JP4030801B2 - Liquid raw material for CVD and manufacturing method of oxide superconductor - Google Patents

Description

【００２７】
従って、本発明のＣＶＤ用液体原料は、調製後長期間に渡って仕込み時の組成比を維持することができるので貯蔵安定性を向上でき、数日間に渡る連続成膜を行う場合であっても、液体原料をまとめて調製しておくことが可能であるため、効率的である。
上記のように本発明のＣＶＤ用液体原料は、調製後長期間に渡って仕込み時の組成比を維持することができるので、長尺の基材上に連続的にＣＶＤ反応生成物質を堆積しても、設計どおりの組成を維持でき、長尺に渡って均一な特性を有する薄膜の形成が可能である。
また、本発明のＣＶＤ用液体原料においては、変性物質の析出がないために、液体原料を調製後長期間保存した場合でも、先に記載の課題のような不具合が発生しないので、液体ポンプの解体清掃や毛細管の交換が不要になり、メンテナンスに掛かるコストや手間を大幅に低減することができる。
【００２８】
（酸化物超電導体の製造方法）
次に、本発明のＣＶＤ用液体原料を用いた酸化物超電導体の製造方法について説明する。
まず、本発明のＣＶＤ用液体原料を用いて酸化物超電導体を製造することができる酸化物超電導体の製造装置について図面を参照して説明する。
図１は、上記の製造装置の一例を模式的に示した構成図であり、この酸化物超電導体の製造装置は、液体原料供給装置１０とＣＶＤ反応装置６０から概略構成されている。
【００２９】
液体原料供給装置１０は、図１に示すように、液体原料供給器３０と原料供給装置４０と気化器５０とから概略構成されている。
この液体原料供給装置１０は、目的とする化合物の元素を含む液体原料を原料供給装置４０から液体原料供給器３０を介して気化器５０に供給し、この気化器５０により液体原料を気化して原料ガスを生成するものである。生成された原料ガスはＣＶＤ反応装置６０に供給されてＣＶＤ反応に供される。
【００３０】
液体原料供給器３０は、図１に示すように、内部に液体原料が供給される毛細管３１ａと、毛細管３１ａが着脱交換可能に挿入される筒状の冷却ガス供給部３２と、冷却ガス供給部３２の外周を取り囲んで設けられた外装部３３とから概略構成される。
【００３１】
毛細管３１ａは、原料供給装置４０から圧送されてくる液体原料３４が内部に供給されるものである。毛細管３１ａは、外径が３７５μｍ（１０^-6ｍ）程度であり、内径が数十〜数百μｍ（１０^-6ｍ）程度である。
上記構成の毛細管３１ａは着脱交換可能に冷却ガス供給部３２に挿入され、その先端部３１ｃは、冷却ガス供給部の先端部３２ａよりもやや気化器５０側に突出されている。
【００３２】
上述の数１０〜数百μｍ（１０^-6ｍ）程度の内径を有する毛細管３１ａ内に、液体原料３４を圧送するためには、数１０ｋｇ／ｃｍ²程度の液送圧力が必要であるため、図１に示すように原料供給装置４０から接続管４１を介して送り込まれてくる液体原料３４を毛細管３１ａ内に圧送するための加圧式液体ポンプ３５が接続管３５ａを介して液体供給部３１ｄに接続されている。
【００３３】
冷却ガス供給部３２は、内部に毛細管３１ａが挿入されて、毛細管３１ａとの隙間にＡｒガス、Ｎ₂ガス等の冷却ガスが供給されるものである。
冷却ガス供給部３２の上部には、図１に示す冷却ガス用ＭＦＣ３６ａを介して冷却ガス供給源３６が接続され、冷却ガス供給部３２へ冷却ガスを供給する構成となっている。
【００３４】
液体原料供給器３０は、ガラス等からなる毛細管３１ａを除いて、全てステンレス鋼等の金属部品により構成することができ、該液体原料供給器３０を構成する冷却ガス供給部３２と該冷却ガス供給部３２を支持する外装部３３は上端部で接合一体化されている。
【００３５】
毛細管３１ａの先端部３１ｃおよび冷却ガス供給部３２の先端部３２ａは、液体原料供給器３０の外装部３３の先端部３３ａよりも、気化器５０への挿入方向に対して大きく突出された構造であり、その突出長さは、気化器５０の液体原料導入部５１ａに設けられた伝熱部５６の長さに合わせて最適な長さに調整される。
さらに、毛細管３１ａの先端部３１ｃは冷却ガス供給部３２の先端部３２ａよりも気化器５０側へ１〜１０ｍｍ程度突出されている。
【００３６】
上記構成の液体原料供給器３０において、液体原料３４を液体供給部３１ｄから毛細管３１ａ内に一定流量にて圧送すると、液体原料３４は毛細管３１ａの先端部３１ｃに達して液滴状になり気化器５０に連続的に供給され、気化器５０内に供給された液滴状の液体原料３４は気化器５０内で加熱されて気化する。
また、上記液体原料３４の圧送と同時に冷却ガスを冷却ガス供給部３２に一定流量で流すと、毛細管３１ａはこの冷却ガスにより冷却されるので、気化器５０の加熱ヒータ５２による過熱を防いで、毛細管３１ａ内で液体原料３４が気化するのを防止することができる。
この冷却ガスは冷却ガス供給部３２内で毛細管３１ａを冷却した後、冷却ガス供給部の先端部３２ａから気化器５０内に放出されて、液体原料３４が気化されたガスと混合されて原料ガスを構成する。
【００３７】
図１に示すように原料供給装置４０は、収納容器４２と、不活性ガス源４３を具備し、収納容器４２内部には液体原料３４が収納される。原料供給装置４０は、不活性ガス源４３により収納容器４２内にＡｒガス等の不活性ガスを供給して、収納容器４２内を不活性雰囲気に保つ。このＡｒガス等の不活性ガスは、不活性ガスの出口４３ａより大気に解放され、収納容器４２内は常圧を維持される。
【００３８】
液体原料供給装置１０において、液体原料供給器３０の下方には気化器５０が配設されている。
図１に示す気化器５０は、箱状の気化室５１と、気化器５０の外周に配置されて気化室５１を加熱する加熱ヒータ５２とから概略構成されている。
気化室５１には、液体原料導入部５１ａが液体原料供給器３０側に突出して設けられており、この液体原料導入部５１ａはステンレス鋼等の保熱部材からなる筒状の伝熱部５６を備えている。
液体原料供給器３０は、冷却ガス供給部３２及びこれの内部の毛細管３１ａを伝熱部５６に収納されて、Ｏリング５３によって気化室５１を密閉状態にして気化器５０に接続される。
【００３９】
気化器５０の外周には、気化室５１内部を加熱するための加熱ヒータ５２が配設されていて、この加熱ヒータ５２により毛細管３１ａの先端部３１ｃから供給された液体原料３４を所望の温度に加熱して気化させ、さらに冷却ガス供給部３２の先端部３２ａと毛細管３１ａの先端部３１ｃの隙間から気化室５１に流れ込む冷却ガスと混合させて原料ガスを得る。
【００４０】
また、加熱ヒータ５２は、液体原料導入部５１ａに設けられた伝熱部５６を介して冷却ガス供給部３２を加熱し、気化室５１内に流れ込む冷却ガスの温度を上昇させて、冷却ガス供給部３２に対流する原料ガスからの再析出を防止するとともに、毛細管３１ａの温度もある程度上昇させるため、毛細管３１ａとその先端部３１ｃにおける温度の低下を防止し、毛細管３１ａの先端部３１ｃにおける液体原料の再析出を効果的に防止できるようになっている。
上記伝熱部５６は冷却ガス供給部３２に概ね密着するように設けられているため、冷却ガス供給部３２は加熱されて高温になるが、毛細管３１ａとの隙間には冷却ガスが導入されているため、毛細管３１ａは、冷却ガス供給部３２よりも低温に保たれ、毛細管３１ａ内部の液体原料３４は気化しない。
【００４１】
また、図１に示すように、気化室５１内部は仕切板５４を挟んで領域５１ｄと領域５１ｅの２つの領域に分割され、これら２つの領域は気化室５１の底部５１ｂと仕切板５４との隙間により連通している。
毛細管３１ａから供給された液体原料３４が気化したガスと冷却ガスとから生成された原料ガスは、領域５１ｄから、仕切板５４の下側の隙間を通過して領域５１ｅに移動し、さらに領域５１ｅに対応する気化室５１の上端部に設けられた原料ガス導出口５１ｃから気化器５１外へ輸送される。
原料ガス導出口５１ｃから導出された原料ガスは、輸送管５７を介して気化器５０に接続されたＣＶＤ反応装置６０に供給される。
なお、気化室５１の構造は、上記のように仕切板５４を用いて２つに分けられた構造の他に、例えば、Ｕ字状のものでもよい。このように気化室がＵ字状である場合には、このＵ字状の気化室の一方の端部側に液体原料供給器３０から液体原料３４が供給され、他方の端部側から原料ガスが輸送管５７を介してＣＶＤ反応装置６０に供給されるようになっている。このように気化室をＵ字状の構造にすると、気化室内の温度を一定に保ちやすい。
【００４２】
ＣＶＤ反応装置６０は、石英製の反応チャンバ６１を有する。この反応チャンバ６１は、横長の両端を封止した筒状であり、基材が導入される側から順に基材導入部６２と、反応生成室６３と、基材導出部６４とに隔壁（図示せず）によって区画されている。
