JPH02172821A - Formation of superconducting thin film - Google Patents
Formation of superconducting thin filmInfo
- Publication number
- JPH02172821A JPH02172821A JP63323296A JP32329688A JPH02172821A JP H02172821 A JPH02172821 A JP H02172821A JP 63323296 A JP63323296 A JP 63323296A JP 32329688 A JP32329688 A JP 32329688A JP H02172821 A JPH02172821 A JP H02172821A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- thin film
- film
- superconducting thin
- superconducting
- 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.)
- Pending
Links
- 239000010409 thin film Substances 0.000 title abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 239000010408 film Substances 0.000 claims abstract description 21
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 6
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004544 sputter deposition Methods 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 238000007740 vapor deposition Methods 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 229910015901 Bi-Sr-Ca-Cu-O Inorganic materials 0.000 claims abstract 3
- 229910002480 Cu-O Inorganic materials 0.000 claims abstract 3
- 229910052788 barium Inorganic materials 0.000 claims abstract 2
- 239000002131 composite material Substances 0.000 claims description 4
- 238000003852 thin film production method Methods 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract 2
- 239000002887 superconductor Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- -1 Bi4Ti30 are Bi Chemical class 0.000 description 1
- 229910014454 Ca-Cu Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Physical Vapour Deposition (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は高出力のマグネット、ジョセフソン素子、５Ｑ
ＵＩＤ等に用いられている超電導材料に係り、特に液体
窒素温度以上で動作する酸化物系高温超電導体の薄膜の
作製に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention applies to high-output magnets, Josephson elements, 5Q
The present invention relates to superconducting materials used in UIDs and the like, and particularly relates to the production of thin films of oxide-based high-temperature superconductors that operate at temperatures above liquid nitrogen temperature.
１９８８年１月に金属材料研究所の前出らによって発見
されたＢｉ−Ｓｒ Ｃａ−Ｃｕ−０系超電導体は１０
０Ｋ以上の臨界温度を示す。しかしこの系は組成の異な
る多くの相が混在しており単−相が得られていない。エ
レクトロニクス応用を目的として、薄膜化は重要である
が、現在ＭｇＯ基板あるいはＳｒＴｉＯ３基板上ではＣ
軸配向した超電導膜が得られているが、超電導相以外の
他の相も含んでいる。薄膜の作製に関する代表的なもの
としてはジャパニーズ ジャーナル オブ アプライド
フィジックス ２６．（１９８８）第５６２５頁から
第Ｌ６２７頁（Ｊ ｐｎ、 Ｊ 、 Ａｐｐｌ。The Bi-Sr Ca-Cu-0 superconductor discovered by Mae et al. of the Institute for Materials Research in January 1988 has 10
Indicates a critical temperature of 0K or higher. However, this system contains many phases with different compositions, and a single phase cannot be obtained. Film thinning is important for electronics applications, but currently C
Although an axially oriented superconducting film has been obtained, it also contains phases other than the superconducting phase. A typical book on thin film production is Japanese Journal of Applied Physics 26. (1988) pp. 5625-L627 (J pn, J, Appl.
Ｐｈｙｓ、２６ （１９８８）Ｌ６２５〜Ｌ６２７）等
が挙げられる。Phys, 26 (1988) L625-L627).
臨界温度１００Ｋを越えるＢｉ−３ｒ−Ｃａ−Ｃｕ系超
電導体は第２図に示すような層状構造をもっている。Ｂ
ｉ２０２Ｍの間のペロブスカイト構造のＣｕ−０面数が
異なる相やＣａ２Ｃｕｂ、、ＣｕＯなど他の相が存在す
るため、単一相を得ることができない。薄膜化した場合
超電導がＣ軸配向した膜が得られるが、この場合も多く
の他の相を含んでいる。A Bi-3r-Ca-Cu superconductor with a critical temperature exceeding 100K has a layered structure as shown in FIG. B
A single phase cannot be obtained because other phases such as Ca2Cub, CuO, and other phases with different numbers of Cu-0 planes in the perovskite structure between i202M exist. When the film is made thin, a film in which the superconductor is C-axis oriented is obtained, but in this case also it contains many other phases.
