid = 3: 1. The etch pit density (EPD) after etching at 140 ° C. for 140 minutes was 5 × 10 5 / cm 2 . The specific measurement procedure of EPD was as follows. First, a 120 × 150 micron field of view was randomly selected with a 400 × lens using a differential interference microscope, and five images were taken. Next, the number of pits in a 100 micron square area was counted from the photographed image data. For example, if there are 10 pits, the EPD is 1 × 10 5 / cm 2 . As the number of images increases, the accuracy becomes higher. Here, the average value of five image data is used as EPD. Note that carbon was hardly taken into the Zn-doped GaN crystal and was below the lower limit of detection (about 0.1 ppm or less) by SIMS analysis.
［実施例２］
亜鉛を３１０ｍｇにした以外は実施例１と同様にＺｎドープＧａＮ結晶の育成を行った。このときのＮａに対する亜鉛の割合は０．３２ｍｏｌ％、Ｇａに対する亜鉛の割合は０．８７ｍｏｌ％であった。このＺｎドープＧａＮ結晶板は、大きさがφ２インチであり、厚さが約１．２ｍｍであり、実施例１よりも濃い焦げ茶色を呈していた。このＺｎドープＧａＮ結晶板を研磨し、ホール測定により室温における比抵抗を測定したところ、測定上限オーバーであった。このときの測定上限が１０4Ω・ｃｍであったことから、それ以上の高抵抗であることがわかった。次に、サンプルの表裏にオーミック電極を形成し、２端子法により室温における比抵抗を測定したところ、室温において、１０5Ω・ｃｍであった。また、ＳＩＭＳ分析によるＧａＮ結晶中のＺｎ濃度は５×１０18ａｔｏｍｓ／ｃｍ3であった。基板中央のＸＲＣ半値幅は（０００２）反射が１３０秒、（１０−１２）反射が１７０秒であり、リン酸：硫酸＝３：１の混合液を用いて２５０℃、１４０分エッチングしたときのＥＰＤは７×１０5ｃｍ2であった。
[Example 2]
A Zn-doped GaN crystal was grown in the same manner as in Example 1 except that the amount of zinc was 310 mg. At this time, the ratio of zinc to Na was 0.32 mol%, and the ratio of zinc to Ga was 0.87 mol%. This Zn-doped GaN crystal plate had a size of φ2 inches, a thickness of about 1.2 mm, and a darker brown color than that of Example 1. When this Zn-doped GaN crystal plate was polished and the specific resistance at room temperature was measured by hole measurement, the measurement upper limit was exceeded. Since the upper limit of measurement at this time was 10 4 Ω · cm, it was found that the resistance was higher than that. Next, ohmic electrodes were formed on the front and back of the sample, and the specific resistance at room temperature was measured by the two-terminal method, which was 10 5 Ω · cm at room temperature. Further, the Zn concentration in the GaN crystal by SIMS analysis was 5 × 10 18 atoms / cm 3 . The XRC half-width at the center of the substrate is (0002) reflection is 130 seconds, (10-12) reflection is 170 seconds, and etching is performed at 250 ° C. for 140 minutes using a mixed solution of phosphoric acid: sulfuric acid = 3: 1. The EPD was 7 × 10 5 cm 2 .
