JPH01100813A - High temperature superconducting material - Google Patents
High temperature superconducting materialInfo
- Publication number
- JPH01100813A JPH01100813A JP62258772A JP25877287A JPH01100813A JP H01100813 A JPH01100813 A JP H01100813A JP 62258772 A JP62258772 A JP 62258772A JP 25877287 A JP25877287 A JP 25877287A JP H01100813 A JPH01100813 A JP H01100813A
- Authority
- JP
- Japan
- Prior art keywords
- superconducting
- superconducting layer
- group
- elements
- periodic table
- 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
- 239000000463 material Substances 0.000 title claims abstract description 52
- 230000000737 periodic effect Effects 0.000 claims abstract description 21
- 238000004544 sputter deposition Methods 0.000 claims abstract description 21
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 9
- 238000000151 deposition Methods 0.000 abstract description 7
- 229910052758 niobium Inorganic materials 0.000 abstract 2
- 239000002887 superconductor Substances 0.000 description 17
- 239000013078 crystal Substances 0.000 description 13
- 238000007740 vapor deposition Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052705 radium Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- -1 and specifically Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 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
- Crystals, And After-Treatments Of Crystals (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］
この発明は、ジョセフソン素子や超電導記憶素子等の超
電導デバイス、あるいは超電導マグネット用コイルなど
として使用可能な高温超電導材に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a high-temperature superconducting material that can be used as a superconducting device such as a Josephson element or a superconducting memory element, or a coil for a superconducting magnet.
［従来の技術］
最近に至り、常電導状態から超電導状態に遷移する臨界
温度（Ｔｃ）が液体窒素温度以上の高い値を示す酸化物
系の超電導体が種々発見されつつある。そして、このよ
うな酸化物系の超電導体は、液体ヘリウムで冷却する必
要のあった従来の合金系あるいは金属間化合物系の超電
導体に比較して格段に育利な冷却条件で使、用できるこ
とから、実用上極めて有望な超電導材料として種々の研
究と開発がなされている。[Prior Art] Recently, various oxide-based superconductors have been discovered that exhibit a critical temperature (Tc) for transitioning from a normal conducting state to a superconducting state that is higher than the temperature of liquid nitrogen. Furthermore, such oxide-based superconductors can be used under much more convenient cooling conditions than conventional alloy-based or intermetallic compound-based superconductors, which require cooling with liquid helium. Since then, various research and development efforts have been carried out as superconducting materials that are extremely promising for practical use.
ところで、このような酸化物系の超電導体における臨界
温度や臨界電流密度（Ｊｃ）は、製造方法、製造条件な
どの種々のファクターにより極めて大きく変動すること
が知られている。そして現在のところでは、スパッタリ
ング法、レーザ蒸着法等の薄膜形成手段により形成され
た超電導体が比較的良好な超電導特性を発揮することが
知られている。Incidentally, it is known that the critical temperature and critical current density (Jc) of such an oxide-based superconductor vary considerably depending on various factors such as the manufacturing method and manufacturing conditions. At present, it is known that superconductors formed by thin film forming means such as sputtering and laser vapor deposition exhibit relatively good superconducting properties.
［発明が解決しようとする問題点］
ところで、前記スパッタリング法を用いた製造方法によ
れば、比較的配向性の良好な結晶構造の超電導層を生成
できるために、臨界電流密度の高い超電導体を製造でき
る利点を有するが、十分な膜厚の超電導層を得るために
は製造時間が長くなる問題がある。また、スパッタリン
グ法によって成膜する場合、欠陥などを生じることなく
マイクロオーダーまで膜厚を大きくすることは極めて困
難なために、十分な電流容量の超電導層を得ることがで
きない問題がある。[Problems to be Solved by the Invention] By the way, according to the manufacturing method using the sputtering method, a superconducting layer having a crystal structure with relatively good orientation can be produced, so it is possible to produce a superconducting layer with a high critical current density. Although it has the advantage of being easy to manufacture, there is a problem in that it takes a long time to manufacture in order to obtain a superconducting layer of sufficient thickness. Furthermore, when a film is formed by a sputtering method, it is extremely difficult to increase the film thickness to the micro order without causing defects, so there is a problem that a superconducting layer with sufficient current capacity cannot be obtained.