基材導入部６２にはテープ状の基材６５を導入するための導入孔が形成されるとともに、基材導出部６４には基材６５を導出するための導出孔が設けられており、導入孔と導出孔の周縁部には、基材６５を通過させている状態で各孔の隙間を閉じて基材導入部６２と基材導出部６４を密閉する封止部材（図示せず）が設けられている。
また、反応生成室６３の天井部には、反応生成室６３に連通するピラミッド型のガス拡散部６６が取り付けられている。
【００４３】
ＣＶＤ反応装置６０の外部には、基材導入部６２の反応生成室６３側方の部分から、基材導出部６４の反応生成室６３側方の部分までを覆う加熱ヒータ４７が設けられ、基材導入部６２が不活性ガス供給源６８に、また、基材導出部６４が不活性ガス供給源６９にそれぞれ接続されている。
また、ガス拡散部６６には原料供給装置１０の気化器５０と接続された輸送管５７が接続されている。
この輸送管５７の周囲には原料ガスが液体原料３４となって析出するのを防止するための加熱手段（図示せず）が設けられている。
尚、輸送管５７の途中には、酸素ガス供給源５４ａが分岐接続され、輸送管５７に酸素ガスを供給できる構成となっている。
【００４４】
また、上記ＣＶＤ反応装置６０の底部には排気管７０が設けられており、真空ポンプ７１を備えた圧力調整装置７２に接続されていて、ＣＶＤ反応装置６０の内部のガスを排気できるようになっている。
さらに、ＣＶＤ反応装置６０の基材導出部６４の側方側には、ＣＶＤ反応装置６０内を通過する基材６５を巻き取るためのテンションドラム７３と巻き取りドラム７４とからなる基材搬送機構７５が設けられている。
また、基材導入部６２の側方側には、基材６５をＣＶＤ反応装置６０に供給するためのテンションドラム７６と送出ドラム７７とからなる基材搬送機構７８が設けられている。
【００４５】
次に、上記構成の酸化物超電導体の製造装置を用いた、本発明の酸化物超電導体の製造方法について説明する。
図１に示す製造装置を用いて酸化物超電導体を製造するには、まずテープ状の基材６５と液体原料３４を用意する。
この基材６５は、長尺のものを用いることができるが、熱膨張係数の低い耐熱性の金属テープ、あるいはその上面にセラミックス製の中間層を被覆してなるものが好ましい。
上記耐熱性の金属テープの構成材料としては、銀、白金、ステンレス鋼、銅、ハステロイ（Ｃ２７６等）などの金属材料、合金が好ましい。
特に、{１００}<００１>や{１１０}<１１０>集合組織を有する銀からなる金属テープを用いる場合には、該金属テープ上に直接超電導体を形成でき、かつ形成する酸化物超電導体の配向を制御することができるため、より好ましい。
また、上記金属テープ以外では、ガラステープ、マイカテープ或いはセラミックス製のテープを用いてもよい。
【００４６】
次に、上記中間層を構成する材料は、熱膨張係数が金属よりも酸化物超電導体に近い、ＹＳＺ（イットリウム安定化ジルコニア）、ＳｒＴｉＯ₃、ＭｇＯ、Ａｌ₂Ｏ₃、ＬａＡｌＯ₃、ＬａＧａＯ₃、ＹＡｌＯ₃、ＺｒＯ₂等のセラミックスが好ましく、これらの中でも、できる限り結晶配向性の整ったものがより好ましい。
次に、先に記載のように、酸化物超電導体の構成金属元素の有機金属錯体を目的の組成比となるように数種混合したものを、テトラヒドロフランとエチレングリコールジメチルエーテルの混合物に混合、溶解して液体原料を作製する。
【００４７】
上記有機金属錯体は、上記溶媒に可溶なものであれば、目的化合物を構成する金属元素のアルコキシド、アセチルアセトナト、ジピバロイルメタナト、シクロペンタジエニル、またはそれらの誘導体などを用いることができる。
また、液体原料の濃度、混合溶媒の混合比等は目的とする化合物の種類により適宜変更し、最適な条件としておく。
例えば、Ｙ−Ｂａ−Ｃｕ−Ｏ系酸化物超電導体を製造する場合には、濃度は５〜２０重量％が好ましく、６〜１０重量％であればより好ましい。
また、テトラヒドロフランとエチレングリコールジメチルエーテルの混合比は、その体積比にして、好ましくは１：１〜９：１であり、より好ましくは６：１の混合比である。
【００４８】
上記のテープ状の基材６５を用意したならば、これを反応チャンバ６１内に基材搬送機構７８により基材導入部６２から所定の移動速度で送り込むとともに基材搬送機構７５の巻取ドラム７４で巻き取り、更に反応生成室６３内の基材６５を加熱ヒータ４７で所定の温度に加熱する。
基材６５の移動速度、および加熱ヒータ４７の設定温度は、目的とする酸化物超電導体の組成系にもよるが、それぞれ１〜１０ｍ／時間、６００〜８００℃程度であるのが好ましい。
なお、基材６５を送り込む前に、不活性ガス供給源６８及び６９から不活性ガスをパージガスとして反応チャンバ６１内に送り込み、同時に圧力調整装置７２を作動させて反応チャンバ６１の内部を排気することで反応チャンバ６１内の水分等の不用ガスを排除して内部を洗浄しておくことが好ましい。
【００４９】
続いて、加圧式液体ポンプ３５を用いて収納容器４２から液体原料３４を吸い込み、液体原料３４を０．１〜１．０ｍｌ／分程度の速度で毛細管３１ａ内に圧送し、これと同時に冷却ガスを冷却ガス供給部３２に流量３００〜６００ｃｃｍ（ｍｌ／分）程度で送り込む。同時に圧力調整装置７２を作動させ、反応チャンバ６１の内部のガスを排気する。この際、冷却ガスの温度は室温程度になるように調節しておく。
また、気化室５１の内部温度、液体原料導入部５１ａの内部温度及び液体原料供給器３０の温度が、上記原料のうちの最も気化温度の高い原料の最適温度になるようにヒータ５２により調節しておく。こうすることにより冷却ガス供給部３２がヒータ５２により予熱されるとともに気化室５１内での原料ガスの再析出が防止される。
【００５０】
すると、液体原料３４は毛細管３１ａの先端部３１ｃから気化室５１内に液滴状となって供給される、そして、気化器５０の内部に供給された液滴状の液体原料３４は、加熱ヒータ５２により加熱されるとともに冷却ガスと混合されて気化して原料ガスとなり、この原料ガスは輸送管５３を介してＣＶＤ反応装置６０のガス拡散部６６に連続的に供給される。
この時、輸送管５７の内部温度が上記原料のうちの最も気化温度の高い原料の最適温度になるように上記加熱手段により調節しておく。同時に、酸素ガス供給源５４ａから酸素ガスを供給して原料ガス中に酸素ガスを混合する操作も行う。
【００５１】
次に、反応チャンバ６１の内部においては、輸送管５７の出口部分からガス拡散部６６に放出された原料ガスが、ガス拡散部６６から拡散しながら反応生成室６３側に移動し、反応生成室６３の内部を通り、次いで基材６５の近傍を移動してガス排気管７０に引き込まれるように移動する。
従って、加熱された基材６５の上面側で原料ガスを反応させて酸化物超電導薄膜を生成させることができる。この後、酸化物超電導薄膜が形成された基材６５に熱処理を施して、酸化物超電導薄膜に超電導特性を現出あるいは向上させて酸化物超電導体８０とすることができる。
以上の成膜操作を所定時間継続して行なうことにより、基材６５上に所望の厚さの膜質の安定した酸化物超電導体８０を備えた酸化物超電導導体を得ることができる。
【００５２】
上記本発明の酸化物超電導体の製造方法によれば、液体原料として上記ＣＶＤ用液体原料を用いているために、ＴＨＦを溶媒として用いた液体原料を使用する場合のように液体原料中に変性物質が析出しないので、成膜中の液体原料の組成比を、仕込み時の組成比のまま長時間維持することができる。
そのために、長時間成膜する場合でも、一定の組成の酸化物超電導薄膜を安定して成膜することができ、長尺に渡って均一な特性を備えた酸化物超電導体を製造できる。上記のような製造方法によれば長尺に渡って優れた臨界電流密度等の超電導特性を有する酸化物超電導体を製造できる。
また、液体原料内に不要な固体が析出しないため、加圧液体ポンプ３５の解体清掃、毛細管３１ａの交換が不要になり、長期間メンテナンスなしに成膜を続けて行うことができ、メンテナンスに掛かるコストや手間を大幅に低減することができる。
【００５３】
【実施例】
以下に実施例を示して、本発明をより具体的に説明する。
（液体原料の調製）
まず、Ｂａ−ビス−２，２，６，６−テトラメチル−３，５−ヘプタンジオン（Ｂａ（ｔｈｄ）_２）と、Ｙ（ｔｈｄ） _３ と、Ｃｕ（ｔｈｄ）_２を、Ｙ：Ｂａ：Ｃｕ＝１．０：１．９：２．５のモル比で混合したものを、エチレングリコールジメチルエーテルに７重量％となるように添加して液体原料Ａを作製した。
【００５４】
次に、テトラヒドロフラン(ＴＨＦ)に、上記と同等の有機金属錯体をＹ：Ｂａ：Ｃｕ＝１．０：１．９：２．５のモル比で混合したものを７重量％となるように添加して液体原料Ａを作製した。
【００５５】