本発明の目的は超電導相と非常に類似した構造をもつ基
板を使用することにより、配向性の高い超電導相単結晶
薄膜あるいはエピタキシャル成長した超電導相単結晶薄
膜を作製し、高臨界温度、高臨界電流の高品質膜を得る
ことにある。The purpose of the present invention is to fabricate a highly oriented superconducting phase single crystal thin film or an epitaxially grown superconducting phase single crystal thin film by using a substrate with a structure very similar to that of the superconducting phase, and to produce a superconducting phase single crystal thin film with high critical temperature and high critical current. The aim is to obtain high quality membranes.
Ｂｉ−５ｒ−Ｃａ−Ｃｕ−０系超電導体と類似した結晶
構造をもつ基板材料を使用することで達成される。This is achieved by using a substrate material with a crystal structure similar to the Bi-5r-Ca-Cu-0 superconductor.
すなわち、本発明の特徴は、Ｂｉ−５ｒ−Ｃａ−Ｃｕ−
０系またはＴｉ−Ｂａ−Ｃａ−Ｃｕ−０系超電導薄膜作
製法において、
（Ｂｉｔ ｏｚ）２′″（Ａ、−４Ｒ，０３，、、）２
− ［Ａは、Ｋ。That is, the feature of the present invention is that Bi-5r-Ca-Cu-
0 system or Ti-Ba-Ca-Cu-0 system superconducting thin film production method, (Bit oz)2'''(A, -4R,03,,)2
- [A is K.
Ｎａ、 Ｌｉ、 Ｂｉ、 Ｍｇ、 Ｓｒ、 Ｃａ、 Ｂ
ａ、またはＹ、Ｌａその他の希土類元素から選ばれるペ
ロブスカイト構造のＡサイトオン、Ｒは、Ｔｊ。Na, Li, Bi, Mg, Sr, Ca, B
a, or the A site of the perovskite structure selected from Y, La, and other rare earth elements, and R is Tj.
Ｎｂ、Ｃｕ、Ｎｉ、Ｃｒから選ばれるＢサイトオン］の
構造をもつ層状複合ビスマス酸化物を基板として用い、
スパッタ法または蒸着法により膜を作製する超電導薄膜
作製法にある。Using a layered composite bismuth oxide with a structure of B site selected from Nb, Cu, Ni, and Cr as a substrate,
A method for producing a superconducting thin film in which a film is produced using a sputtering method or a vapor deposition method.
上記層状複合ビスマス酸化物は、Ｂｉ−Ｓｒ−Ｃａ −
Ｃｕ −０系またはＴｉ−Ｂａ−Ｃａ−Ｃｕ−〇系超電
導体と類似した結晶構造をもつため、基板として用いる
と堆積した膜が結晶化する際、基板との相互作用によっ
て基板の面方位に薄膜の面方位が合うように配向した膜
あるいはエピタキシャル成長した膜を作製することがで
きる。The layered composite bismuth oxide is Bi-Sr-Ca-
Since it has a crystal structure similar to that of Cu-0-based or Ti-Ba-Ca-Cu-〇-based superconductors, when used as a substrate, when the deposited film crystallizes, the surface orientation of the substrate changes due to interaction with the substrate. It is possible to produce a film that is oriented so that the plane orientation of the thin film matches, or a film that is epitaxially grown.
Ｂｉ−３ｒ−Ｃａ−Ｃｕ−０系超電導体と類似した結晶
Ｊｃ造をもつ基板を使用するため、堆積した膜が結晶化
する際、基板との相互作用によって基板の面方位に薄膜
の面方位が合うように配向した膜あるいはエピタキシャ
ル成長した膜を作製することができる。この際、選択的
に結晶が成長するため目的とする超電導相以外の相の生
成を抑制し、単一相を得ることができる。Since a substrate with a crystal Jc structure similar to that of Bi-3r-Ca-Cu-0 superconductors is used, when the deposited film crystallizes, the plane orientation of the thin film changes depending on the plane direction of the substrate due to interaction with the substrate. It is possible to produce a film that is oriented so that the two directions match, or a film that is epitaxially grown. At this time, since crystals grow selectively, the formation of phases other than the intended superconducting phase is suppressed, and a single phase can be obtained.