［問題点を解決するための手段］
この発明は、Ａ−Ｂ−Ｃ−Ｄ系（ただし、ＡはＹ、Ｓｃ
、Ｌａ、Ｙｂ、Ｅｒ、Ｈｏ、Ｄｙ等の周期律表ＩＩＩａ
族元素のうち１種以上を示し、ＢはＳｒ、Ｂａ、Ｃａ等
の周期律表Ｉｌａ族元素のうち１種以上を示し、ＣはＣ
ｕ、Ａｇ、Ａｕなどの周期律表Ｉｂ族元素とＮｂのうち
ＣｕあるいはＣｕを含む２種以上を示し、Ｄは０、Ｓ、
Ｓｅ等の周期律表ＶＩｂ族元素およびＰ 、ＣＩ。[Means for solving the problem] This invention is based on the A-B-C-D system (where A is Y, Sc
, La, Yb, Er, Ho, Dy, etc. Periodic Table IIIa
B represents one or more of the Group Ila elements of the periodic table such as Sr, Ba, Ca, etc., and C represents C.
Denotes Cu or two or more of Nb, group Ib elements of the periodic table such as u, Ag, and Au, and D is 0, S,
Group VIb elements of the periodic table such as Se and P, CI.
Ｂｒ等の周期律表ＶＩＩｂ族元素のうちＯを含む１種以
上を示す。）の高温超電導材であって、スパッタリング
法により形成されたＡ−Ｂ−Ｃ−Ｄ系の第１の超電導層
と、この第１の超電導層上にレーザ蒸着法法により形成
されたＡ−Ｂ−Ｃ−Ｄ系の第２の超電導層とからなるこ
とを解決手段とした。One or more elements including O among group VIIb elements of the periodic table, such as Br. ), which is a high-temperature superconducting material having an A-B-C-D system first superconducting layer formed by a sputtering method, and an A-B C-D system superconducting layer formed by a laser vapor deposition method on this first superconducting layer. -C-D type second superconducting layer was used as a solution.
［作用］
スパッタリング法により生成された結晶配向性の良好な
第■の超電導層の上に第２の超電導層が形成されるので
、第２の超電導層の結晶の配向性も良好になる。[Operation] Since the second superconducting layer is formed on the second superconducting layer produced by sputtering and having good crystal orientation, the crystal orientation of the second superconducting layer also becomes good.
また、第２の超電導層かレーザ蒸着法で生成されるので
、超電導層の成膜速度が向上し、全体をスパッタリング
法で積層する場合に比較して短時間で膜厚の大きな超電
導材の生成が可能になる。In addition, since the second superconducting layer is produced by laser vapor deposition, the deposition rate of the superconducting layer is improved, and a thicker superconducting material can be produced in a shorter time than when the entire layer is laminated by sputtering. becomes possible.
以下に本発明を更に詳細に説明する。The present invention will be explained in more detail below.
第１図は、この発明の酸化物系の高温超電導材の一例を
示すもので、図中符号ｌは基体である。FIG. 1 shows an example of the oxide-based high-temperature superconducting material of the present invention, and the reference numeral l in the figure represents a substrate.
この基体ｌの表面には、２層構造の酸化物系の高温超電
導材２が形成されている。この高温超電導材２は、スパ
ッタリング法により形成された第１の超電導層２ａと、
レーザ蒸着法により形成された第２の超電導層２ｂとか
ら構成されている。A two-layered oxide-based high-temperature superconducting material 2 is formed on the surface of this base 1. This high temperature superconducting material 2 includes a first superconducting layer 2a formed by a sputtering method,
and a second superconducting layer 2b formed by laser vapor deposition.
次に、このような高温超電導材２の形成方法の一例につ
いて説明する。Next, an example of a method for forming such a high temperature superconducting material 2 will be explained.