［実施例３］
ガリウムを３．３ｇ、ナトリウムを４．８ｇ、炭素を１０ｍｇ、亜鉛を５．７ｍｇ用い、育成容器５０としてφ１７ｍｍ×高さ５０ｍｍの円筒平底坩堝を用い、１３ｍｍ×１８ｍｍのＧａＮ自立基板（市販のハイドライド気相成長法（ＨＶＰＥ法）による）を斜めに配置（約７０度）して、８７０℃、４．１ＭＰａにて１２０時間保持したこと以外は実施例１と同様の結晶育成を行った。そうしたところ、種結晶基板上に焦げ茶色を呈したＧａＮ結晶が約１ｍｍ成長した。このときのＮａに対する亜鉛の割合は０．０４２ｍｏｌ％、Ｇａに対する亜鉛の割合は０．１８ｍｏｌ％であった。種結晶基板を除去し、厚さ０．５ｍｍ、３〜５ｍｍ角の研磨したサンプルを切り出し、ホール測定にて室温における比抵抗を測定したところ、１０2Ω・ｃｍであった。ＳＩＭＳ分析により亜鉛濃度を調べたところ、１．３×１０18ａｔｏｍｓ／ｃｍ3であった。ＸＲＣ半値幅は（０００２）反射が１１０秒、（１０−１２）反射が１１０秒であった（図７参照）。リン酸：硫酸＝３：１の混合液を用いて２５０度、１４０分エッチングしたときのＥＰＤは１×１０5／ｃｍ2 であった。
[Example 3]
Using 3.3 g of gallium, 4.8 g of sodium, 10 mg of carbon, and 5.7 mg of zinc, and using a cylindrical flat bottom crucible of φ17 mm × height 50 mm as the growth vessel 50, a 13 mm × 18 mm freestanding GaN substrate (commercially available hydride) Crystal growth was performed in the same manner as in Example 1 except that the vapor phase growth method (HVPE method) was obliquely arranged (about 70 degrees) and held at 870 ° C. and 4.1 MPa for 120 hours. As a result, a dark brown GaN crystal grew about 1 mm on the seed crystal substrate. At this time, the ratio of zinc to Na was 0.042 mol%, and the ratio of zinc to Ga was 0.18 mol%. The seed crystal substrate was removed, a polished sample having a thickness of 0.5 mm and a 3 to 5 mm square was cut out, and the specific resistance at room temperature was measured by hole measurement, which was 10 2 Ω · cm. When the zinc concentration was examined by SIMS analysis, it was 1.3 × 10 18 atoms / cm 3 . The XRC half-width was 110 seconds for (0002) reflection and 110 seconds for (10-12) reflection (see FIG. 7). The EPD when etched with a mixed solution of phosphoric acid: sulfuric acid = 3: 1 at 250 ° C. for 140 minutes was 1 × 10 5 / cm 2 .
［実施例４］
亜鉛を２５ｍｇ用いた以外は、実施例３と同様にしてＺｎドープＧａＮ結晶板を作製した。実施例３と同様にして比抵抗、亜鉛濃度、ＸＲＣ半値幅及びＥＰＤを測定したところ、比抵抗は１×１０6Ω・ｃｍ、ＳＩＭＳ分析による亜鉛濃度は８×１０18ａｔｏｍｓ／ｃｍ3、ＸＲＣ半値幅は（０００２）反射が１５０秒、（１０−１２）反射が１８０秒、ＥＰＤは７×１０5／ｃｍ2であった。
[Example 4]
A Zn-doped GaN crystal plate was produced in the same manner as in Example 3 except that 25 mg of zinc was used. When the specific resistance, zinc concentration, XRC half width and EPD were measured in the same manner as in Example 3, the specific resistance was 1 × 10 6 Ω · cm, the zinc concentration by SIMS analysis was 8 × 10 18 atoms / cm 3 , XRC. The half-value width was 150 seconds for (0002) reflection, 180 seconds for (10-12) reflection, and EPD was 7 × 10 5 / cm 2 .
［実施例５］
亜鉛を２０５ｍｇ用いた以外は、実施例３と同様にしてＺｎドープＧａＮ結晶板を作製した。実施例１と同様にして亜鉛濃度、ＸＲＣ半値幅及びＥＰＤを測定したところ、ＳＩＭＳ分析による亜鉛濃度は１．８×１０19ａｔｏｍｓ／ｃｍ3、ＸＲＣ半値幅は（０００２）反射が２９０秒、（１０−１２）反射が３８０秒（図８参照）、ＥＰＤは５×１０6／ｃｍ2であった。また、室温において、２端子法で測定した時の電圧と比抵抗との関係を図９に示す。図９からわかるように、比抵抗は、１０〜２０Ｖの低電圧領域では１×１０10〜１×１０12Ω・ｃｍと非常に高い値であったが、１００〜５００Ｖの高電圧領域では１×１０8〜１×１０9Ω・ｃｍになった。これは、オーミック電極のオーミックコンタクトが不十分であり、低電圧領域では電流が流れにくくなっているために本来より高めの値となっていると考えられる。よって、本結果での比抵抗の値は、漸近した値の２×１０8Ω・ｃｍを採用した。
[Example 5]
A Zn-doped GaN crystal plate was produced in the same manner as in Example 3 except that 205 mg of zinc was used. When the zinc concentration, XRC half width and EPD were measured in the same manner as in Example 1, the zinc concentration by SIMS analysis was 1.8 × 10 19 atoms / cm 3 , the XRC half width was (0002) reflection for 290 seconds, ( 10-12) Reflection was 380 seconds (see FIG. 8), and EPD was 5 × 10 6 / cm 2 . Further, FIG. 9 shows the relationship between the voltage and the specific resistance when measured by the two-terminal method at room temperature. As can be seen from FIG. 9, the specific resistance was 1 × 10 10 to 1 × 10 12 Ω · cm in the low voltage region of 10 to 20V, but 1 in the high voltage region of 100 to 500V. × 10 8 to 1 × 10 9 Ω · cm. This is probably because the ohmic contact of the ohmic electrode is insufficient, and it is difficult for current to flow in the low voltage region, so that the value is higher than the original value. Therefore, an asymptotic value of 2 × 10 8 Ω · cm was adopted as the specific resistance value in this result.