次に、テトラヒドロフラン(ＴＨＦ)とエチレングリコールジメチルエーテル（ＤＭＥ）を９：１の体積比で混合したものに、上記と同等の有機金属錯体をＹ：Ｂａ：Ｃｕ＝１．０：１．９：２．５のモル比で混合したものを７重量％となるように溶解して液体原料Ｂを作製した。
次に、テトラヒドロフラン(ＴＨＦ)とエチレングリコールジメチルエーテル（ＤＭＥ）を５：１の体積比で混合したものに、上記と同等の有機金属錯体をＹ：Ｂａ：Ｃｕ＝１．０：１．９：２．５のモル比で混合したものを７重量％となるように溶解して液体原料Ｃを作製した。
次に、テトラヒドロフラン(ＴＨＦ)とエチレングリコールジメチルエーテル（ＤＭＥ）を１：１の体積比で混合したものに、上記と同等の有機金属錯体をＹ：Ｂａ：Ｃｕ＝１．０：１．９：２．５のモル比で混合したものを７重量％となるように溶解して液体原料Ｄを作製した。
【００５６】
次に、テトラヒドロフラン(ＴＨＦ)とエチレングリコールジメチルエーテル（ＤＭＥ）を1：５の体積比で混合したものに、上記と同等の有機金属錯体をＹ：Ｂａ：Ｃｕ＝１．０：１．９：２．５のモル比で混合したものを７重量％となるように溶解して液体原料Ｅを作製した。
次に、テトラヒドロフラン(ＴＨＦ)とエチレングリコールジメチルエーテル（ＤＭＥ）を１：９の体積比で混合したものに、上記と同等の有機金属錯体をＹ：Ｂａ：Ｃｕ＝１．０：１．９：２．５のモル比で混合したものを７重量％となるように溶解して液体原料Ｆを作製した。
【００５７】
次に、エチレングリコールジメチルエーテル（ＤＭＥ）に、上記と同等の有機金属錯体をＹ：Ｂａ：Ｃｕ＝１．０：１．９：２．５のモル比で混合したものを７重量％となるように溶解して液体原料Ｇを作製した。
【００５８】
次に、メチル−ｔ−ブチルエーテルに、上記と同等の有機金属錯体をＹ：Ｂａ：Ｃｕ＝１．０：１．９：２．５のモル比で混合したものを７重量％となるように添加して液体原料Ｈを作製した。
次に、エチレングリコールジメチルエーテルとメチル−ｔ−ブチルエーテルを１：１の体積比で混合したものに、上記と同等の有機金属錯体をＹ：Ｂａ：Ｃｕ＝１．０：１．９：２．５のモル比で混合したものを７重量％となるように溶解して液体原料Ｉを作製した。
【００５９】
上記の液体原料Ａ〜Ｉを、別々のガラス製の容器に満たし、容器内に窒素ガスを充填して密閉した状態で３０日間常温にて貯蔵した後、各々の液体原料を目視観察した。その結果を下記表１に示す。表１中、△はガラス製の容器底部に明らかな沈殿物が認められたものを示し、○はガラス製の容器底部にわずかに沈殿物あるいは微結晶の存在が認められたものを示し、◎はガラス製の容器内に沈殿物や微結晶が全く認められなかったものを示す。
【００６０】
【表１】

【００６１】
表１に示す結果から、ＴＨＦを溶媒とした液体原料Ａは、３０日間常温で貯蔵後に白色沈殿物生成（白色の変性物質の析出）が認められたのに対して、ＴＨＦとＤＭＥの混合物を溶媒として用いた液体原料Ｂ〜Ｆと、ＤＭＥを溶媒として用いた液体原料Ｇ、メチル−ｔ−ブチルエーテルを溶媒として用いた液体原料Ｈ、ＤＭＥとメチル−ｔ−ブチルエーテルの混合物を溶媒として用いた液体原料Ｉでは、３０日間常温で貯蔵後に白色沈殿物生成が認められず、特に、ＴＨＦとＤＭＥの混合物を溶媒として用いた液体原料Ｂ〜Ｄは貯蔵性が優れていることから、ＴＨＦとＤＭＥの混合比は、その体積比にして、１：１〜９：１の範囲に調製するのがＢａ系原料の安定性が向上し、白色沈殿物生成を抑制できる点で好ましいことがわかる。
【００６２】
（酸化物超電導体の作製）
図１に示す構成の酸化物超電導体の製造装置を用いて酸化物超電導体の作製する際、反応生成室に供給される原料ガスの溶液として用いる液体原料として先に調製した液体原料Ａ〜Ｉにそれぞれ変更し、各種の酸化物超電導体（サンプルＮｏ．１〜９）を作製した。酸化物超電導体を作製する際の加圧式液体ポンプと毛細管のそれぞれのメンテナンス周期について調べた結果を表２に示す。また、得られた各種の酸化物超電導体の臨界電流密度（Ｊｃ）を４端子法により測定した結果を表２に合わせて示す。
【００６３】
なお、酸化物超電導体を作製する際には、内径４０μｍ（１０^-6ｍ）の毛細管が取り付けられた、図１に示す構成の酸化物超電導体の製造装置を用い、幅１０ｍｍ、長さ１００ｃｍ、厚さ０．２ｍｍのＡｇテープ基材（無配向Ａｇテープ）を用い、該基材の移動速度を３．０ｍ／時間、反応生成室の温度を７００℃に設定し、反応生成室に供給される原料ガスの溶液として上記で調製した液体原料を用いた。
次に、調製した液体原料を加圧式液体ポンプの圧力３５ｋｇ／ｃｍ²、供給速度０．３ｍｌ／分で圧送し、冷却ガス供給部への冷却ガス供給速度４５０ｃｃｍ、
反応生成室の反応圧力を５．０Torr（＝５×１３３Ｐａ）、酸素分圧１．２５Torr（＝１．２５×１３３Ｐａ）として、ガス拡散部から上記Ａｇテープ基材上に原料ガスを吹き付け、基材上にＹ₁Ｂａ₂Ｃｕ₃Ｏ_xなる組成の酸化物超電導膜を成膜後、５００℃、２時間熱処理を施し、各種の酸化物超電導体を得た。
【００６４】
【表２】

【００６５】
表２に示す結果から、ＴＨＦを溶媒とした液体原料Ａを用いて製造したサンプルＮｏ．１の酸化物超電導体を製造した場合、液体ポンプメンテナンス周期が２ヶ月に１回、毛細管交換周期が１週間に１回であるのに対して、ＴＨＦとＤＭＥの混合物を溶媒とした液体原料Ｂ〜Ｆを用いて製造したサンプルＮｏ．２〜６の酸化物超電導体と、ＤＭＥを溶媒とした液体原料Ｇを用いて製造したサンプルＮｏ．７の酸化物超電導体、メチル−ｔ−ブチルエーテルを溶媒とした液体原料Ｈを用いて製造したサンプルＮｏ．８の酸化物超電導体、ＤＭＥとメチル−ｔ−ブチルエーテルの混合物を溶媒とした液体原料Ｉを用いて製造したサンプルＮｏ．９の酸化物超電導体を製造した場合、液体ポンプメンテナンス周期及び毛細管交換周期が改善されており、特に、ＴＨＦとＤＭＥの混合物を溶媒とした液体原料Ｂ〜Ｄを用いて製造したサンプルＮｏ．２〜４の酸化物超電導体を製造した場合は液体ポンプメンテナンス周期が６ヶ月に１回、毛細管交換周期が５週間に１回と大幅に長くなっていることがわかる。
【００６６】
また、サンプルＮｏ．１、８の酸化物超電導体の臨界電流密度は３５０００Ａ／ｃｍ²以下であるのに対して、サンプルＮｏ．２〜６の酸化物超電導体の臨界電流密度は３７０００Ａ／ｃｍ²以上得られており、特にサンプルＮｏ．２〜４の酸化物超電導体の臨界電流密度は３９０００Ａ／ｃｍ²以上得られており、超電導特性においても優れたものであることが確認された。
【００６７】
【発明の効果】
以上説明したように本発明のＣＶＤ用液体原料は、有機金属錯体を溶解するための溶媒として、ＴＨＦとＤＭＥの混合物を採用したので、液体原料を調製した後での経時的な変成物質の析出を防止することができるため、液体原料調製後、長期間にわたって一定の組成比を維持することができる。そのため、長時間の連続成膜を行う場合であっても、本発明のＣＶＤ用液体原料は作り置きが可能であるので、効率的な原料供給を行うことができる。このように本発明のＣＶＤ用液体原料は、調製後長期間に渡って仕込み時の組成比を維持することができるので、長尺の基材上に連続的にＣＶＤ反応生成物質を堆積しても、設計どおりの組成を維持でき、長尺に渡って均一な特性を有する酸化物超電導薄膜や誘電体薄膜等の薄膜の形成が可能である。
また、本発明のＣＶＤ用液体原料は、経時的に変成物質が析出することが無いために、液体ポンプの解体清掃や毛細管の交換といったメンテナンス周期を長くでき、これらに要するコストや手間を大幅に低減することができる。
【００６８】
次に、本発明の酸化物超電導体の製造方法によれば、上記のような本発明のＣＶＤ用液体原料を用いて酸化物超電導体の形成を行うため、長期間メンテナンスなしに液体原料の連続供給が可能であり、基材の長さ方向に渡って安定した品質の酸化物超電導体を製造することができる。
【図面の簡単な説明】
【図１】 図１は、本発明に係る酸化物超電導体の製造装置の一例を模式的に示した構成図である。
【図２】 図２は、ＣＶＤ用液体原料供給装置の一例を示す図である。
【符号の説明】
１０ ＣＶＤ用液体原料供給装置
３０ 液体原料供給器
３１ 毛細管挿入部
３１ａ 毛細管
３１ｃ 毛細管の先端部
３２ 冷却ガス供給部
３４ ＣＶＤ用液体原料
５０ 気化器
５１ 気化室
５２ 加熱ヒータ
６０ ＣＶＤ反応装置
６３ 反応生成室
６５ 基材[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a liquid raw material for CVD used for forming a thin film such as an oxide superconducting thin film or a dielectric thin film on a substrate by a chemical vapor deposition method (CVD method).