高温超電導材２を形成するための基体１は、板材、線材
、テープ材、筒状体、柱状体など、種々の形状のものが
用いられる。そして、このような基体ｌの構成材料とし
ては、酸化物系の高温超電導材の生成時に加える熱処理
時の高温に耐えうる材料が選択され、具体的には、銀、
金、白金、アルミニウム、銅等の金属材料、あるいはこ
れらの合金材料、またはこれら金属または金属の、窒化
物、炭化物、あるいはステンレス鋼などであり、更には
チタン酸ストロンチウム（Ｓ ｒＴ ｉｏ 、）５．ア
ルミナ（ＡｌｚＯｓ）、シリコン（Ｓ ｉ）、シリカ（
Ｓｉｆｔ）、ニオブ酸リチウム（Ｌ ｉＮ ｂＯｙ）、
サファイア、ルビー等の結晶材料などが好適に用いられ
る。The substrate 1 for forming the high-temperature superconducting material 2 may be of various shapes, such as a plate, a wire, a tape, a cylinder, a column, or the like. As the constituent material of such a substrate l, a material is selected that can withstand the high temperature during the heat treatment applied during the production of the oxide-based high-temperature superconducting material, and specifically, silver,
Metal materials such as gold, platinum, aluminum, copper, alloy materials thereof, nitrides, carbides, stainless steel, etc. of these metals or metals, and further strontium titanate (S rT io )5. Alumina (AlzOs), silicon (Si), silica (
Sift), lithium niobate (L iN bOy),
Crystal materials such as sapphire and ruby are preferably used.
次に、このような基板ｌの表面に２層構造の酸化物系の
高温超電導材２を形成する。この例の高温超電導材２の
形成工程は、２つの工程からなっている。Next, a two-layered oxide-based high-temperature superconducting material 2 is formed on the surface of such a substrate 1. The process of forming the high temperature superconducting material 2 in this example consists of two steps.
第１の工程では、スパッタリング法を用いて第１の超電
導層２ａを形成し、第２の工程では、レーザ蒸着法を用
いて第２の超電導層２ｂを形成する。In the first step, a first superconducting layer 2a is formed using a sputtering method, and in the second step, a second superconducting layer 2b is formed using a laser evaporation method.
第１の工程におけるスパッタリング法としては、絶縁物
のスパッタリングに適した高周波スパッタリング法が好
適であるが、これ以外にマグネトロンスパッタリング法
、イオンビームスパッタリング法などの種々のスパッタ
リング法も使用可能である。そして、スパッタリング時
の前記基体ｌの温度は、６００〜１０００℃程度が好ま
しく、スパッタリング雰囲気は、例えば、アルゴンガス
、窒素ガスなどの不活性ガス雰囲気が好ましい。また、
この工程では、予め酸化物超電導体の種類、組成などに
応じてターゲットを用意する必要がある。このターゲッ
トは、酸化物超電導体を構成する元素を含む材料、ある
いは、この材料と前記酸化物超電導体との混合材料など
を仮焼、焼結するなどして得ることができる。As the sputtering method in the first step, a high frequency sputtering method suitable for sputtering an insulator is suitable, but various other sputtering methods such as magnetron sputtering method and ion beam sputtering method can also be used. The temperature of the substrate 1 during sputtering is preferably about 600 to 1000°C, and the sputtering atmosphere is preferably an inert gas atmosphere such as argon gas or nitrogen gas. Also,
In this step, it is necessary to prepare a target in advance depending on the type, composition, etc. of the oxide superconductor. This target can be obtained by calcining or sintering a material containing elements constituting the oxide superconductor, or a mixed material of this material and the oxide superconductor.
このような酸化物超電導体としては、Ａ−Ｂ−Ｃ−Ｄ系
（ただし、Ａは、Ｙ ＳＳ ｃＳＬ ａＳＣｅｓ Ｐｒ
、 Ｎｄ、 Ｐｍ、 Ｓｍ、 Ｅｕ１Ｇｄｑ Ｔｂ５Ｄ
ｙｓ Ｈｏ。Such oxide superconductors include A-B-C-D system (where A is Y SS cSL aSCes Pr
, Nd, Pm, Sm, Eu1Gdq Tb5D
ys Ho.
