JP2814404B2 - Heat treatment method for superconducting thin film - Google Patents
Heat treatment method for superconducting thin filmInfo
- Publication number
- JP2814404B2 JP2814404B2 JP1318856A JP31885689A JP2814404B2 JP 2814404 B2 JP2814404 B2 JP 2814404B2 JP 1318856 A JP1318856 A JP 1318856A JP 31885689 A JP31885689 A JP 31885689A JP 2814404 B2 JP2814404 B2 JP 2814404B2
- Authority
- JP
- Japan
- Prior art keywords
- heat treatment
- thin film
- temperature
- superconductor
- treatment method
- 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 - Lifetime
Links
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)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は超伝導薄膜の熱処理方法に関し、特にBi−Pb
−Sr−Ca−Cu−Ｏ系超伝導薄膜の熱処理方法に関するも
のである。Description: TECHNICAL FIELD The present invention relates to a heat treatment method for a superconducting thin film, and particularly to a Bi-Pb
The present invention relates to a heat treatment method for a -Sr-Ca-Cu-O-based superconducting thin film.
Bi−Pb−Sr−Ca−Cu−Ｏ系超伝導体は臨界温度が100K
を超える110K級超伝導体としての優れた材料である。Critical temperature of Bi-Pb-Sr-Ca-Cu-O superconductor is 100K
It is an excellent material as a 110K class superconductor that exceeds 110%.
〔従来の技術〕 このBi−Pb−Sr−Ca−Cu−Ｏ系超伝導体の薄膜をつく
る場合、Bi、Pb、Sr、Ca及びCuから構成されている酸化
物を基板に堆積させたのち、Bi−Pb−Sr−Ca−Cu−Ｏ系
超伝導体を生成させる最適熱処理温度まで急速に昇温
し、空気中で熱処理する方法が採られていた。[Prior Art] When forming a thin film of this Bi-Pb-Sr-Ca-Cu-O-based superconductor, an oxide composed of Bi, Pb, Sr, Ca and Cu is deposited on a substrate. In addition, a method has been adopted in which the temperature is rapidly raised to an optimum heat treatment temperature for producing a Bi-Pb-Sr-Ca-Cu-O-based superconductor, and the heat treatment is performed in the air.
前記の方法で薄膜を熱処理すると、薄膜の場合はバル
クの場合に比べ、Pbの含有量が多いため、薄膜中にBi−
Pb−Ｏ系化合物が最初に生成したのち溶融し、110K級超
伝導体の生成に必要な、半溶融状態ができず、Bi系超伝
導体の多形である80K級超伝導体が主として生成し、目
的とする110K級超伝導体が得られにくいという問題点が
あった。When the thin film is heat-treated by the above-described method, the content of Pb is larger in the case of the thin film than in the case of the bulk, so that the Bi-
The Pb-O-based compound is first formed and then melts, and the semi-molten state required for the formation of the 110K-class superconductor cannot be formed, and the 80K-class superconductor, which is a polymorph of the Bi-based superconductor, mainly forms However, there is a problem that it is difficult to obtain a desired 110K-class superconductor.
本発明者らは、前記の薄膜の熱処理方法について研究
した結果、上記問題点のない方法を見出し、本発明を完
成するに到った。The present inventors have studied the heat treatment method for the thin film, and as a result, have found a method that does not have the above problems, and have completed the present invention.
すなわち、本発明の要旨は、Bi、Pb、Sr、Ca及びCuか
ら構成されている酸化物薄膜を、Bi−Pb−Sr−Ca−Cu−
Ｏ系超伝導体を生成させる最適熱処理温度より10〜150
℃低い温度に保持して熱処理（一次熱処理）した後、再
度Bi−Pb−Sr−Ca−Cu−Ｏ系超伝導体を生成させる最適
熱処理温度に保持して熱処理（二次熱処理）することを
特徴とする超伝導薄膜の熱処理方法である。That is, the gist of the present invention is to form an oxide thin film composed of Bi, Pb, Sr, Ca and Cu into Bi-Pb-Sr-Ca-Cu-.
10 to 150 from the optimal heat treatment temperature for forming O-based superconductor
After the heat treatment (primary heat treatment) with the temperature kept lower by ℃, the heat treatment (secondary heat treatment) with the optimal heat treatment temperature to produce the Bi-Pb-Sr-Ca-Cu-O-based superconductor again This is a characteristic heat treatment method for a superconducting thin film.