[0002]
[Prior art]
In recent years, oxide superconductors having a critical temperature (Tc) higher than the liquid nitrogen temperature (77 K) include Y—Ba—Cu—O, Bi—Sr—Ca—Cu—O, and Tl—Ba—Ca—Cu—. O-based oxide superconductors have been discovered. These oxide superconductors have been studied for the purpose of using them in fields such as power cables, magnets, energy storage, generators, medical devices, and current leads.
[0003]
As one method for producing the above oxide superconductor, there is known a method of forming an oxide superconducting thin film on the surface of a substrate by means of thin film forming means such as a CVD method. It is known that an oxide superconducting thin film formed by this type of thin film forming means has a large critical current density (Jc) and exhibits excellent superconducting properties.
In addition, among CVD methods, a CVD method using an organometallic complex such as a metal alkoxide as a raw material is attracting attention as a mass production method for oxide superconducting thin films because of its high film formation rate.
[0004]
In such a method for producing an oxide superconductor by the CVD method, as a commonly used raw material compound, β-diketone compound, cyclopentadienyl compound or the like of an element constituting the oxide superconductor is used. For example, Y (thd) is used to manufacture a Y-Ba-Cu-O-based oxide superconductor._Three, Ba (thd)₂Or Ba (thd)₂・ Phen₂, Cu (thd)₂An organometallic complex in which an organic substance such as a β-diketone compound is coordinated to a metal element is used.^*(Thd = 2,2,6,6-tetramethyl-3,5-heptanedione, phen = phenanthroline)
[0005]
The organometallic complex as described above is a raw material that is solid at room temperature, and exhibits high sublimation characteristics when heated to 200 to 300 ° C., but has sublimation efficiency due to changes in the surface area of the charged raw material depending on the purity of the raw material and heating time Since it is greatly influenced, it is difficult to control the composition of the obtained superconducting thin film, and the reproducibility of characteristics is insufficient.
Therefore, it is also considered that these solid organic complexes are dissolved in an organic solvent and used as a liquid raw material. Examples of the organic solvent include tetrahydrofuran (THF), isopropanol, toluene, diglyme (2,5,8-trioxononane). In addition, an organic solvent such as butyl acetate, or a mixed solvent obtained by mixing these at a constant ratio has been used.
In particular, it is known that an oxide superconductor exhibiting a relatively high critical current density (Jc) can be produced by using a liquid raw material using THF as a solvent.
[0006]
[Problems to be solved by the invention]
However, in the liquid raw material in which the organometallic complex is dissolved in the THF solvent as described above, it has been clarified that a fine white precipitate is deposited with time in the solution after storage for several days.
This white precipitate has been found to contain Ba, and Ba (thd) dissolved in THF.₂The complex is presumed to have been transformed into a component insoluble in THF, either due to hydrolysis by a small amount of water contained in THF, or due to reaction with peroxide generated by the reaction of THF with oxygen. It is believed that there is.
[0007]
Here, FIG. 2 shows an example of a liquid source supply apparatus for vaporizing the liquid source and supplying it to the CVD reactor.
A liquid source supply apparatus 100 shown in FIG. 2 includes a liquid source supplier 130 that supplies a liquid source into the vaporizer 150, and vaporizes the supplied liquid source into a source gas. The vaporizer 150 is supplied into the reactor.
[0008]
2 is proposed in Japanese Patent Application No. 2000-132800 by the inventors of the present invention, and a capillary 131a into which liquid raw material is supplied and a capillary 131a are detachably inserted. The capillary insertion part 131, the cooling gas supply part 132, and the carrier gas supply part 133 are comprised roughly.
[0009]
The liquid source supply unit 130 includes a cooling gas source 136 that supplies a cooling gas to the cooling gas supply unit 132 via an MFC (mass flow controller) 136a, and a carrier that supplies a carrier gas to the carrier gas supply unit 133 via an MFC 139a. A gas supply source 139 is connected.
Further, a connecting tube 141 is attached to the capillary tube 131a, and a pressurizing pump (liquid pump) 135 is inserted into the connecting tube 141 and a storage containing a liquid raw material 134 in which an organometallic complex is dissolved in the above THF solvent is stored. A container 142 is attached.
An inert gas source 143 that makes the inside of the container an inert atmosphere is attached to the storage container 142, and Ar gas or the like is supplied from the inert gas source 143 into the storage container 142 to make the inert atmosphere, The liquid raw material 134 can be continuously supplied to the capillary 131a through the connecting pipe 141 at a constant flow rate. In addition, the code | symbol 143a in a figure is an exit of an inert gas.
[0010]
The vaporizer 150 includes a box-shaped vaporization chamber 151 and a heater 152 that is disposed on the outer periphery of the vaporization chamber 151 and heats the inside of the vaporization chamber 151.
Further, the vapor source 151 is provided with a liquid source introduction part 151a protruding above the vaporization chamber 151, and the liquid source supplier 130 is housed and fixed in the liquid source supply part 151a.
[0011]
In order to manufacture a long oxide superconductor using the oxide superconductor manufacturing apparatus provided with the liquid source supply apparatus 100, the liquid source 134 is pumped into the capillary 131a of the liquid source supply unit 130, The liquid material 134 in the form of droplets supplied from the tip 131c of the capillary tube 131a into the vaporizer 150 is vaporized in the vaporizer 150 and mixed with the carrier gas flowing from the carrier gas supply unit 133 to obtain a raw material gas. Gas is supplied from the source gas outlet 151c to a CVD reactor (not shown).
At the same time, a long oxide superconductor is obtained by running a tape-shaped substrate in the CVD reactor and further heating the tape-shaped substrate to deposit the reaction product on the substrate. It is like that.
[0012]
In the liquid raw material supply apparatus 100 as described above, when a precipitate such as the above-described precipitate generated by the transformation of the solute in the liquid raw material 134 is generated, in the solution in which the organometallic complex is dissolved in THF. Since the composition ratio of each element is different from the composition ratio at the time of raw material charging, the composition of the CVD reaction product deposited on the base material is different from the design, so the target characteristics Therefore, it becomes difficult to form a thin film having uniform characteristics on a long base material.
Therefore, since the liquid raw material on which the modified substance is deposited cannot be used for the CVD reaction, the liquid raw material after a certain period of time after the preparation is not discarded, and the liquid raw material needs to be frequently prepared. There is a problem.
[0013]
Further, the precipitate as described above may stay in the liquid pump 135 and cause a malfunction of the liquid pump 135, or may be an introduction part 131d or a tip part 132a of the capillary 131a of the liquid raw material supplier 130, or a capillary. There is also a problem that the inside of 131a is blocked and liquid feeding stops.
For this reason, it is necessary to frequently disassemble and clean the liquid pump 135 and replace the capillary tube 131a, and there is a problem that the maintenance cycle of the liquid material supply apparatus 100 is short.
