JPS5938197B2 - Melt for growth of barium lead bismuthate single crystals - Google Patents
Melt for growth of barium lead bismuthate single crystalsInfo
- Publication number
- JPS5938197B2 JPS5938197B2 JP57074510A JP7451082A JPS5938197B2 JP S5938197 B2 JPS5938197 B2 JP S5938197B2 JP 57074510 A JP57074510 A JP 57074510A JP 7451082 A JP7451082 A JP 7451082A JP S5938197 B2 JPS5938197 B2 JP S5938197B2
- Authority
- JP
- Japan
- Prior art keywords
- melt
- barium
- single crystal
- growth
- bismuthate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】
本発明は、極低温素子用材料として有望な鉛ビスマス酸
バリウム単結晶を成長させるに適した溶融物に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a melt suitable for growing barium lead bismuthate single crystals, which are promising as materials for cryogenic devices.
鉛ビスマス酸バリウム（化学式：ＢａＰｂ１ ｘＢｉ
ｘＣ）ｓ）は、鉛酸バリウム（化学式：ＢａＰｂＯ５）
とビスマス酸バリウム（化学式： ＢａＢ１０３）、の
固宕体で、Ｘが０．０５から０．３５の組成範囲では、
超伝導性を示すことが知られている。Barium lead bismuthate (chemical formula: BaPb1 xBi
xC)s) is barium leadate (chemical formula: BaPbO5)
and barium bismuthate (chemical formula: BaB103), in the composition range of X from 0.05 to 0.35,
It is known to exhibit superconductivity.
本固溶体は、酸化物であるので、酸化雰囲気に対して安
定で、また通常のセラミックスと同様な手段で作れる超
伝導素子用材料として極めて注目されている。Since this solid solution is an oxide, it is stable in an oxidizing atmosphere and is attracting much attention as a material for superconducting elements that can be produced by the same method as ordinary ceramics.
しかしながら、この鉛ビスマス酸バリウム固溶体は高温
で分解しやすく、このため常圧下で溶融状態より単結晶
を成長させることは現在においては不可能である。However, this barium lead bismuthate solid solution is easily decomposed at high temperatures, and therefore it is currently impossible to grow a single crystal from a molten state under normal pressure.
したがって、高温高圧装置を用いて単結晶を成長させる
方法も検討されたが、装置が非常に高価とならざるをえ
ず、この方法も事実上不可能である。Therefore, a method of growing a single crystal using a high-temperature, high-pressure device has been considered, but the device must be extremely expensive, and this method is also virtually impossible.
このためとるべく低温において単結晶を成長させる方法
が提案されている。For this reason, methods have been proposed in which single crystals are grown at low temperatures.
すなわち、単結晶を成長させようとする材料（鉛ビスマ
ス酸バリウムの焼結体）を溶媒中に溶解し、この溶融物
を徐冷したり、あるいは前記溶媒を蒸発せしめたりして
結晶を成長させる、いわゆるフラックス法である。That is, the material for which a single crystal is to be grown (a sintered body of barium lead bismuthate) is dissolved in a solvent, and the molten material is slowly cooled or the solvent is evaporated to grow a crystal. This is the so-called flux method.
この方法を用いるにあたっては、まず溶媒となる物質を
選択しなくてはならない。To use this method, you must first select a substance to serve as the solvent.
この溶媒としては、■単結晶を成長させようとする材料
をかなり啓解する、■有害な不純物を結晶中へ導入しな
い、■粘性が適度である、などの条件を充足するものを
選択する必要があるが、このような溶媒は数多くの実験
データの検討により、最良のものを捜し出さねばならな
い。As this solvent, it is necessary to select a solvent that satisfies the following conditions: 1) It has a good understanding of the material used to grow the single crystal, 2) It does not introduce harmful impurities into the crystal, 2) It has an appropriate viscosity. However, the best such solvent must be found by examining a large amount of experimental data.
現在において、鉛ビスマス酸バリウム単結晶を成長させ
るに適した啓媒は知られておらず、したがってこの方法
においても鉛ビスマス酸バリウム単結晶を製造すること
は不可能であった。At present, no growth medium suitable for growing barium lead bismuthate single crystals is known, and therefore it has been impossible to produce barium lead bismuthate single crystals using this method.
本発明は従来不可能であった鉛ビスマス酸バリウム単結
晶を容易に成長しうる溶融物を提供することを目的とす
る。An object of the present invention is to provide a melt that allows easy growth of barium lead bismuthate single crystals, which was previously impossible.