Ｅｒ、 Ｔｎ＋、 Ｙｂ、 Ｌｕなどの周期律表Ｉ［１
ｅ族元素のうち１種あるいは２種以上を示し、Ｂは５ｒ
１Ｂａ。Periodic table I [1
Indicates one or more types of e group elements, B is 5r
1Ba.
Ｃａ、Ｂｅ％Ｍｇ、Ｒａなどの周期律表Ｉｒａ族元素の
うち１種あるいは２種以上を示し、ＤはＯ，Ｓｅ。It represents one or more elements of the Ira group of the periodic table such as Ca, Be%Mg, and Ra, and D is O and Se.
Ｔｅ、Ｐｏなどの周期率表ｖｔｂ族元素およびＦ、ＣＩ
。Vtb group elements of the periodic table such as Te and Po, as well as F and CI
.
Ｂｒ、Ｉ、Ａｔなどの周期律表ＶＩＩｂ族元索のうちＯ
あるいはＯを含む２種以上を示す）のものが用いられる
。なお、この酸化物超電導体の各構成元素の組成は、例
えば、Ｙ−Ｂａ−Ｃｕ−０系の酸化物超電導体の場合、
Ｙ：Ｂａ：Ｃｕ：Ｏ＝ １ ：（１〜３）：（２〜４）
：（７−Ｘ）とされ、Ｘは０≦Ｘ≦５の範囲とされる。O of group VIIb elements of the periodic table such as Br, I, At
Alternatively, those showing two or more types containing O) are used. In addition, the composition of each constituent element of this oxide superconductor is, for example, in the case of a Y-Ba-Cu-0 based oxide superconductor,
Y:Ba:Cu:O=1:(1-3):(2-4)
:(7-X), where X is in the range of 0≦X≦5.
そして、前述のような第１の工程により形成された第１
の超電導層２ａは、その膜厚が小さいものであるが、結
晶の配向性が良好なことから特に高い臨界電流密度を示
すものとなる。Then, the first
Although the superconducting layer 2a has a small thickness, it exhibits a particularly high critical current density because of its good crystal orientation.
次に、この第１の超電導層２ａの上に、レーザ蒸着法を
用いて第１の超電導層２ａより厚い第２の超電導層２ｂ
を形成する。Next, on this first superconducting layer 2a, a second superconducting layer 2b which is thicker than the first superconducting layer 2a is formed using a laser vapor deposition method.
form.
第２の工程で用いるレーザ蒸着装置として、例えば第２
図に示す装置を用いる。第２図に示す装置は、内部を真
空雰囲気や酸素ガス雰囲気に保持可能な容器１０と、こ
の容器ｌＯの側方に付設されたレーザビーム発射装置９
を具備して構成されている。As a laser evaporation device used in the second step, for example, a second
Use the apparatus shown in the figure. The apparatus shown in FIG. 2 includes a container 10 whose interior can be maintained in a vacuum atmosphere or an oxygen gas atmosphere, and a laser beam emitting device 9 attached to the side of this container IO.
It is configured with the following.
前記容器１０の内部には、基板ホルダ１１と円筒状の回
転基材！２が対向して設けられ、回転基材１２の側方側
の容器１０の外壁には導入孔１３が形成され、この導入
孔Ｉ３には、Ｚｎ５ｅなどからなる透明窓１４が装着さ
れている。また、容器ｌＯの内部の基板ホルダ１１の側
方には、凹面鏡１５がその鏡面部分を前記回転基材１２
と透明窓１４に向けるように設置されていて、レーザビ
ーム発射装置９から容器内に透明窓１４を介して入射さ
れたレーザビームを前記回転基材１２に照射できるよう
になっている。一方、基板ホルダ１１には回転基材１２
に対向して基板ｌが装着されるとともに、基板ホルダ１
１には基板ｌを加熱可能なヒータ１６が付設されている
。なお、回転基材１２は容器ｌＯの内部に設けられた図
示路の回転装置によってその周回りに回転自在に支持さ
れてい、る。Inside the container 10, there is a substrate holder 11 and a cylindrical rotating base material! An introduction hole 13 is formed in the outer wall of the container 10 on the side of the rotary base material 12, and a transparent window 14 made of Zn5e or the like is attached to the introduction hole I3. Further, on the side of the substrate holder 11 inside the container 10, a concave mirror 15 extends its mirror surface to the rotating base material 12.