[0014]
The present invention has been made in order to solve the above-described problems, and it is possible to prevent the deposition of metamorphic substances in a liquid material for CVD and to maintain a constant composition ratio for a long time. For the purpose of provision.
Another object of the present invention is to provide a method for producing an oxide superconductor using such a liquid material for CVD.
[0015]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have used the above-mentioned problem of using a mixture of tetrahydrofuran (THF) and ethylene glycol dimethyl ether (DME) as a solvent for the liquid raw material for CVD. It came to be a solution. More preferably, by setting the mixing ratio of tetrahydrofuran and ethylene glycol dimethyl ether to a specific ratio, the present invention has been solved.
[0016]
  That is, the liquid raw material for CVD of the present invention isOne or moreIn a liquid raw material for CVD formed by dissolving an organometallic complex in a solvent, the solvent is a mixture of tetrahydrofuran and ethylene glycol dimethyl ether.The organometallic complex is RE ₁ Ba ₂ Cu ₃ O _x (Wherein RE represents one or more selected from Y, La, Ce, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, and Yb) An organic complex of a metal element forming a superconductor, wherein the organometallic complex includes an organic barium complex, and the solvent is a mixture of tetrahydrofuran and ethylene glycol dimethyl ether in a volume ratio of 1: 1 to 9: 1. AhIt is characterized by that.
[0017]
  In the above-described liquid material for CVD, the organic materialbariumComplexBut Ba (thd) ₂ Or Ba (thd) ₂ ・ Phen ₂ It is preferable that
[0018]
  Next, the method for producing an oxide superconductor according to the present invention includes a step of preparing a liquid raw material by dissolving an organometallic complex in a solvent, and a step of generating a raw material gas by vaporizing the liquid raw material with a vaporization supply device. A method of producing an oxide superconductor comprising introducing the source gas into a CVD reactor and forming an oxide superconductor on a substrate,
  The solvent for dissolving the organometallic complex is a mixture of tetrahydrofuran and ethylene glycol dimethyl ether.The
  The organometallic complex is an RE ₁ Ba ₂ Cu ₃ O _x (Wherein RE represents one or more selected from Y, La, Ce, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, and Yb) An organic complex of a metal element forming a superconductor, the organometallic complex comprising an organic barium complex,
  The solvent for dissolving the organometallic complex is a mixture of tetrahydrofuran and ethylene glycol dimethyl ether in a volume ratio of 1: 1 to 9: 1.It is characterized by
[0019]
  Further, in the above method for producing an oxide superconductor, the organic superconductorbariumComplexBut Ba (thd) ₂ Or Ba (thd) ₂ ・ Phen ₂ It is preferable that
[0020]
In the method for producing the oxide superconductor, as a solvent for dissolving the organometallic complex, tetrahydrofuran and ethylene glycol dimethyl ether mixed at a volume ratio of 1: 1 to 9: 1 are used. This is preferable in that the characteristics of the oxide superconductor produced by the production method of the present invention can be improved.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
Although one embodiment of the present invention is described in detail below, the present invention is not limited to the following embodiment.
[0022]
(Liquid material for CVD)
The liquid raw material for CVD of the present invention uses a mixture of several organometallic complexes of a metal element constituting the target compound so as to achieve the composition ratio of the target compound as a solute, and a mixture of tetrahydrofuran and ethylene glycol dimethyl ether as a solvent. It is what. The mixing ratio of tetrahydrofuran and ethylene glycol dimethyl ether is preferably 1: 1 to 9: 1 and more preferably 6: 1 in terms of volume ratio.
As the organometallic complex, a metal alkoxide, acetylacetonato, dipivaloylmethanato, cyclopentadienyl, or a derivative thereof can be used.
[0023]
  The above organometallic complex is converted to RE₁Ba₂Cu₃O_x(Wherein RE represents one or more selected from Y, La, Ce, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, and Yb) If it is composed of an organic complex of a metal forming a superconductor, it becomes a liquid raw material for CVD for producing an oxide superconductor.
  For example, in the case of manufacturing a Y—Ba—Cu—O-based oxide superconductor, Y (thd)₃, Ba (thd)₂Or Ba (thd)₂・ Phen₂, Cu (thd) ₂ NaAny organometallic complex is dissolved in the above solvent to prepare a liquid raw material for producing an oxide superconductor.
  Moreover, when manufacturing oxide superconductors other than the above, Bi (C₆H₅)₃, Sr (DPM)₂, Ca (DPM)₂, La (DPM)₃An organic metal complex such as can be used as a liquid raw material for each oxide superconductor.
[0024]
Since the liquid raw material for CVD of the present invention uses a mixture of tetrahydrofuran and ethylene glycol dimethyl ether as a solvent, precipitation of the modified substance does not occur as in the case where THF is used as the solvent.
[0025]
  The reason can be assumed to be as follows.
  originally,Ba (thd) ₂ NaSince any organic barium complex is easily deteriorated by moisture in the air or carbon dioxide, careful handling is required for its handling and storage method. This is thought to be due to an empty orbit due to the tetracoordination of the organic barium complex while the metal barium is hexacoordinate.
  When such an organic barium complex is dissolved in a solvent composed of THF to obtain a liquid raw material, THF, which is a kind of aromatic ether, has a pentagonal cyclic structure, but is affected by oxygen and light in the air. It is easy to form peroxide. Such a peroxide is chemically active and is considered to react with the Ba-based raw material to form a precipitate.
  On the other hand, when dissolved in the solvent employed by the present invention described above, the contribution of functional groups in the solvent shown below prevents moisture or carbon dioxide gas from acting on the above empty orbit. Can be considered. That is, when ethylene glycol dimethyl ether is included in addition to THF as a solvent for dissolving the organometallic complex, the structure shown below is more than the action of peroxide caused by the influence of THF on oxygen and light in the air. This is because the function of the functional group reaches the above-mentioned empty orbit.
[0026]
[Chemical 1]

[0027]
Therefore, the liquid material for CVD of the present invention can maintain the composition ratio at the time of preparation for a long period after preparation, so that the storage stability can be improved, and continuous film formation for several days is performed. However, since it is possible to prepare liquid raw materials collectively, it is efficient.
As described above, the liquid material for CVD of the present invention can maintain the composition ratio at the time of preparation for a long period after preparation, so that a CVD reaction product is continuously deposited on a long substrate. However, a composition as designed can be maintained, and a thin film having uniform characteristics over a long length can be formed.
Moreover, in the liquid raw material for CVD of the present invention, since there is no precipitation of the denatured substance, even when the liquid raw material is stored for a long time after the preparation, problems such as the problems described above do not occur. Dismantling and replacement of capillaries are not required, and the cost and labor required for maintenance can be greatly reduced.
[0028]
(Manufacturing method of oxide superconductor)
Next, the manufacturing method of the oxide superconductor using the liquid raw material for CVD of this invention is demonstrated.
First, an oxide superconductor manufacturing apparatus capable of manufacturing an oxide superconductor using the CVD liquid raw material of the present invention will be described with reference to the drawings.
FIG. 1 is a configuration diagram schematically showing an example of the manufacturing apparatus described above, and this oxide superconductor manufacturing apparatus is generally configured by a liquid source supply apparatus 10 and a CVD reaction apparatus 60.
[0029]
As shown in FIG. 1, the liquid raw material supply apparatus 10 is schematically configured from a liquid raw material supply device 30, a raw material supply device 40, and a vaporizer 50.
The liquid raw material supply device 10 supplies a liquid raw material containing an element of the target compound from the raw material supply device 40 to the vaporizer 50 via the liquid raw material supply device 30, and vaporizes the liquid raw material by the vaporizer 50. It generates raw material gas. The generated source gas is supplied to the CVD reactor 60 and used for the CVD reaction.
[0030]
As shown in FIG. 1, the liquid source supply unit 30 includes a capillary 31 a into which the liquid source is supplied, a cylindrical cooling gas supply unit 32 into which the capillary 31 a is detachably inserted, and a cooling gas supply unit. And an exterior portion 33 provided so as to surround the outer periphery of 32.
[0031]
The capillary 31 a is supplied with the liquid raw material 34 fed from the raw material supply device 40. The capillary 31a has an outer diameter of 375 μm (10^-6m) and the inner diameter is several tens to several hundreds μm (10^-6m) degree.
The capillary 31a having the above-described configuration is inserted into the cooling gas supply unit 32 so as to be detachable and replaceable, and the tip 31c projects slightly toward the vaporizer 50 than the tip 32a of the cooling gas supply.
[0032]
The above-mentioned several tens to several hundreds μm (10^-6m) In order to pump the liquid raw material 34 into the capillary 31a having an inner diameter of about several tens of kg / cm²Since a liquid feeding pressure of a certain level is required, a pressurizing liquid pump 35 for feeding the liquid raw material 34 fed from the raw material supply device 40 through the connection pipe 41 into the capillary tube 31a as shown in FIG. It is connected to the liquid supply part 31d via the connecting pipe 35a.