図１０は、実施例３〜５の結果に基づいて作成したＺｎ添加量とＺｎドープＧａＮ中のＺｎ濃度（Ｚｎドープ量）との関係を表すグラフである。このグラフからわかるように、Ｚｎ添加量が増加するにつれてＺｎ濃度が増加した。図１１及び図１２は、実施例１〜５の結果に基づいて作成した比抵抗のＺｎ濃度依存性のグラフである。このグラフからわかるように、Ｚｎ濃度が増加するにつれて比抵抗も増加した。なお、実施例３〜５の結果から、Ｚｎ濃度が増加するにつれて、ＸＲＣ半値幅が広くなりＥＰＤが大きくなることもわかった。 FIG. 10 is a graph showing the relationship between the Zn addition amount created based on the results of Examples 3 to 5 and the Zn concentration (Zn doping amount) in Zn-doped GaN. As can be seen from this graph, the Zn concentration increased as the Zn addition amount increased. 11 and 12 are graphs showing the Zn concentration dependence of the specific resistance created based on the results of Examples 1 to 5. FIG. As can be seen from this graph, the specific resistance increased as the Zn concentration increased. From the results of Examples 3 to 5, it was also found that the XRC half-value width was widened and the EPD was increased as the Zn concentration was increased.
［実施例６］
ガリウムを８０ｇ、ナトリウムを１２２ｇ、炭素を３１５ｍｇ、亜鉛を７５４ｍｇ用い、育成容器５０としてφ１２０ｍｍ×高さ５０ｍｍの円筒平底坩堝を用い、φ４インチのＧａＮテンプレート（厚さ１ｍｍのｃ面サファイア基板に厚さ５ミクロンのＧａＮ薄膜を気相法でエピタキシャル成長させたもの）を育成容器５０の底に配置して、８７０℃、４．１ＭＰａにて１００時間保持したこと以外は実施例１と同様の結晶育成を行った。そうしたところ、種結晶基板上に焦げ茶色を呈したＧａＮ結晶が約１ｍｍ成長した（図１３の全体像を参照）。このときのＮａに対する亜鉛の割合は０．２２ｍｏｌ％、Ｇａに対する亜鉛の割合は１．０ｍｏｌ％であった。
[Example 6]
80g of gallium, 122g of sodium, 315mg of carbon, 754mg of zinc, a cylindrical flat bottom crucible of φ120mm x height 50mm as the growth vessel 50, φ4 inch GaN template (thickness on 1mm thick c-plane sapphire substrate) A 5 micron GaN thin film (epitaxially grown by vapor phase method) was placed on the bottom of the growth vessel 50, and crystal growth was performed in the same manner as in Example 1 except that it was held at 870 ° C. and 4.1 MPa for 100 hours. went. As a result, a GaN crystal having a dark brown color grew on the seed crystal substrate by about 1 mm (see the entire image in FIG. 13). At this time, the ratio of zinc to Na was 0.22 mol%, and the ratio of zinc to Ga was 1.0 mol%.
育成した結晶をｍ面に平行にスライスし、その切断面を研磨し、厚さ０．５ｍｍ、長さ１０ｍｍの短冊状のサンプルを作製した。研磨面（ｍ面）にオーミック電極を成膜し、２端子法にて室温における比抵抗を測定したところ、２×１０5Ω・ｃｍであった。ＳＩＭＳ分析により亜鉛濃度を調べたところ、４×１０18ａｔｏｍｓ／ｃｍ3であった。ＸＲＣ半値幅は（１０−１０）反射が約８０秒であった。 The grown crystal was sliced parallel to the m-plane, and the cut surface was polished to prepare a strip-shaped sample having a thickness of 0.5 mm and a length of 10 mm. When an ohmic electrode was formed on the polished surface (m-plane) and the specific resistance at room temperature was measured by the two-terminal method, it was 2 × 10 5 Ω · cm. When the zinc concentration was examined by SIMS analysis, it was 4 × 10 18 atoms / cm 3 . The XRC half-width was (10-10) reflection about 80 seconds.