以下、本発明を実施例にもとづいて説明する。 Hereinafter, the present invention will be explained based on examples.
Ｂｉ２５ｒ２Ｃａ２Ｃｕ、Ｏｘ薄膜の作成はターゲット
にＢｉ５ｒＣａＣｕ２０ｘ組成の４インチφの焼結体を
用いてアネルバ製マグネトロンスパッタリング装置によ
って行なった。スパッタガスとしてＡｒ＋５０％０□の
混合ガスを用い、圧力は３０ ｍ Ｔｏｒｒとした。基
板として一般式
％式％
（００１）面を使用した。基板温度は８００℃〜５００
℃の範囲で行なった。膜厚は１．０μｍで、Ｘ線回折に
よると基板温度が６００℃以上の膜では基板の（１１０
）面及び（００１）面に対してエピタキシャル成長し、
Ｃ＝３７人の高Ｔｃ用の単層であることがわかった。Ｔ
ｃは１００〜１０７に、Ｊｃは７７にで１０５Ａ ／
ａｍ２台であった。基板温度が５００℃の膜は充分結晶
化しておらず、空気中で熱処理を行う必要があった。The Bi25r2Ca2Cu, Ox thin film was formed using a magnetron sputtering device manufactured by ANELVA, using a 4 inch diameter sintered body having a Bi5rCaCu20x composition as a target. A mixed gas of Ar+50%0□ was used as the sputtering gas, and the pressure was 30 m Torr. A (001) plane was used as a substrate. Substrate temperature is 800℃~500℃
It was carried out in the range of °C. The film thickness is 1.0 μm, and according to X-ray diffraction, the thickness of the substrate is (110
) plane and (001) plane,
It was found that C = 37 monolayers for high Tc. T
c is 100 to 107, Jc is 77 and 105A /
There were 2 ams. The film at a substrate temperature of 500° C. was not sufficiently crystallized and required heat treatment in air.
８６０℃×２時間の熱処理によりＴｃ＝１０２Ｋ。Tc=102K by heat treatment at 860°C for 2 hours.
Ｊ ｃ ＝ ４ Ｘ Ｉ Ｏ！′Ａ／ｃｍ２の高温超電
導単結晶薄膜が得られた。J c = 4 X I O! A high temperature superconducting single-crystalline thin film with a temperature of 'A/cm2 was obtained.
また、スパッタガスとして純Ａｒガスを使用した場合も
、空気中で成膜後に熱処理を加えることでＢｉ□５ｒ２
Ｃａ、Ｃｕ、Ｏｘの高Ｔｃ用の単結晶薄膜を得ることが
できた。熱処理条件としては空気中では８４０℃〜８８
０℃、０．１気圧酸素中では８３０℃〜８６０℃である
。熱処理時間は１５分から２４時間としたが超伝導特性
に差は生じなかった。Furthermore, even when pure Ar gas is used as the sputtering gas, Bi□5r2
Single crystal thin films of Ca, Cu, and Ox for high Tc could be obtained. Heat treatment conditions are 840°C to 88°C in air.
At 0°C and 0.1 atm oxygen, the temperature is 830°C to 860°C. Although the heat treatment time ranged from 15 minutes to 24 hours, no difference occurred in the superconducting properties.
