JPH03183622A - Heat treatment of superconducting thin film - Google Patents
Heat treatment of superconducting thin filmInfo
- Publication number
- JPH03183622A JPH03183622A JP1318856A JP31885689A JPH03183622A JP H03183622 A JPH03183622 A JP H03183622A JP 1318856 A JP1318856 A JP 1318856A JP 31885689 A JP31885689 A JP 31885689A JP H03183622 A JPH03183622 A JP H03183622A
- Authority
- JP
- Japan
- Prior art keywords
- heat treatment
- thin film
- superconductor
- temperature
- heat
- 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.)
- Granted
Links
- 238000010438 heat treatment Methods 0.000 title claims abstract description 44
- 239000010409 thin film Substances 0.000 title claims abstract description 19
- 239000002887 superconductor Substances 0.000 claims abstract description 18
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 6
- 229910052745 lead Inorganic materials 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 229910002480 Cu-O Inorganic materials 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 13
- 239000010408 film Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 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)
- 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１
本究明は超伝導薄膜の熱処理方法に関し、特にＢｉ−Ｐ
ｂ−Ｓｒ−Ｃａ−Ｃｕ−０系超伝導薄膜の熱処理方法に
関するものである。[Detailed Description of the Invention] [Industrial Application Field 1] This study relates to a heat treatment method for superconducting thin films, and in particular,
The present invention relates to a heat treatment method for a b-Sr-Ca-Cu-0 based superconducting thin film.
口１−Ｐｂ−Ｓｒ−にａ−Ｃｕ−０系超伝導体は臨界温
度がｌＯ口Ｋを超えるｌｌｏＫ級超伝導体としての優れ
た材料である。The 1-Pb-Sr-a-Cu-0 based superconductor is an excellent material as a loK class superconductor with a critical temperature exceeding 10K.
［従来の技術１
このロ１−Ｐｂ−Ｓｒ−Ｃａ−Ｃｕ−０系超伝導体の３
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−ＣａＣｕ−０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
する方法が探られていた。[Prior art 1 This B1-Pb-Sr-Ca-Cu-0 system superconductor 3
Create a membrane. In this case, an oxide composed of Bi, Pb, Sr, Ca, and Cu is deposited on a substrate, and then the temperature is rapidly raised to the optimal heat treatment temperature to produce a Bi-Pb-Sr-CaCu-0 superconductor. However, a method of heat treatment in air was being explored.
［発明が解決しようとする課題ｊ
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−０系化合物が最初に生成したのち溶融し、 ｌ
ｌｏＫ級超伝導体の生成に必要な、半溶融状態ができず
、Ｂｉ系超超伝導体多形である８０に級超伝導体が主と
して生成し、目的とするｌｌｏＫ級超伝導体が得られに
くいという問題点があった。[Problem to be Solved by the Invention j] When a thin film is heat-treated by the above method, since the thin film has a higher PB content than the bulk, Bi
-Pb-0 compounds are first formed and then melted, l
The semi-molten state required for the production of a loK class superconductor cannot be created, and the 80 class superconductor, which is a polymorphic Bi-based superconductor, is mainly produced, and the desired loK class superconductor cannot be obtained. The problem was that it was difficult.
〔課題を解決するための手段］
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ｌ去を見出し、本発明を完
成するに到った。[Means for Solving the Problems] As a result of research on the above-mentioned thin film heat treatment method, the present inventors found a method that does not have the above-mentioned problems and 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−
ＰｂＳｒ−Ｃａ−Ｃｕ−０系超伝導体を生成させるＲ通
熱処理温度より１０〜１５０℃低い温度に保持して熱処
理（−・成熱処理）した後、再度Ｂｉ−Ｐｂ−Ｓｒ−Ｃ
ａ−Ｃｕ−０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 that Bi, Pb, Sr,
Bi-
After heat treatment (- heat treatment) at a temperature 10 to 150°C lower than the R heat treatment temperature that produces the PbSr-Ca-Cu-0 system superconductor, the Bi-Pb-Sr-C
This is a heat treatment method for a superconducting thin film, which is characterized in that heat treatment (secondary heat treatment) is carried out while maintaining the temperature at an optimum heat treatment temperature for producing an a-Cu-0 based superconductor.
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２塗面熱分解法の他、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ＭｇＯ１ＳｒＴｉＯ＋等の酸化物又はＡｇ、 Ａ
ｕ、 Ｐｔ等の金属が用いられる。Thin films can be formed on a substrate by a doctor blade method using a slurry or paste of an oxide or its raw material superconductor constituent composition, a screen printing method, a coating surface pyrolysis method, a sputtering method, a vacuum evaporation method, a CVD method, etc. Manufactured. The substrate used is an oxide such as MgO1SrTiO+ that does not react with the elements in the thin film during heat treatment, or Ag, A
Metals such as u, Pt, etc. are 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 within the following range in terms of 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、１１０に綴
紐伝導体が生成され難いことがある。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 Other than the above range If a thin film of the same composition is used, it may be difficult to form a string conductor in 110.