［比較例１］
亜鉛を用いないこと以外は実施例１と同様にＧａＮ結晶育成を行った。得られたＧａＮ結晶の大きさはφ２インチであり、厚さは約１．０ｍｍであり、無色透明であった。このＧａＮ結晶板を研磨し、厚さ０．５ｍｍ、６ｍｍ角の研磨サンプルを切り出して、ホール測定により比抵抗を測定したところ、室温において０．２Ω・ｃｍであった。残留キャリア濃度は４×１０16／ｃｍ3、電子移動度は８００ｃｍ2／Ｖ・ｓｅｃであった。基板中央のＸＲＣ半値幅は（０００２）反射が８０秒、（１０−１２）反射が１００秒であり、リン酸：硫酸＝３：１の混合液を用いて２５０℃、１４０分エッチングしたときのＥＰＤは１×１０4／ｃｍ2 から５×１０5／ｃｍ2 の範囲であり、平均は２×１０5／ｃｍ2 であった。
[Comparative Example 1]
A GaN crystal was grown in the same manner as in Example 1 except that zinc was not used. The obtained GaN crystal had a diameter of 2 inches, a thickness of about 1.0 mm, and was colorless and transparent. This GaN crystal plate was polished, a 0.5 mm thick, 6 mm square polished sample was cut out, and the specific resistance was measured by hole measurement. As a result, it was 0.2 Ω · cm at room temperature. The residual carrier concentration was 4 × 10 16 / cm 3 and the electron mobility was 800 cm 2 / V · sec. The XRC half-width at the center of the substrate is 80 seconds for (0002) reflection and 100 seconds for (10-12) reflection, and when etched at 250 ° C. for 140 minutes using a mixture of phosphoric acid: sulfuric acid = 3: 1. The EPD ranged from 1 × 10 4 / cm 2 to 5 × 10 5 / cm 2 with an average of 2 × 10 5 / cm 2 .
［比較例２］
炭素を用いないこと以外は実施例１と同様にＧａＮ結晶育成を試みた。原料中のガリウムは全く窒化せず、ＧａＮ結晶は全く成長していなかった。
[Comparative Example 2]
GaN crystal growth was attempted in the same manner as in Example 1 except that carbon was not used. The gallium in the raw material was not nitrided at all, and the GaN crystal was not grown at all.
［比較例３］
亜鉛を１ｍｇにし、炭素を用いなかったこと以外は、実施例３と同様にＧａＮ結晶育成を試みた。そうしたところ、種結晶基板上に無色透明のＧａＮ結晶が約１ｍｍ成長した。種結晶基板を除去し、厚さ０．５ｍｍ、６ｍｍ角の研磨したサンプルを切り出し、オーミック電極を形成し、ホール測定にて室温における比抵抗を測定したところ、１．１Ω・ｃｍであった。ＳＩＭＳ分析により、亜鉛濃度を調べたところ、３×１０16ａｔｏｍｓ／ｃｍ3であった。ＸＲＣ半値幅は（０００２）反射が９０秒、（１０−１２）反射が１１０秒であった。リン酸：硫酸＝３：１の混合液を用いて２５０度、１４０分エッチングしたときのＥＰＤは１×１０5／ｃｍ2であった。
[Comparative Example 3]
GaN crystal growth was attempted in the same manner as in Example 3 except that 1 mg of zinc was used and no carbon was used. As a result, a colorless and transparent GaN crystal grew about 1 mm on the seed crystal substrate. The seed crystal substrate was removed, a polished sample having a thickness of 0.5 mm and a 6 mm square was cut out, an ohmic electrode was formed, and the specific resistance at room temperature was measured by hole measurement, which was 1.1 Ω · cm. When the zinc concentration was examined by SIMS analysis, it was 3 × 10 16 atoms / cm 3 . The XRC half-width was 90 seconds for (0002) reflection and 110 seconds for (10-12) reflection. The EPD when etched with a mixed solution of phosphoric acid: sulfuric acid = 3: 1 at 250 ° C. for 140 minutes was 1 × 10 5 / cm 2 .