The rotary base material 12 can be irradiated with a laser beam that is incident from the laser beam emitting device 9 into the container through the transparent window 14 . On the other hand, the rotating base material 12 is attached to the substrate holder 11.
A board l is mounted facing the board holder 1.
1 is attached with a heater 16 that can heat the substrate l. Note that the rotating base material 12 is supported so as to be freely rotatable around it by a rotating device shown in the illustrated path provided inside the container IO.
前記回転基材１２は、酸化物超電導体から構成され、具
体的にはＡ−Ｂ−Ｃ−Ｄ系（ただしＡは、Ｙ 、Ｓｃ、
Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔ
ｂ。The rotating base material 12 is made of an oxide superconductor, specifically an A-B-C-D system (where A is Y, Sc,
La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, T
b.
Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕなどの周期率表１
１Ｉａ族元素のうち１種あるいは２種以上を示し、Ｂは
Ｓｒ。Periodicity table 1 for Dy, Ho, Er, Tm, Yb, Lu, etc.
One or more types of Group 1Ia elements are shown, and B is Sr.
Ｂａ、Ｃａ、Ｂｅ、Ｍｇ、Ｒａなどの周期率表ＩＩａ族
元素のうち１種あるいは２種以上を示し、ＣはＣｕｓ
Ａ ｇｌＡｕなどの周期律表Ｉｂ族元素とＮｂのうちＣ
ｕあるいはＣｕを含む２種以上を示し、Ｄは０．Ｓｅ、
Ｔｅ。It represents one or more elements of Group IIa of the periodic table such as Ba, Ca, Be, Mg, and Ra, and C represents Cu.
A Group Ib elements of the periodic table such as glAu and C of Nb
Indicates two or more types containing u or Cu, and D is 0. Se,
Te.
Ｐｏなどの周期率表ＶＩｂ族元素のうち０あるいは０を
含む２種以上を示す）のものが用いられる。Among the group VIb elements of the periodic table, such as Po, 0 or two or more elements containing 0 are used.
なお、この酸化物超電導体の各構成元素の組成は、例え
ば、Ｙ−Ｂａ−Ｃｕ−０系の酸化物高温超電導体の場合
、Ｙ：Ｂａ：Ｃｕ：０＝ １ ：（１〜３）：（２〜４
）：（７−Ｘ）とされ、Ｘは０≦Ｘ≦５の範囲とされる
。In addition, the composition of each constituent element of this oxide superconductor is, for example, in the case of a Y-Ba-Cu-0-based oxide high temperature superconductor, Y:Ba:Cu:0=1:(1 to 3): (2~4
): (7-X), where X is in the range of 0≦X≦5.
第２図に示す構造のレーザ蒸着装置を使用して第２の超
電導層２ｂを形成するには、基板ホルダ１１に、スパッ
タリング法により形成された第１の超電導層２ａが形成
された基板１を装着し、容器１０の内部を酸素雰囲気と
し、所定の温度にするとともに、回転基材１２を回転さ
せる。次いでレーザビーム発射装置９から発射したレー
ザビームを凹面鏡１５を介して回転基材１２に照射して
回転基材１２の外周部を蒸発させ、蒸発原子を基板ｌに
蒸着させる。このような処理によって第１の超電導層２
ａの上面に第２の超電導層２ｂを形成することができる
。In order to form the second superconducting layer 2b using the laser vapor deposition apparatus having the structure shown in FIG. The rotating base material 12 is rotated while the inside of the container 10 is made to have an oxygen atmosphere and a predetermined temperature. Next, a laser beam emitted from the laser beam emitting device 9 is irradiated onto the rotating base material 12 through the concave mirror 15 to evaporate the outer peripheral portion of the rotating base material 12, and evaporated atoms are deposited on the substrate l. Through such treatment, the first superconducting layer 2
A second superconducting layer 2b can be formed on the upper surface of a.