[0033]
The cooling gas supply unit 32 has a capillary tube 31a inserted therein, and Ar gas, N is inserted into the gap with the capillary tube 31a.₂A cooling gas such as a gas is supplied.
A cooling gas supply source 36 is connected to the upper part of the cooling gas supply unit 32 via a cooling gas MFC 36 a shown in FIG. 1 so that the cooling gas is supplied to the cooling gas supply unit 32.
[0034]
The liquid raw material supply device 30 can be composed entirely of metal parts such as stainless steel except for the capillary tube 31a made of glass or the like, and the cooling gas supply unit 32 and the cooling gas supply constituting the liquid raw material supply device 30 The exterior portion 33 that supports the portion 32 is joined and integrated at the upper end portion.
[0035]
The tip portion 31c of the capillary tube 31a and the tip portion 32a of the cooling gas supply unit 32 have a structure that protrudes larger in the insertion direction into the vaporizer 50 than the tip portion 33a of the exterior portion 33 of the liquid source supply device 30. The protrusion length is adjusted to an optimum length in accordance with the length of the heat transfer section 56 provided in the liquid raw material introduction section 51a of the vaporizer 50.
Furthermore, the tip 31c of the capillary tube 31a protrudes from the tip 32a of the cooling gas supply unit 32 to the vaporizer 50 side by about 1 to 10 mm.
[0036]
In the liquid raw material supply device 30 having the above-described configuration, when the liquid raw material 34 is pumped from the liquid supply portion 31d into the capillary tube 31a at a constant flow rate, the liquid raw material 34 reaches the tip portion 31c of the capillary tube 31a and becomes a liquid droplet. The liquid material 34 in the form of droplets continuously supplied to the vaporizer 50 and supplied into the vaporizer 50 is heated and vaporized in the vaporizer 50.
Further, when the cooling gas is caused to flow at a constant flow rate to the cooling gas supply unit 32 simultaneously with the pressure feeding of the liquid raw material 34, the capillary tube 31a is cooled by the cooling gas, so that overheating by the heater 52 of the vaporizer 50 is prevented, It is possible to prevent the liquid raw material 34 from being vaporized in the capillary tube 31a.
The cooling gas cools the capillary tube 31a in the cooling gas supply unit 32, and then is discharged into the vaporizer 50 from the tip 32a of the cooling gas supply unit, and the liquid raw material 34 is mixed with the vaporized gas to form the raw material gas. Configure.
[0037]
As shown in FIG. 1, the raw material supply apparatus 40 includes a storage container 42 and an inert gas source 43, and the liquid raw material 34 is stored inside the storage container 42. The raw material supply device 40 supplies an inert gas such as Ar gas into the storage container 42 from the inert gas source 43 to keep the inside of the storage container 42 in an inert atmosphere. The inert gas such as Ar gas is released to the atmosphere from the outlet 43a of the inert gas, and the inside of the storage container 42 is maintained at normal pressure.
[0038]
In the liquid material supply apparatus 10, a vaporizer 50 is disposed below the liquid material supply device 30.
The vaporizer 50 shown in FIG. 1 is generally configured by a box-shaped vaporization chamber 51 and a heater 52 that is disposed on the outer periphery of the vaporizer 50 and heats the vaporization chamber 51.
In the vaporization chamber 51, a liquid raw material introduction part 51a is provided so as to protrude toward the liquid raw material supplier 30. The liquid raw material introduction part 51a has a cylindrical heat transfer part 56 made of a heat retaining member such as stainless steel. I have.
The liquid raw material supply unit 30 is connected to the vaporizer 50 with the cooling gas supply unit 32 and the capillary tube 31 a inside thereof being housed in the heat transfer unit 56, with the vaporization chamber 51 sealed by an O-ring 53.
[0039]
A heater 52 for heating the inside of the vaporizing chamber 51 is disposed on the outer periphery of the vaporizer 50, and the liquid raw material 34 supplied from the tip portion 31c of the capillary tube 31a by the heater 52 is brought to a desired temperature. The gas is heated and vaporized, and further mixed with the cooling gas flowing into the vaporizing chamber 51 from the gap between the tip 32a of the cooling gas supply unit 32 and the tip 31c of the capillary tube 31a to obtain a raw material gas.
[0040]
In addition, the heater 52 heats the cooling gas supply unit 32 via the heat transfer unit 56 provided in the liquid raw material introduction unit 51a to increase the temperature of the cooling gas flowing into the vaporizing chamber 51, thereby supplying the cooling gas. In addition to preventing reprecipitation from the source gas convection to the portion 32 and also increasing the temperature of the capillary 31a to some extent, the temperature of the capillary 31a and its tip 31c is prevented from decreasing, and the liquid material at the tip 31c of the capillary 31a is prevented. Can be effectively prevented from reprecipitation.
Since the heat transfer unit 56 is provided so as to be in close contact with the cooling gas supply unit 32, the cooling gas supply unit 32 is heated to a high temperature, but the cooling gas is introduced into the gap with the capillary tube 31a. Therefore, the capillary tube 31a is kept at a lower temperature than the cooling gas supply unit 32, and the liquid raw material 34 inside the capillary tube 31a is not vaporized.
[0041]
Further, as shown in FIG. 1, the inside of the vaporizing chamber 51 is divided into two regions 51d and 51e with a partition plate 54 interposed therebetween. These two regions are formed by the bottom 51b of the vaporizing chamber 51 and the partition plate 54. It communicates through a gap.
The raw material gas generated from the gas vaporized from the liquid raw material 34 supplied from the capillary tube 31a and the cooling gas moves from the region 51d to the region 51e through the gap below the partition plate 54, and further to the region 51e. Is transported out of the vaporizer 51 from a source gas outlet 51c provided at the upper end of the vaporization chamber 51 corresponding to the above.
The source gas derived from the source gas outlet 51 c is supplied to the CVD reactor 60 connected to the vaporizer 50 via the transport pipe 57.
The structure of the vaporizing chamber 51 may be, for example, a U-shape in addition to the structure divided into two using the partition plate 54 as described above. Thus, when the vaporization chamber is U-shaped, the liquid raw material 34 is supplied from the liquid raw material supply device 30 to one end portion side of the U-shaped vaporization chamber, and the raw material gas is supplied from the other end portion side. Is supplied to the CVD reactor 60 through the transport pipe 57. When the vaporization chamber is formed in a U-shape in this way, the temperature in the vaporization chamber can be easily kept constant.
[0042]
The CVD reactor 60 has a reaction chamber 61 made of quartz. The reaction chamber 61 has a cylindrical shape with both horizontally long ends sealed, and in order from the side where the base material is introduced, a base material introduction part 62, a reaction generation chamber 63, and a base material outlet part 64 are partitioned (see FIG. (Not shown).
The base material introduction part 62 is provided with an introduction hole for introducing the tape-like base material 65, and the base material lead-out part 64 is provided with a lead-out hole for leading out the base material 65. A sealing member (not shown) that closes the gap between the holes and seals the base material introduction part 62 and the base material lead part 64 in a state where the base material 65 is allowed to pass is provided at the peripheral part of the hole and the lead hole. Is provided.
In addition, a pyramid type gas diffusion portion 66 communicating with the reaction generation chamber 63 is attached to the ceiling portion of the reaction generation chamber 63.
[0043]
A heater 47 is provided outside the CVD reaction apparatus 60 to cover a portion from the side of the reaction generating chamber 63 of the base material introducing portion 62 to a portion of the base material outlet 64 on the side of the reaction generating chamber 63. The material introducing unit 62 is connected to an inert gas supply source 68, and the base material outlet unit 64 is connected to an inert gas supply source 69.
In addition, a transport pipe 57 connected to the vaporizer 50 of the raw material supply apparatus 10 is connected to the gas diffusion part 66.
A heating means (not shown) is provided around the transport pipe 57 to prevent the source gas from being deposited as the liquid source 34.
An oxygen gas supply source 54 a is branched and connected in the middle of the transport pipe 57 so that oxygen gas can be supplied to the transport pipe 57.
[0044]
In addition, an exhaust pipe 70 is provided at the bottom of the CVD reactor 60 and is connected to a pressure regulator 72 equipped with a vacuum pump 71 so that the gas inside the CVD reactor 60 can be exhausted. ing.
Further, on the side of the base material lead-out portion 64 of the CVD reactor 60, a base material transport mechanism comprising a tension drum 73 and a take-up drum 74 for winding the base material 65 passing through the CVD reactor 60. 75 is provided.
A base material transport mechanism 78 including a tension drum 76 and a delivery drum 77 for supplying the base material 65 to the CVD reactor 60 is provided on the side of the base material introduction part 62.
[0045]
Next, the manufacturing method of the oxide superconductor of the present invention using the oxide superconductor manufacturing apparatus having the above configuration will be described.
In order to manufacture an oxide superconductor using the manufacturing apparatus shown in FIG. 1, first, a tape-shaped substrate 65 and a liquid material 34 are prepared.