［比較例４］
Ｇａに対するＺｎ濃度を１０．０ｍｏｌ％とした以外は、実施例１と同様に育成実験を行った。得られたＧａＮ結晶の大きさはφ２インチであり、厚さは約１．０ｍｍであり、成長厚さは実施例１とほぼ同じであったが、黒色に着色していた。また、一部に結晶の成長していないところがあった（図１４参照）。ＳＩＭＳ分析により、亜鉛濃度を調べたところ、３×１０19ａｔｏｍｓ／ｃｍ3であった。基板中央のＸＲＣ半値幅は（０００２）反射が約５００秒、（１０−１２）反射が約８００秒であり、リン酸：硫酸＝３：１の混合液を用いて２５０℃、１４０分エッチングしたときのＥＰＤはおよそ１×１０7／ｃｍ2であった。
[Comparative Example 4]
A growth experiment was conducted in the same manner as in Example 1 except that the Zn concentration with respect to Ga was 10.0 mol%. The size of the obtained GaN crystal was φ2 inches, the thickness was about 1.0 mm, and the growth thickness was almost the same as in Example 1, but it was colored black. Moreover, there was a place where the crystal did not grow partially (see FIG. 14). When the zinc concentration was examined by SIMS analysis, it was 3 × 10 19 atoms / cm 3 . The XRC half-width at the center of the substrate was (0002) reflection about 500 seconds and (10-12) reflection about 800 seconds, and etching was performed at 250 ° C. for 140 minutes using a mixed solution of phosphoric acid: sulfuric acid = 3: 1. The resulting EPD was approximately 1 × 10 7 / cm 2 .
１０ 結晶板製造装置、１２ 耐圧容器、１２ａ 容器本体、１２ｂ 容器蓋、１４ ヒータカバー、１６ 加熱空間、１８ａ 上段ヒータ、１８ｂ 中段ヒータ、１８ｃ 下段ヒータ、１８ｄ 底部ヒータ、２０ ヒータ断熱材、２２ 窒素ガスボンベ、２４ａ 窒素導入パイプ、２４ｂ 窒素導入パイプ、２５ マスフローコントローラ、２６ 真空ポンプ、２７ バルブ、２８ 真空引き配管、３０ 嵩上げ台、４２ コンテナ、４２ａ コンテナ本体、４２ｂ コンテナ蓋、４８ 窒素排気パイプ、４９ バルブ、５０ 育成容器、５２ 種結晶基板トレー、５４ 種結晶基板、５６ トレー台、６０ 中間容器、７０ 揺動装置、７２ 基台、７３ 柱、７４ ブラケット、７６ 伸縮機構、７７ シリンダ、７８ アクチュエータ、８０ 可動シャフト、８２ ユニバーサルジョイント、８４ 支持シャフト。 DESCRIPTION OF SYMBOLS 10 Crystal plate manufacturing apparatus, 12 Pressure-resistant container, 12a Container main body, 12b Container lid, 14 Heater cover, 16 Heating space, 18a Upper heater, 18b Middle heater, 18c Lower heater, 18d Bottom heater, 20 Heat insulator, 22 Nitrogen gas cylinder 24a Nitrogen introduction pipe, 24b Nitrogen introduction pipe, 25 Mass flow controller, 26 Vacuum pump, 27 Valve, 28 Vacuum pulling pipe, 30 Raising stand, 42 Container, 42a Container body, 42b Container lid, 48 Nitrogen exhaust pipe, 49 Valve, 50 Growth container, 52 seed crystal substrate tray, 54 seed crystal substrate, 56 tray base, 60 intermediate container, 70 swing device, 72 base, 73 pillar, 74 bracket, 76 telescopic mechanism, 77 cylinder, 78 actuator, 80 movable shaft, 2 universal joint, 84 support shaft.
Claims (6)
請求項１に記載のＺｎドープ３Ｂ族窒化物結晶。 The 3B nitride is gallium nitride.
The Zn-doped group 3B nitride crystal according to claim 1.
請求項２に記載のＺｎドープ３Ｂ族窒化物結晶。 Emits broad fluorescence having a peak at 440 to 470 nm when irradiated with light having a wavelength of 330 to 385 nm,
The Zn-doped group 3B nitride crystal according to claim 2.
前記混合融液として炭素が添加されたものを用い、該混合融液中の亜鉛濃度を３Ｂ族金属に対して０．０４〜８ｍｏｌ％とする、
Ｚｎドープ３Ｂ族窒化物結晶の製法。 A Zn-doped group 3B nitride crystal is grown on the seed crystal substrate while the seed crystal substrate is immersed in a mixed melt containing a group 3B metal, a flux and zinc and heated in a pressurized atmosphere containing nitrogen gas. A method,
Using the carbon melt added as the mixed melt, the zinc concentration in the mixed melt is 0.04 to 8 mol% with respect to the group 3B metal,
A method for producing a Zn-doped group 3B nitride crystal.
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