そして、このようなレーザ蒸着法によれば、レーザの出
力調節と回転基材１２の回転速度の調節と、回転基材１
２の温度調節により０．５〜１．０時間で１μｍ程度の
厚さの超電導層を形成することができるので、十分な厚
さを有する第２の超電導層２ｂを得ることができる。ま
た、下地となる第１の超電導層２ａは配向性の良い結晶
構造であり、第２の超電導層２ｂの結晶は前記第１の超
電導層２ａの結晶を核として成長するために、第２の超
電導層２ｂの結晶構造も第１の超電導層２ａに近い配向
性の良好な結晶構造となる。According to such a laser vapor deposition method, it is possible to adjust the output of the laser, adjust the rotation speed of the rotating base material 12, and adjust the rotation speed of the rotating base material 1.
Since a superconducting layer with a thickness of about 1 μm can be formed in 0.5 to 1.0 hours by adjusting the temperature in step 2, a second superconducting layer 2b having a sufficient thickness can be obtained. Further, the first superconducting layer 2a serving as the base has a crystal structure with good orientation, and the crystals of the second superconducting layer 2b grow using the crystals of the first superconducting layer 2a as nuclei. The crystal structure of the superconducting layer 2b also has a good orientation close to that of the first superconducting layer 2a.
以上のように形成された高温超電導材２は、必要に応じ
て酸素ガスを含む雰囲気中で熱処理することが好ましい
。この熱処理は、４００ Ｓ−１０００℃程度の温度に
おいてｔ−ｔｏｏ時間程度加熱することで行う。このよ
うな熱処理により、高温超電導体２内の各構成元素が更
に十分に反応しあうことから、高温超電導材２の超電導
特性の向上を計ることができる。さらに第１の超電導層
２ａが配向性の良好な結晶構造を有し、この層に第２の
超電導層２ｂが密着しているために、両者を熱処理する
ことによって第２の超電導層２ｂの結晶構造が第１の超
電導層２ａに揃い、超電導特性が更に向上することにな
る。このため高温超電導材２は高い臨界温度と臨界電流
密度とを示す。また、前述のレーザ蒸着法によれば十分
な厚さの第２の超電導層２ｂでも短時間で生成できるた
めに十分な厚さを有する高温超電導材２でも効率良く製
造することができる。The high-temperature superconducting material 2 formed as described above is preferably heat-treated in an atmosphere containing oxygen gas, if necessary. This heat treatment is performed by heating at a temperature of about 400 S-1000° C. for about t-too hours. By such heat treatment, the constituent elements within the high temperature superconductor 2 react more sufficiently with each other, so that the superconducting properties of the high temperature superconductor material 2 can be improved. Furthermore, since the first superconducting layer 2a has a crystal structure with good orientation and the second superconducting layer 2b is in close contact with this layer, by heat-treating both, the crystals of the second superconducting layer 2b are The structure is aligned with the first superconducting layer 2a, and the superconducting properties are further improved. Therefore, the high temperature superconducting material 2 exhibits a high critical temperature and critical current density. Further, according to the laser vapor deposition method described above, even a second superconducting layer 2b having a sufficient thickness can be produced in a short time, so that even a high temperature superconducting material 2 having a sufficient thickness can be efficiently manufactured.
なお、前記熱処理時の雰囲気には、酸素ガス以外に、５
ＳＳｅなどの周期律表ｖｔｂ族元素のガスまたはＦ、Ｃ
１％Ｂｒなどの周期律表ＶＩＩｂ族元素のガスを含める
こともできる。これらの元素ガスは、得られた高温超電
導体の構成元素の一部として結晶内部に侵入し、超電導
特性の向上に寄与するものとなる。また、高温超電導材
２が形成された基体ｌとして、銀あるいは銀合金からな
るものを用いれば、熱処理雰囲気中の酸素が基体１の内
部を透過することから、第１の超電導層２ａに十分な酸
素を供給することができ、このようにしても超電導特性
を向上させることが可能となる。In addition, in addition to oxygen gas, the atmosphere during the heat treatment includes 5
Gases of group Vtb elements of the periodic table such as SSe, or F, C
Gases of Group VIIb elements of the periodic table, such as 1% Br, may also be included. These elemental gases penetrate into the crystal as part of the constituent elements of the obtained high-temperature superconductor and contribute to improving the superconducting properties. Furthermore, if the substrate l on which the high-temperature superconducting material 2 is formed is made of silver or a silver alloy, oxygen in the heat treatment atmosphere will permeate through the inside of the substrate 1, so that it will be sufficient for the first superconducting layer 2a. Oxygen can be supplied, and the superconducting properties can also be improved in this way.