本発明による溶融物を概説すれば、基本的に酸化バリウ
ムと酸化ビスマスと過剰の酸化鉛から成ることを特徴と
する鉛ビスマス酸バリウム単結晶成長用溶融物である。Briefly, the melt according to the invention is a melt for growing barium lead bismuthate single crystals, which is characterized in that it basically consists of barium oxide, bismuth oxide and an excess of lead oxide.
本発明による溶融物によれば、従来不可能であった鉛ビ
スマス酸バリウム単結晶を良好に、制御性良く、かつ容
易に成長させうると言う利点がある。The melt according to the present invention has the advantage that a barium lead bismuthate single crystal, which was previously impossible to grow, can be easily grown with good controllability.
本発明を更に詳しく説明する。The present invention will be explained in more detail.
本発明において単結晶を成長させる鉛ビスマス酸バリウ
ムは下記の一般式（１）：
％式％（１）
（ただしＸは１より小さい実数を示す）
で示されるものであり、本発明においては、特にＸが０
．０５〜０．３５の値を示す超伝導素子用材料として用
いられる鉛ビスマス酸バリウムを対象とするが、これに
限定されるものでないことは明かである。The barium lead bismuthate on which the single crystal is grown in the present invention is represented by the following general formula (1): % formula % (1) (where X is a real number smaller than 1), and in the present invention, Especially when X is 0
．． Although the present invention is directed to barium lead bismuthate, which is used as a material for superconducting elements and exhibits a value of 0.05 to 0.35, it is clear that the present invention is not limited to this.
本発明による溶融物は、前述のように酸化バリウム、酸
化ビスマス及び過剰の酸化鉛より基本的に成るものであ
り、これに種々の添加物を添カロしてもよいのはもちろ
んである。The melt according to the present invention basically consists of barium oxide, bismuth oxide and excess lead oxide as described above, and it goes without saying that various additives may be added thereto.
前述のような０．０５〈Ｘ≦０．３５の範囲の鉛ビスマ
ス酸バリウム単結晶を成長させる際の溶融物の組成比は
、好ましくは酸化バリウム５〜２５、酸化ビスマス２０
以下、酸化鉛６０〜９０（重量比）である。The composition ratio of the melt when growing a barium lead bismuthate single crystal in the range of 0.05 <
Below, lead oxide is 60 to 90 (weight ratio).
この重量比を逸脱すると０．０５≦Ｘ≦０．３５の組成
範囲から外れるおそれがでるからである。This is because if the weight ratio deviates from this, there is a risk that the composition will deviate from the composition range of 0.05≦X≦0.35.
コノヨうな溶融物より鉛ビスマス酸バリウム単結晶を成
長させるには、溶融状態に保持した前記溶融物を徐冷し
、単結晶を析出させ、残余の廃液を流し出したり、適当
なエンチング剤を用い選択的に除去したりして結晶と廃
液を分離することにより行なうことができる。In order to grow barium lead bismuthate single crystals from such a molten material, the molten material kept in a molten state is slowly cooled, a single crystal is precipitated, and the remaining waste liquid is poured out, or an appropriate enquenching agent is used. This can be done by selectively removing the crystals and separating the waste liquid.
また溶融物に白金線あるいは種子結晶を接触させ回転引
上げることにより単結晶を成長させることも可能であり
、さらに、格子整合性のよい結晶基板上へとの溶融物を
接触させて単結晶薄膜を成長させることもできる。It is also possible to grow a single crystal by bringing a platinum wire or seed crystal into contact with the melt and pulling it up by rotation.Furthermore, it is possible to grow a single crystal thin film by bringing the melt into contact with a crystal substrate with good lattice matching. can also be grown.
すなわち、本発明の溶融物より単結晶を成長させる方法
は基本的に限定されるものではない。That is, the method of growing a single crystal from a melt according to the present invention is basically not limited.
以下本発明の実施例について説明する。Examples of the present invention will be described below.
実施例 １
まずＢａＯ：Ｂｉ２Ｏ３：ＰｂＯ２＝１５ ： １５ニ
ア０となるよう炭酸バリウム、３酸化２ビスマス、２酸
化鉛をそれぞれ秤量した。Example 1 First, barium carbonate, bismuth trioxide, and lead dioxide were each weighed so that BaO:Bi2O3:PbO2=15:15Nia0.
次に、温合混合し、脱水、乾燥後、白金ルツボに装填し
て、電気炉内で加熱した。Next, the mixture was warm mixed, dehydrated, and dried, then loaded into a platinum crucible and heated in an electric furnace.
１０００’Ｃの温度に約８時間保持した後、約２°Ｃ／
ｈｒの速度で徐冷した。After being kept at a temperature of 1000'C for about 8 hours, the temperature of about 2°C/
It was slowly cooled at a rate of hr.