The substrate 65 may be a long one, but is preferably a heat-resistant metal tape having a low coefficient of thermal expansion, or an upper surface thereof coated with a ceramic intermediate layer.
As a constituent material of the heat-resistant metal tape, metal materials such as silver, platinum, stainless steel, copper, hastelloy (C276, etc.), and alloys are preferable.
In particular, when a metal tape made of silver having {100} <001> or {110} <110> texture is used, a superconductor can be formed directly on the metal tape, and the oxide superconductor to be formed Since orientation can be controlled, it is more preferable.
Besides the metal tape, a glass tape, a mica tape, or a ceramic tape may be used.
[0046]
Next, the material constituting the intermediate layer is composed of YSZ (yttrium stabilized zirconia), SrTiO, whose thermal expansion coefficient is closer to that of the oxide superconductor than that of the metal._Three, MgO, Al₂O_ThreeLaAlO_ThreeLaGaO_ThreeYAlO_Three, ZrO₂Ceramics such as these are preferable, and among these, those having as much crystal orientation as possible are more preferable.
Next, as described above, a mixture of several kinds of organometallic complexes of the constituent metal elements of the oxide superconductor so as to have the desired composition ratio is mixed and dissolved in a mixture of tetrahydrofuran and ethylene glycol dimethyl ether. To produce a liquid raw material.
[0047]
As long as the organometallic complex is soluble in the solvent, the metal element alkoxide, acetylacetonato, dipivaloylmethanato, cyclopentadienyl, or derivatives thereof constituting the target compound should be used. Can do.
In addition, the concentration of the liquid raw material, the mixing ratio of the mixed solvent, and the like are appropriately changed depending on the type of the target compound, and the optimum conditions are set.
For example, when producing a Y—Ba—Cu—O-based oxide superconductor, the concentration is preferably 5 to 20% by weight, more preferably 6 to 10% by weight.
Moreover, the mixing ratio of tetrahydrofuran and ethylene glycol dimethyl ether is preferably 1: 1 to 9: 1, more preferably 6: 1 in terms of volume ratio.
[0048]
When the tape-shaped base material 65 is prepared, it is fed into the reaction chamber 61 from the base material introduction part 62 by the base material transport mechanism 78 at a predetermined moving speed and the take-up drum 74 of the base material transport mechanism 75. Then, the substrate 65 in the reaction generation chamber 63 is heated to a predetermined temperature by the heater 47.
Although the moving speed of the base material 65 and the set temperature of the heater 47 depend on the composition system of the target oxide superconductor, they are preferably about 1 to 10 m / hour and about 600 to 800 ° C., respectively.
Before feeding the base material 65, the inert gas is fed from the inert gas supply sources 68 and 69 into the reaction chamber 61 as a purge gas, and at the same time, the pressure regulator 72 is operated to exhaust the inside of the reaction chamber 61. Thus, it is preferable to clean the interior by eliminating unnecessary gas such as moisture in the reaction chamber 61.
[0049]
Subsequently, the liquid raw material 34 is sucked from the storage container 42 using the pressurized liquid pump 35, and the liquid raw material 34 is pumped into the capillary tube 31a at a speed of about 0.1 to 1.0 ml / min. Is fed into the cooling gas supply unit 32 at a flow rate of about 300 to 600 ccm (ml / min). At the same time, the pressure adjusting device 72 is operated, and the gas inside the reaction chamber 61 is exhausted. At this time, the temperature of the cooling gas is adjusted to be about room temperature.
In addition, the heater 52 adjusts the internal temperature of the vaporizing chamber 51, the internal temperature of the liquid raw material introducing portion 51a, and the temperature of the liquid raw material supply device 30 so that the optimal temperature of the raw material having the highest vaporization temperature among the above raw materials is obtained. Keep it. In this way, the cooling gas supply unit 32 is preheated by the heater 52 and reprecipitation of the raw material gas in the vaporization chamber 51 is prevented.
[0050]
Then, the liquid raw material 34 is supplied in the form of droplets from the tip 31c of the capillary 31a into the vaporizing chamber 51, and the liquid droplet 34 supplied to the inside of the vaporizer 50 is supplied by a heater. While being heated by 52 and mixed with a cooling gas, it is vaporized to become a raw material gas, and this raw material gas is continuously supplied to the gas diffusion portion 66 of the CVD reactor 60 through the transport pipe 53.
At this time, it is adjusted by the heating means so that the internal temperature of the transport pipe 57 becomes the optimum temperature of the raw material having the highest vaporization temperature among the raw materials. At the same time, an operation of supplying oxygen gas from the oxygen gas supply source 54a and mixing the oxygen gas into the raw material gas is also performed.
[0051]
Next, in the reaction chamber 61, the source gas released from the outlet portion of the transport pipe 57 to the gas diffusion portion 66 moves toward the reaction generation chamber 63 while diffusing from the gas diffusion portion 66, and the reaction generation chamber 63. 63 passes through the inside of 63 and then moves in the vicinity of the base material 65 so as to be drawn into the gas exhaust pipe 70.
Therefore, the oxide superconducting thin film can be generated by reacting the raw material gas on the upper surface side of the heated substrate 65. Thereafter, the base material 65 on which the oxide superconducting thin film is formed is subjected to a heat treatment, so that the superconducting characteristics are exhibited or improved in the oxide superconducting thin film, whereby the oxide superconductor 80 can be obtained.
By continuously performing the above film forming operation for a predetermined time, an oxide superconductor including a stable oxide superconductor 80 having a desired film quality on the base material 65 can be obtained.
[0052]
According to the method for producing an oxide superconductor of the present invention, since the liquid raw material for CVD is used as the liquid raw material, the liquid raw material is modified as in the case of using the liquid raw material using THF as a solvent. Since no substance is precipitated, the composition ratio of the liquid raw material during film formation can be maintained for a long time with the composition ratio at the time of preparation.
Therefore, even when a film is formed for a long time, an oxide superconducting thin film having a constant composition can be stably formed, and an oxide superconductor having uniform characteristics over a long length can be manufactured. According to the manufacturing method as described above, an oxide superconductor having superconducting characteristics such as a critical current density excellent over a long length can be manufactured.
Further, since unnecessary solids do not precipitate in the liquid raw material, dismantling cleaning of the pressurized liquid pump 35 and replacement of the capillary tube 31a are unnecessary, and film formation can be continuously performed without maintenance for a long period of time. Costs and labor can be greatly reduced.
[0053]
【Example】
  The present invention will be described more specifically with reference to the following examples.
(Preparation of liquid raw materials)
  First, Ba-bis-2,2,6,6-tetramethyl-3,5-heptanedione (Ba (thd)₂) And Y (thd) ₃ And Cu (thd)₂Was mixed at a molar ratio of Y: Ba: Cu = 1.0: 1.9: 2.5 to ethylene glycol dimethyl ether so as to be 7% by weight to prepare liquid raw material A.
[0054]
Next, an organic metal complex equivalent to the above mixed in tetrahydrofuran (THF) at a molar ratio of Y: Ba: Cu = 1.0: 1.9: 2.5 is added so as to be 7% by weight. Thus, a liquid raw material A was produced.
[0055]
Next, a mixture of tetrahydrofuran (THF) and ethylene glycol dimethyl ether (DME) at a volume ratio of 9: 1 is mixed with an organometallic complex equivalent to the above Y: Ba: Cu = 1.0: 1.9: 2. The liquid raw material B was prepared by dissolving the mixture at a molar ratio of 0.5 to 7 wt%.
Next, a mixture of tetrahydrofuran (THF) and ethylene glycol dimethyl ether (DME) at a volume ratio of 5: 1 is mixed with an organometallic complex equivalent to the above Y: Ba: Cu = 1.0: 1.9: 2. A liquid raw material C was prepared by dissolving the mixture at a molar ratio of 5 to 7 wt%.
Next, a mixture of tetrahydrofuran (THF) and ethylene glycol dimethyl ether (DME) at a volume ratio of 1: 1 is mixed with an organometallic complex equivalent to the above Y: Ba: Cu = 1.0: 1.9: 2. A liquid raw material D was prepared by dissolving the mixture at a molar ratio of 0.5 to 7 wt%.
[0056]
Next, a mixture of tetrahydrofuran (THF) and ethylene glycol dimethyl ether (DME) at a volume ratio of 1: 5 is mixed with an organometallic complex equivalent to the above Y: Ba: Cu = 1.0: 1.9: 2. A liquid raw material E was prepared by dissolving the mixture at a molar ratio of 5 to 7 wt%.
Next, a mixture of tetrahydrofuran (THF) and ethylene glycol dimethyl ether (DME) in a volume ratio of 1: 9 is mixed with an organometallic complex equivalent to the above Y: Ba: Cu = 1.0: 1.9: 2. The liquid raw material F was prepared by dissolving the mixture at a molar ratio of 0.5 to 7 wt%.