第１図に一例として（１１０）基板面にエピタキシャル
成長した膜の断面図を示す。第２図はＢｉ、Ｓｒ、Ｃａ
２Ｃｕ、Ｏ工高温超電導体の構造を示している。図では
酸素原子を省略して陽イオンのスタッキングのみを示し
ている。Ｂｉ２Ｏ２層の間にＣｕのペロブスカイト構造
がある。第３図はＢｉ４Ｔｉ、○、２の結晶構造を示し
ている。酸素原子は省略して陽イオンのスタッキングの
みを示している。Ｂ ｉ２Ｓ ｒ２Ｃａ２Ｃｕ、０８と
非常に似た構造をもっている。FIG. 1 shows, as an example, a cross-sectional view of a film epitaxially grown on a (110) substrate surface. Figure 2 shows Bi, Sr, Ca
It shows the structure of a 2Cu, O high temperature superconductor. The figure omits oxygen atoms and only shows stacking of cations. There is a Cu perovskite structure between the Bi2O2 layers. FIG. 3 shows the crystal structure of Bi4Ti, ○, 2. Oxygen atoms are omitted and only the stacking of cations is shown. It has a structure very similar to B i2S r2Ca2Cu, 08.
本発明はＢｉ−８ ｒ−Ｃａ−Ｃｕ−０系超電導体に限
らず、同様の構造をもつ他の超電導体、たとえばＴＱ−
Ｂａ−Ｃａ−Ｃｕ−０系、ＴＱ−Ｓｒ−Ｃａ−Ｃｕ−〇
系、Ｂｉ−Ｐｂ−３ｒ−Ｃａ−Ｃｕ−０系にも適用でき
る。また基板と膜の格子定数がかなり異なる場合は、第
４図に示すように基板をななめに切断することで、高配
向の超電導薄膜を得ることができる。The present invention is not limited to Bi-8 r-Ca-Cu-0 superconductors, but also applies to other superconductors having a similar structure, such as TQ-
It can also be applied to Ba-Ca-Cu-0 system, TQ-Sr-Ca-Cu-○ system, and Bi-Pb-3r-Ca-Cu-0 system. If the lattice constants of the substrate and film are considerably different, a highly oriented superconducting thin film can be obtained by cutting the substrate diagonally as shown in FIG.
Ｂｉ４Ｔｉ３０工２のような層状ビスマス酸化物の他の
例としてはＢｉ、Ｎｂ０ｓＦ、ＢａＢｉ４Ｔｉ４０に、
などがあり、Ｂ Ｌ４ Ｔ １３０ ｘ ２と同様な効
果がある。Other examples of layered bismuth oxides such as Bi4Ti30 are Bi, Nb0sF, BaBi4Ti40,
etc., and has the same effect as B L4 T 130 x 2.
また、ＣＵＤ法によっても同様の高い配向性を持つ単相
膜が得られた。A single-phase film with similar high orientation was also obtained by the CUD method.
本発明によれば、高い臨界温度をもつ
Ｂ ｉ２Ｓ ｒ２Ｃａ２Ｃｕ、０８膜やこれと類似した
構造をもつ超電導体の高配向膜やエピタキシャル成長し
た単結晶薄膜を作製でき、その効果は極めて大きい。According to the present invention, a B i2S r2Ca2Cu,08 film having a high critical temperature, a highly oriented superconductor film having a similar structure, and an epitaxially grown single crystal thin film can be produced, and the effects thereof are extremely large.
第１図は本発明により得られた膜の断面図、第２図はＢ
１２ Ｓ ｒ２Ｃａ、 Ｃｕ、 Ｏｘの陽イオンのス
クッキングを示した略式図、第３図はＢ ｉ、 Ｔ ｉ
、 Ｏ□２の陽イオンのスクッキングを示した略式図、
第４図は本発明の他の方法により得られた膜の断面図で
ある。
１・・・一般式（Ｂｉ２０２）（Ａ、、Ｒｎ Ｏ３ｎ
＋、）をもつ薄状複合ビスマス酸化物の基板、
２−Ｂｉ２Ｓｒ、Ｃａ２Ｃｕ、Ｏｘ超電導薄膜、３・・
・基板のＢｉ２Ｏ□暦、４・・・超電導体のＢｉｇｏｔ
／ｉｌｌ、５− Ｂ ｉ、６− Ｃｕ、７− Ｃａ、８
＝−Ｓｒ。
９・・Ｔｉ、３′・・・基板のペロブスカイト類似構造
の部分、４′・・・超電導体のベロジスカイ１−類似構
造の部分。
≠４′
・
・
・
争−一一タ
・
・Ｎ−一＼
、？３′
・
・
・Figure 1 is a cross-sectional view of the membrane obtained by the present invention, and Figure 2 is B
Schematic diagram showing the scooking of cations of 12S r2Ca, Cu, Ox, Figure 3 shows B i, Ti
, a schematic diagram showing the cation scooking of O□2,
FIG. 4 is a cross-sectional view of a membrane obtained by another method of the present invention. 1... General formula (Bi202) (A,, Rn O3n
+, ) thin composite bismuth oxide substrate, 2-Bi2Sr, Ca2Cu, Ox superconducting thin film, 3...