この操作の間、ＢａＯとＢｉ２Ｏ３と酸化鉛が反応して
ＢａＰｂ１−ｘＢｉｘＯ３の結晶核が生成し、成長する
。During this operation, BaO, Bi2O3, and lead oxide react to form and grow BaPb1-xBixO3 crystal nuclei.
８００〜８５０℃の温度に達したら白金ルツボを傾斜し
て、溶融状態の廃液（主成分がＰｂＯからなる）を別の
容器に移した。When the temperature reached 800 to 850° C., the platinum crucible was tilted and the molten waste liquid (mainly composed of PbO) was transferred to another container.
その結果、廃液を流し出した白金ルツボ内にはＢａＰｂ
１ ｘＢｉｘ０３結晶のみが残り、かくして成長した結
晶と廃液な分離できた。As a result, BaPb was found inside the platinum crucible from which the waste liquid was poured out.
Only 1xBix03 crystals remained, and the thus grown crystals could be separated from the waste liquid.
ここで、結晶と廃液の分離は、廃液の入った白金ルツボ
な室温まで冷却した後、廃液のみを適当なエツチング剤
で選択的に除くことによっても可能である。Separation of the crystals and the waste liquid can also be achieved by cooling the platinum crucible containing the waste liquid to room temperature and then selectively removing only the waste liquid using an appropriate etching agent.
成長終了後、白金ルツボな電気炉から取り出したところ
、白金ルツボ内には、いろいろな形と寸法をもった結晶
が付着していた。When the platinum crucible was removed from the electric furnace after growth, crystals of various shapes and sizes were found attached to the platinum crucible.
得られた結晶の大部分が単結晶であり、その組成は、お
およそＸが０．２５であることがＸ線回折法で明らかと
なった。It was revealed by X-ray diffraction that most of the obtained crystals were single crystals, and their composition had an X of approximately 0.25.
また電気抵抗の温度変化を測定したところ、超伝導転移
を示した。Furthermore, when we measured the change in electrical resistance with temperature, we found that it showed a superconducting transition.
かくして、Ｘが０．０５から０．３５の組成範囲にある
超伝導ＢａＰｂ、 ｘＢｉｘ０３の単結晶を成長でき
た。In this way, we were able to grow a single crystal of superconducting BaPb, xBix03, with a composition in which X was in the range of 0.05 to 0.35.
実施例 ２
次に、ＢａＯ：Ｂｉ２Ｏ３： ＰｂＯ２＝１５ ：５：
８０と２５ ： ２５ ： ５０の組成比からなる混合
物を実施例１と同様の方法で、溶解、徐冷したところ、
前者ではＸ中０．１５、後者では、Ｘ中０．５０の組成
を有する単結晶を得ることができた。Example 2 Next, BaO:Bi2O3:PbO2=15:5:
A mixture having a composition ratio of 80 and 25:25:50 was dissolved and slowly cooled in the same manner as in Example 1.
In the former case, a single crystal having a composition of 0.15 in X was obtained, and in the latter case, a single crystal having a composition in X of 0.50 was obtained.
かくして、ＢａＯとＢｉ２Ｏ３とＰｂＯ２との配合組成
比をＰｂＯ２の過剰組成側で変えることにより、ＢａＰ
ｂ１ ｘＢｉｘ０３の単結晶が得られるだけでなく、得
られる単結晶の組成も制御できることが明らかとなった
。Thus, by changing the blending composition ratio of BaO, Bi2O3, and PbO2 toward the excess composition of PbO2, BaP
It has become clear that not only a single crystal of b1 xBix03 can be obtained, but also the composition of the obtained single crystal can be controlled.
また、ＰｂＯ過剰の容赦を用いて、その液上に白金線、
または、上記方法で得たＢａＰｂ、ｘＢｉｘＯａ単結晶
を白金線でしばりつけ固定したものを種子として、回転
しながら、引上げることにより種子上に超伝導ＢａＰｂ
１ ｘＢｉｘ０３の単結晶を成長させることもできた。In addition, by using excess PbO, a platinum wire was placed on top of the liquid.
Alternatively, the BaPb, xBixOa single crystal obtained by the above method is tied and fixed with a platinum wire as a seed, and superconducting BaPb is placed on the seed by pulling it up while rotating.
It was also possible to grow a single crystal of 1 x Bix03.
以上のように、本発明は、これまで成功を収めていなか
ったＢａＰｂ１ ｘＢｉｘ０３の単結晶成長を可能と
する新規な方法を提供するもので、次の利点がある。As described above, the present invention provides a novel method that enables single crystal growth of BaPb1 x Bix03, which has not been successful so far, and has the following advantages.