薄膜は、酸化物又はその原料の超伝導体構成組成物の
スラリー又はペーストによるドクターブレード法、スク
リーン印刷法、塗布熱分解法の他、スパッタリング法、
真空蒸着法、CVD法等によって基板上で製造される。用
いられる基板としては、熱処理中に薄膜中の元素と反応
しないMgO、SrTiO3等の酸化物又はAg、Au、Pt等の金属
が用いられる。The thin film is a doctor blade method, a screen printing method, a coating thermal decomposition method, and a sputtering method using a slurry or a paste of a superconductor constituent composition of an oxide or a raw material thereof,
It is manufactured on a substrate by a vacuum evaporation method, a CVD method, or the like. As a substrate to be used, an oxide such as MgO or SrTiO 3 or a metal such as Ag, Au, or Pt that does not react with elements in the thin film during heat treatment is used.
製造された薄膜の組成は、原子比で下記の範囲にする
ことが好ましい。The composition of the manufactured thin film is preferably in the following range in atomic ratio.
Bi:0.5〜1.0 Pb:0.5〜1.0 Sr:0.8〜1.2 Ca:0.8〜1.2 Cu:1.4〜2.0 上記の範囲以外の組成の薄膜を使用すると、110K級超
伝導体が生成され難いことがある。Bi: 0.5 to 1.0 Pb: 0.5 to 1.0 Sr: 0.8 to 1.2 Ca: 0.8 to 1.2 Cu: 1.4 to 2.0 When a thin film having a composition other than the above range is used, a 110K class superconductor may not be easily produced.
以下、本発明の二段階熱処理方法（一次、二次熱処
理）について説明する。Hereinafter, the two-step heat treatment method (primary and secondary heat treatment) of the present invention will be described.
一次熱処理 一次熱処理では、Bi−Pb−Sr−Ca−Cu−Ｏ系超伝導体
を生成させる最適熱処理温度より10〜150℃程度低い温
度、好ましくは、10〜60℃程度低い温度に１時間以上保
持する。具体的な温度として、790〜840℃程度で加熱保
持するのが好ましい。熱処理の雰囲気としては空気中で
十分であるが、好ましくはPbOの蒸気が存在する雰囲気
で行うことにより、熱処理中にPbOが揮発するのを防ぐ
ことができる。Primary heat treatment In the primary heat treatment, the temperature is about 10 to 150 ° C lower than the optimal heat treatment temperature for generating the Bi-Pb-Sr-Ca-Cu-O-based superconductor, preferably, about 10 to 60 ° C lower temperature for 1 hour or more. Hold. As a specific temperature, it is preferable to heat and hold at about 790 to 840 ° C. Although the atmosphere for the heat treatment is sufficient in the air, preferably, the heat treatment is performed in an atmosphere in which PbO vapor is present, so that volatilization of PbO during the heat treatment can be prevented.
二次熱処理 二次熱処理では、Bi−Pb−Sr−Ca−Cu−Ｏ系超伝導体
を生成させる最適熱処理温度、通常850℃前後に保持し
１時間以上熱処理する。熱処理が長時間におよぶと膜質
が悪化し特性を下げるので、１〜100時間の熱処理が好
ましい。熱処理中の雰囲気は一次熱処理の場合と同様で
よく、空気中もしくはPbO蒸気の存在下で行う。一次熱
処理から二次熱処理への昇温速度は速くても遅くても特
に問題はなく、一次熱処理後、室温に冷却した後に二次
熱処理を行なってもよい。Secondary heat treatment In the second heat treatment, the heat treatment is performed at an optimum heat treatment temperature for generating a Bi-Pb-Sr-Ca-Cu-O-based superconductor, usually about 850 ° C, and heat treatment is performed for one hour or more. If the heat treatment is performed for a long time, the film quality is deteriorated and the characteristics are deteriorated. Therefore, a heat treatment for 1 to 100 hours is preferable. The atmosphere during the heat treatment may be the same as in the case of the primary heat treatment, and is performed in the air or in the presence of PbO vapor. The rate of temperature rise from the primary heat treatment to the secondary heat treatment may be fast or slow without any particular problem. After the primary heat treatment, the secondary heat treatment may be performed after cooling to room temperature.
二次熱処理終了後は炉内で放冷する。 After the completion of the secondary heat treatment, it is allowed to cool in the furnace.
実施例１〜３ Bi、Pb、Sr、Ca及びCuから構成されている酸化物薄膜
を、スパッタリング法により製造した。用いた基板はMg
O単結晶で、該基板上に堆積した薄膜組成は、原子比でB
i:Pb:Sr:Ca:Cu＝0.8:0.8:1.0:1.0:1.8であった。Examples 1 to 3 Oxide thin films composed of Bi, Pb, Sr, Ca and Cu were produced by a sputtering method. The substrate used was Mg
O single crystal, the composition of the thin film deposited on the substrate is B atomic ratio.
i: Pb: Sr: Ca: Cu = 0.8: 0.8: 1.0: 1.0: 1.8
この薄膜を、800℃に加熱されている炉内に入れて、
空気中で一次熱処理をした。熱処理時間は１時間、15時
間及び100時間の３種類とした。Put this thin film in a furnace heated to 800 ° C,
The primary heat treatment was performed in air. The heat treatment time was of three types: 1 hour, 15 hours, and 100 hours.