・Bi2O□ calendar of substrate, 4... Bigot of superconductor
/ill, 5-Bi, 6-Cu, 7-Ca, 8
=-Sr. 9... Ti, 3'... Part of perovskite-like structure of substrate, 4'... Part of Belogisky 1-like structure of superconductor. ≠4' ・ ・ ・ Conflict - 11 ta ・ N - 1\ ,? 3' ・ ・ ・
Claims (1)
Ｃａ−Ｃｕ−Ｏ系超電導薄膜作製法において、（Ｂｉ＿
２Ｏ＿２）＾２＾＋（Ａ＿ｎ＿−＿１Ｒ＿ｎＯ＿３＿ｎ
＿＋＿１）＾２＾−［Ａは、Ｋ、Ｎａ、Ｌｉ、Ｂｉ、Ｍ
ｇ、Ｓｒ、Ｃａ、Ｂａ、またはＹ、Ｌａその他の希土類
元素から選ばれるペロブスカイト構造のＡサイトオン、
Ｒは、Ｔｉ、Ｎｂ、Ｃｕ、Ｎｉ、Ｃｒから選ばれるＢサ
イトオン］の構造をもつ層状複合ビスマス酸化物を基板
として用い、スパッタ法または蒸着法により膜を作製す
る超電導薄膜作製法。1. Bi-Sr-Ca-Cu-O system or Ti-Ba-
In the Ca-Cu-O based superconducting thin film production method, (Bi_
2O_2)^2^+(A_n_-_1R_nO_3_n
＿＋＿１）＾２＾－[A is K, Na, Li, Bi, M
g, Sr, Ca, Ba, or Y, La and other rare earth elements selected from the A site of the perovskite structure,
A superconducting thin film production method in which a layered composite bismuth oxide having a structure of "R is a B site selected from Ti, Nb, Cu, Ni, and Cr" is used as a substrate and a film is produced by sputtering or vapor deposition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63323296A JPH02172821A (en) | 1988-12-23 | 1988-12-23 | Formation of superconducting thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63323296A JPH02172821A (en) | 1988-12-23 | 1988-12-23 | Formation of superconducting thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02172821A true JPH02172821A (en) | 1990-07-04 |
Family
ID=18153202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63323296A Pending JPH02172821A (en) | 1988-12-23 | 1988-12-23 | Formation of superconducting thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02172821A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5434126A (en) * | 1992-09-29 | 1995-07-18 | Matsushita Electric Industrial Co., Ltd. | Thin-film high Tc superconductor comprising a ferroelectric buffer layer |
| CN104087904A (en) * | 2014-07-08 | 2014-10-08 | 天津大学 | Preparation method for BMNT film material with high tunability |
-
1988
- 1988-12-23 JP JP63323296A patent/JPH02172821A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5434126A (en) * | 1992-09-29 | 1995-07-18 | Matsushita Electric Industrial Co., Ltd. | Thin-film high Tc superconductor comprising a ferroelectric buffer layer |
| CN104087904A (en) * | 2014-07-08 | 2014-10-08 | 天津大学 | Preparation method for BMNT film material with high tunability |
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