（１）過剰な量のために溶媒の作用も行なう酸化鉛がＢ
ａＰｂ１ ｘＢｉｘ０３の構成物であるため、溶媒から
成長結晶へ不純物が混入する心配が皆無で、高純度の単
結晶が得られる。(1) Lead oxide, which also acts as a solvent due to its excessive amount, is B
Since it is a composition of aPb1 xBix03, there is no concern that impurities will be mixed into the growing crystal from the solvent, and a highly pure single crystal can be obtained.
（２）ＢａＯとＢｉ２Ｏ３とＰｂＯ□の配合組成比を変
えることにより、望みの組成を有する単結晶を得ること
ができる。(2) By changing the composition ratio of BaO, Bi2O3, and PbO□, a single crystal having a desired composition can be obtained.
また本発明の溶融物によれば、いろいろな組成のＢａＰ
ｂ１ ｘＢｉｘ０３の高品質単結晶製造に対しては勿論
、格子整合の良い結晶基板上への単結晶薄膜の成長に適
用しても極めて有効であると言う種々の利点がある。Moreover, according to the melt of the present invention, BaP of various compositions can be used.
It has various advantages that are extremely effective not only for manufacturing high quality single crystals of b1 xBix03 but also for growing single crystal thin films on crystal substrates with good lattice matching.
Claims (1)
鉛からなることを特徴とする鉛ビスマス酸バリウム単結
晶の成長用溶融物。1. A melt for the growth of barium lead bismuthate single crystals, characterized in that it essentially consists of barium oxide, bismuth oxide and excess lead oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57074510A JPS5938197B2 (en) | 1982-05-06 | 1982-05-06 | Melt for growth of barium lead bismuthate single crystals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57074510A JPS5938197B2 (en) | 1982-05-06 | 1982-05-06 | Melt for growth of barium lead bismuthate single crystals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58194800A JPS58194800A (en) | 1983-11-12 |
| JPS5938197B2 true JPS5938197B2 (en) | 1984-09-14 |
Family
ID=13549388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57074510A Expired JPS5938197B2 (en) | 1982-05-06 | 1982-05-06 | Melt for growth of barium lead bismuthate single crystals |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5938197B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61168530A (en) * | 1985-01-21 | 1986-07-30 | Nippon Telegr & Teleph Corp <Ntt> | Superconductive oxide material and production thereof |
| JPS61215296A (en) * | 1985-03-18 | 1986-09-25 | Shinichi Hirano | Production of bapbi-xbixo3 single crystal |
-
1982
- 1982-05-06 JP JP57074510A patent/JPS5938197B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58194800A (en) | 1983-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3384919B2 (en) | Preparation method of oxide crystal | |
| US5999833A (en) | Method for production of superconducting oxide tape and superconducting oxide tape produced thereby | |
| JPS5938197B2 (en) | Melt for growth of barium lead bismuthate single crystals | |
| JP3330962B2 (en) | Manufacturing method of oxide superconductor | |
| JPH034518B2 (en) | ||
| JP2557882B2 (en) | Method for growing superconducting oxide single crystal | |
| JPH0255298A (en) | Method for growing oxide superconductor single crystal | |
| EP0867951B1 (en) | Method for preparing oxide superconductors | |
| JPH04182394A (en) | Production of single crystal superconductor | |
| JPS623092A (en) | Production of bapbo3 based oxide superconductor single crystal by solution pulling up method | |
| JPS58135199A (en) | Growing method for single crystal from barium lead bismuthate | |
| JPH0465395A (en) | Superconducting fibrous crystal and its production | |
| JPH0714818B2 (en) | Superconducting fibrous crystal and method for producing the same | |
| JPH02243519A (en) | Oxide superconductor and production thereof | |
| JPH01122921A (en) | Method for treating oxide superconductor | |
| JP4153651B2 (en) | Seed crystal of oxide superconducting material and manufacturing method of oxide superconducting material using the same | |
| JP3444930B2 (en) | Manufacturing method of oxide superconductor | |
| JPH02229787A (en) | Production of oxide superconductor | |
| JP3411048B2 (en) | Manufacturing method of oxide superconductor | |
| RU1522792C (en) | Method of growing high-temperature superconducting monocrystals on base of rbq2 cu3 o7-delta | |
| Goeking et al. | Single-phase synthesis of Bi-Ca-Sr-Cu oxides by high-temperature solution growth technique | |
| JPH03112810A (en) | Production of oxide superconducting film | |
| JPS63274695A (en) | Production of cupric acid-lanthanum single crystal | |
| JPS63274696A (en) | Production of cupric acid-lanthanum single crystal | |
| JPH07172835A (en) | Production of oxide superconductor |