[0057]
Next, 7% by weight is obtained by mixing ethylene glycol dimethyl ether (DME) with an organometallic complex equivalent to the above in a molar ratio of Y: Ba: Cu = 1.0: 1.9: 2.5. To prepare a liquid raw material G.
[0058]
Next, 7% by weight is obtained by mixing methyl-t-butyl ether with an organometallic complex equivalent to the above in a molar ratio of Y: Ba: Cu = 1.0: 1.9: 2.5. The liquid raw material H was prepared by adding.
Next, a mixture of ethylene glycol dimethyl ether and methyl-t-butyl ether in a volume ratio of 1: 1 is mixed with an organometallic complex equivalent to the above by Y: Ba: Cu = 1.0: 1.9: 2.5. A liquid raw material I was prepared by dissolving the mixture at a molar ratio of 7 wt%.
[0059]
The liquid raw materials A to I were filled in separate glass containers, and the containers were filled with nitrogen gas and sealed in a sealed state for 30 days at room temperature, and then each liquid raw material was visually observed. The results are shown in Table 1 below. In Table 1, Δ indicates that a clear precipitate was observed at the bottom of the glass container, ○ indicates that a slight amount of precipitate or microcrystal was observed at the bottom of the glass container, Indicates that no precipitates or microcrystals were observed in the glass container.
[0060]
[Table 1]

[0061]
From the results shown in Table 1, the liquid raw material A using THF as a solvent showed white precipitate formation (precipitation of a white modified substance) after storage at room temperature for 30 days, whereas a mixture of THF and DME was used. Liquid raw material B to F used as a solvent, liquid raw material G using DME as a solvent, liquid raw material H using methyl-t-butyl ether as a solvent, liquid using a mixture of DME and methyl t-butyl ether as a solvent In the raw material I, no white precipitate was formed after storage at room temperature for 30 days. In particular, the liquid raw materials B to D using a mixture of THF and DME as a solvent have excellent storage properties. It can be seen that it is preferable to adjust the mixing ratio in the range of 1: 1 to 9: 1 in terms of improving the stability of the Ba-based raw material and suppressing the formation of a white precipitate.
[0062]
(Production of oxide superconductor)
When the oxide superconductor is manufactured using the oxide superconductor manufacturing apparatus having the configuration shown in FIG. 1, the liquid raw materials A to I previously prepared as liquid raw materials used as a solution of the raw material gas supplied to the reaction generation chamber. And various oxide superconductors (Sample Nos. 1 to 9) were produced. Table 2 shows the results of examining the maintenance periods of the pressurized liquid pump and the capillary tube when manufacturing the oxide superconductor. The results of measuring the critical current density (Jc) of the various oxide superconductors obtained by the four-terminal method are also shown in Table 2.
[0063]
When producing an oxide superconductor, an inner diameter of 40 μm (10^-61) Using an oxide superconductor manufacturing apparatus having the configuration shown in FIG. 1 to which a capillary tube of FIG. 1 is attached, an Ag tape substrate (non-oriented Ag tape) having a width of 10 mm, a length of 100 cm, and a thickness of 0.2 mm is used. The moving speed of the base material was set to 3.0 m / hour, the temperature of the reaction generation chamber was set to 700 ° C., and the liquid raw material prepared above was used as the raw material gas solution supplied to the reaction generation chamber.
Next, the pressure of the pressurized liquid pump is adjusted to 35 kg / cm², Pumping at a supply rate of 0.3 ml / min, a cooling gas supply rate of 450 ccm to the cooling gas supply unit,
The reaction pressure in the reaction generation chamber was 5.0 Torr (= 5 × 133 Pa) and the oxygen partial pressure was 1.25 Torr (= 1.25 × 133 Pa), and the raw material gas was sprayed onto the Ag tape base material from the gas diffusion portion. Y on material₁Ba₂Cu_ThreeO_xAfter forming an oxide superconducting film having the following composition, heat treatment was performed at 500 ° C. for 2 hours to obtain various oxide superconductors.
[0064]
[Table 2]

[0065]
From the results shown in Table 2, sample Nos. Produced using liquid raw material A using THF as a solvent were obtained. When the oxide superconductor 1 is manufactured, the liquid pump maintenance cycle is once every two months and the capillary exchange cycle is once a week, whereas the liquid raw material B using a mixture of THF and DME as a solvent is used. Sample No. manufactured using F. Sample No. 2 produced using a liquid raw material G using 2 to 6 oxide superconductors and DME as a solvent. Sample No. 7 produced using the liquid raw material H using the oxide superconductor No. 7 and methyl-t-butyl ether as a solvent. Sample No. 8 produced using liquid raw material I using a mixture of oxide superconductor No. 8 and DME and methyl-t-butyl ether as a solvent. When the oxide superconductor of No. 9 was produced, the liquid pump maintenance cycle and the capillary exchange cycle were improved. In particular, Sample No. 9 produced using liquid raw materials B to D using a mixture of THF and DME as a solvent. It can be seen that when 2 to 4 oxide superconductors are manufactured, the liquid pump maintenance cycle is significantly longer once every six months and the capillary exchange cycle is once every five weeks.
[0066]
Sample No. The critical current density of oxide superconductors 1 and 8 is 35000 A / cm²In contrast to the following, sample no. The critical current density of 2-6 oxide superconductors is 37000 A / cm²In particular, sample no. The critical current density of 2-4 oxide superconductors is 39000 A / cm.²Thus, it was confirmed that the superconducting properties were excellent.
[0067]
【The invention's effect】
As described above, the liquid material for CVD of the present invention employs a mixture of THF and DME as a solvent for dissolving the organometallic complex. Therefore, a constant composition ratio can be maintained over a long period of time after the liquid raw material is prepared. Therefore, even when continuous film formation is performed for a long time, the liquid material for CVD according to the present invention can be prepared, so that efficient material supply can be performed. As described above, the liquid material for CVD of the present invention can maintain the composition ratio at the time of preparation for a long period after preparation, so that the CVD reaction product is continuously deposited on a long substrate. However, it is possible to form a thin film such as an oxide superconducting thin film or a dielectric thin film that can maintain the composition as designed and has uniform characteristics over a long length.
In addition, since the liquid raw material for CVD of the present invention does not deposit metamorphic substances over time, maintenance cycles such as disassembly cleaning of liquid pumps and replacement of capillaries can be lengthened, greatly reducing the cost and labor required for these. Can be reduced.
[0068]
Next, according to the method for producing an oxide superconductor of the present invention, the oxide superconductor is formed using the above-described liquid material for CVD of the present invention. It is possible to supply an oxide superconductor having a stable quality over the length of the substrate.
[Brief description of the drawings]
FIG. 1 is a configuration diagram schematically showing an example of an apparatus for manufacturing an oxide superconductor according to the present invention.
FIG. 2 is a diagram showing an example of a CVD liquid source supply apparatus.
[Explanation of symbols]
10 Liquid material supply device for CVD
30 Liquid material feeder
31 Capillary insertion part
31a capillary tube
31c Capillary tip
32 Cooling gas supply unit
34 Liquid material for CVD
50 Vaporizer
51 Vaporization room
52 Heater
60 CVD reactor
63 Reaction generation chamber
65 base material

Claims (4)

One or more organic metal complexes in the CVD liquid material obtained by dissolving in a solvent, said solvent, Ri mixture der tetrahydrofuran and ethylene glycol dimethyl ether,
The organometallic complex is composed of RE ₁ Ba ₂ Cu ₃ O _x (where RE is selected from Y, La, Ce, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, and Yb) An organic complex of a metal element that forms an oxide superconductor represented by 1 or 2 or more, wherein the organometallic complex includes an organic barium complex,
The solvent, tetrahydrofuran and ethylene glycol dimethyl ether, 1: 1 to 9: CVD liquid material, characterized in der Rukoto those mixed at a volume ratio. The liquid material for CVD according to claim 1, wherein the organic barium complex is Ba (thd) ₂ or Ba (thd) ₂ · phen ₂ . A step of dissolving the organometallic complex in a solvent to prepare a liquid source, a step of generating a source gas by vaporizing the liquid source with a vaporizer, and introducing the source gas into a reaction generation chamber for performing a CVD reaction A method for producing an oxide superconductor comprising a step of forming an oxide superconductor on a substrate,
The solvent for dissolving the organometallic complex, Ri mixture der tetrahydrofuran and ethylene glycol dimethyl ether,
The organometallic complex is composed of RE ₁ Ba ₂ Cu ₃ O _x (where RE is selected from Y, La, Ce, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, and Yb) An organic complex of a metal element that forms an oxide superconductor represented by 1 or 2 or more, wherein the organometallic complex includes an organic barium complex,
The solvent for dissolving the organometallic complex, tetrahydrofuran and ethylene glycol dimethyl ether, 1: 1-9: method of manufacturing an oxide superconductor, characterized in der Rukoto those mixed at a volume ratio. The method for producing an oxide superconductor according to claim 3 , wherein the organic barium complex is Ba (thd) ₂ or Ba (thd) ₂ · phen ₂ .

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