一次熱処理後、炉内より試料を取り出し、各試料とも
850℃に加熱されている炉内に入れ15時間二次熱処理を
行なった。二次熱処理終了後、炉内で放冷した。After the primary heat treatment, remove the samples from the furnace and
A secondary heat treatment was performed for 15 hours in a furnace heated to 850 ° C. After the completion of the secondary heat treatment, it was allowed to cool in the furnace.
一次及び二次の熱処理中、炉内にBi0.96Pb0.24Sr1.0C
a1.0Cu1.6OX燃焼体（850℃で50時間、空気中で焼成した
もの）を1.0g入れてPbO蒸気の存在雰囲気を保持した。Bi 0.96 Pb 0.24 Sr 1.0 C in furnace during primary and secondary heat treatment
a 1.0 g of a 1.0 Cu 1.6 O X burner (fired at 850 ° C. for 50 hours in air) was charged to maintain the atmosphere in which PbO vapor was present.
比較例１ 比較のため各実施例に用いたと同じ薄膜を、一次熱処
理なしで850℃で15時間の熱処理を行った。Comparative Example 1 For comparison, the same thin film used in each example was subjected to a heat treatment at 850 ° C. for 15 hours without a primary heat treatment.
実施例及び比較例で得られた試料について、臨界温度
を測定し、また、膜中の結晶相をＸ線回折法により調
べ、110K級超伝導体と80K級超伝導体の（002）の回折線
の強度比により、110K級超伝導体の割合を算出した。For the samples obtained in Examples and Comparative Examples, the critical temperature was measured, and the crystal phase in the film was examined by X-ray diffraction, and the diffraction of (002) of 110K class superconductor and 80K class superconductor was performed. The ratio of the 110K class superconductor was calculated from the intensity ratio of the wire.
得られた結果を第１表に示す。 Table 1 shows the obtained results.
〔発明の効果］ 本発明の方法によれば、従来の熱処理方法と比較し
て、一次熱処理、二次熱処理をすることにより、110K級
超伝導体が生成し易く、臨界温度の高い薄膜が容易に作
製でき、工業化を行う場合非常に有用である。 [Effects of the Invention] According to the method of the present invention, a 110K-class superconductor is easily formed and a thin film having a high critical temperature is easily formed by performing the first heat treatment and the second heat treatment as compared with the conventional heat treatment method. It is very useful for industrialization.
フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C01G 1/00 - 57/00 H01B 12/00 H01L 39/00 - 39/24Continuation of the front page (58) Field surveyed (Int. Cl. 6 , DB name) C01G 1/00-57/00 H01B 12/00 H01L 39/00-39/24
Claims (1)
酸化物薄膜を、Bi−Pb−Sr−Ca−Cu−Ｏ系超伝導体を生
成させる最適熱処理温度より10〜150℃低い温度に保持
して熱処理した後、再度Bi−Pb−Sr−Ca−Cu−Ｏ系超伝
導体を生成させる最適熱処理温度に保持して熱処理する
ことを特徴とする超伝導薄膜の熱処理方法。An oxide thin film composed of Bi, Pb, Sr, Ca and Cu is heated to a temperature of 10 to 150 ° C. from an optimum heat treatment temperature for forming a Bi—Pb—Sr—Ca—Cu—O-based superconductor. A heat treatment method for a superconducting thin film, wherein the heat treatment is performed at a low temperature, and then the heat treatment is performed at an optimum heat treatment temperature at which a Bi-Pb-Sr-Ca-Cu-O-based superconductor is again formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1318856A JP2814404B2 (en) | 1989-12-11 | 1989-12-11 | Heat treatment method for superconducting thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1318856A JP2814404B2 (en) | 1989-12-11 | 1989-12-11 | Heat treatment method for superconducting thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03183622A JPH03183622A (en) | 1991-08-09 |
| JP2814404B2 true JP2814404B2 (en) | 1998-10-22 |
Family
ID=18103716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1318856A Expired - Lifetime JP2814404B2 (en) | 1989-12-11 | 1989-12-11 | Heat treatment method for superconducting thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2814404B2 (en) |
-
1989
- 1989-12-11 JP JP1318856A patent/JP2814404B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03183622A (en) | 1991-08-09 |
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