以下、本発明の二段階熱処理方法（−次、二次熱処理）
について説明する。Hereinafter, the two-step heat treatment method of the present invention (-secondary heat treatment)
I will explain about it.
一次熱処理
一次熱処理では、Ｂｉ−Ｐｂ−３ｒ−Ｃａ−Ｃｕ−０系
超伝導体を生成させる最適熱処理温度より１０〜１５０
′ｃ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、７
９０〜８４０℃程度で加熱保持するのが好ましい。Primary heat treatment In the primary heat treatment, 10 to 150
The temperature is maintained at a temperature as low as 10°C to 60°C for at least 1 hour. As a specific temperature, 7
It is preferable to heat and maintain the temperature at about 90 to 840°C.
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。Although air is sufficient as the heat treatment atmosphere, it is preferable to carry out the heat treatment in an atmosphere in which PbO vapor is present.
It is possible to prevent PbO from volatilizing during heat treatment.
二次熱処理
二次熱処理では、Ｂｉ−Ｐｂ−Ｓｒ−にａ−Ｃｕ−０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。−成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、−成熱処理後、室温に冷
却した後に二次熱処理を行なって６よい。Secondary heat treatment In the secondary heat treatment, the optimum heat treatment temperature for producing an a-Cu-0 based superconductor in Bi-Pb-Sr- is maintained at approximately 850° C. for one hour or more. If the heat treatment lasts for a long time, the film quality will deteriorate and the properties will be lowered, so the heat treatment for 1 to 100 hours is preferable. The atmosphere during the heat treatment may be the same as that for the primary heat treatment, and is carried out in air or in the presence of PbO vapor. - There is no particular problem whether the temperature increase rate from the heat-forming treatment to the secondary heat treatment is fast or slow. - After the heat-forming 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 secondary heat treatment is completed, it is left to cool in the furnace.
〔実施例）
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。[Example] Examples 1 to 3 Oxide thin films composed of Bi, Pb, Sr, Ca, and Cu were manufactured by a sputtering method.
用いた基板はＭｇＯ単結晶で、該基板−Ｌに堆積した薄
膜組成は、原子比でＢｉ：Ｐｂ：Ｓｒ：Ｃａ：Ｃｕ＝
０．８：０．８：１．０：１．０：１．８であった。The substrate used was an MgO single crystal, and the thin film deposited on the substrate-L had an atomic ratio of Bi:Pb:Sr:Ca:Cu=
The ratio was 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。This thin film was placed in a furnace heated to 800°C,
Primary heat treatment was performed in air. Heat treatment time is 1 hour, 15
There were three types: time and 100 hours.
−成熱処理後、炉内より試料を取り出し、各試料と６８
５０℃に加熱されている炉内に入れ１５時間で放冷した
。-After the heat treatment, take out the samples from the furnace, and
It was placed in a furnace heated to 50°C and allowed to cool for 15 hours.
一次及び二次の熱処理中、炉内にＢｊｏ、 ｅｅＰｔ）
ｏ、 ２４Ｓｒ＋、 ｏ Ｃａｂ、 ｏｃ１１＋６０ｘ
燃焼体（８５０°Ｃで５０時間、空気中で焼成したもの
）を１．Ｏｇ入れてｐｂｏｇ気の存在雰囲気を保持した
。Bjo, eePt) in the furnace during the primary and secondary heat treatments.
o, 24Sr+, o Cab, oc11+60x
A combustion body (fired at 850°C for 50 hours in air) was heated to 1. Og was added to maintain the atmosphere of pbog.
比較例１
比較のため各実施例に用いたと同じ薄膜を、成熱処理な
しで８５０°Ｃ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 heat-treated at 850° C. for 15 hours without any heat-forming 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、
ｌｌｏＫ級超伝導体と８０に綴紐伝導体の（００２）の
回折線の強度比により、ｌｌｏＫ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,
The proportion of the lloK class superconductor was calculated based on the intensity ratio of the (002) diffraction lines of the lloK class superconductor and the 80-string conductor.
得られた結果を第１表に示す。The results obtained are shown in Table 1.
第
１
表
［発明の効果１
本発明の方法によれば、従来の熱処理方法と比較して、
−成熱処理、二次熱処理をすることにより、ｌｌｏＫ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。Table 1 [Effect of the invention 1 According to the method of the present invention, compared to the conventional heat treatment method,
- By performing heat formation treatment and secondary heat treatment, loK-class superconductors can be easily produced, and thin films with high critical temperatures can be easily produced, which is very useful for industrialization.
Claims (1)
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１０〜１５
０℃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。(1) An oxide thin film composed of Bi, Pb, Sr, Ca and Cu is made of Bi-Pb-Sr-Ca-Cu-O
10 to 15% lower than the optimum heat treatment temperature for producing a superconductor.
After heat treatment at a temperature lower than 0°C, the Bi-Pb
- A method for heat treatment of a superconducting thin film, characterized in that the heat treatment is carried out at an optimum heat treatment temperature for producing a Sr-Ca-Cu-O based superconductor.
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 true JPH03183622A (en) | 1991-08-09 |
| JP2814404B2 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 |
|---|---|
| JP2814404B2 (en) | 1998-10-22 |
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