［実施例］
Ｙ ＋Ｂ ａｔ、ｓｃ ｕｓ、ｒｏ ？−Ｘの組成の酸
化物超電導焼結体をスパッタリングターゲットとして厚
さ０゜５ｍｍのＡｇテープに厚さ０．２μｍのスパッタ
リング超電導層を形成し、これに第２図に示す装置と同
等の構成のレーザ蒸着装置を用いてレーザ蒸着を施した
。レーザ蒸着は、上記のスパッタリングが施されたＡｇ
テープをレーザ蒸着装置の基板ホルダに装着し、回転基
材として、円筒状のＹ ｒ Ｂ ａｍ、ｓｃ ｕａ、ｓ
Ｏ？−Ｘの組成の酸化物超電導焼結体製の基材を用い、
容器の内部圧をＩ Ｏ−’Ｔｏｒｒとした。[Example] Y + B at, sc us, ro? A sputtering superconducting layer with a thickness of 0.2 μm was formed on an Ag tape with a thickness of 0°5 mm using an oxide superconducting sintered body having the composition of Laser deposition was performed using a laser deposition device. Laser deposition is performed on the above-mentioned sputtered Ag.
The tape is attached to the substrate holder of the laser vapor deposition apparatus, and a cylindrical Y r B am, sc ua, s is used as a rotating base material.
O? - Using a base material made of an oxide superconducting sintered body with a composition of X,
The internal pressure of the container was IO-'Torr.
次に炭酸ガスレーザビームを発射して回転基材に照射す
るとともに回転基材を１回／秒で回転させた。以上の操
作により回転基材の原子をレーザによって溶融飛散させ
て基板表面に厚さ１．０μｍの第２の超電導層を形成し
た。Next, a carbon dioxide gas laser beam was emitted to irradiate the rotating base material, and the rotating base material was rotated once per second. Through the above operations, the atoms of the rotating base material were melted and scattered by a laser to form a second superconducting layer with a thickness of 1.0 μm on the substrate surface.
以上の工程において、スパッタリング装置にょる成膜に
４時間、レーザ蒸着装置にょる成膜に１時間要した。こ
の後に酸化雰囲気中において９゜０℃に２時間加熱する
熱処理を行って最終製品の高温超電導材を得た。In the above steps, it took 4 hours to form a film using a sputtering device, and 1 hour to form a film using a laser evaporation device. Thereafter, heat treatment was performed at 9.degree. C. for 2 hours in an oxidizing atmosphere to obtain a final high-temperature superconducting material.
この超電導材は、
臨界温度（Ｔｃ） ９２．８に
臨界電流密度（Ｊ ｃ） １ 、ＯＸ １０ ’Ａ／
、ｃｍ”（７７Ｋにおいて）
を示した。This superconducting material has a critical temperature (Tc) of 92.8, a critical current density (Jc) 1, and OX 10'A/
, cm” (at 77K).
なお、厚さ１．２μｍの超電導層をスパッタリング法の
みで製造しようとすると、膜厚を十分に確保することは
困難である。Note that when attempting to manufacture a superconducting layer with a thickness of 1.2 μm using only a sputtering method, it is difficult to ensure a sufficient film thickness.
以上の結果から本発明構造を採用することによって高い
臨界電流密度と臨界温度を有し、厚さも十分な超電導層
を製造できることが判明した。From the above results, it was found that by employing the structure of the present invention, a superconducting layer having high critical current density and critical temperature and sufficient thickness could be manufactured.
［発明の効果］
以上説明したように本発明の高温超電導材は、スパッタ
リング法により形成され、臨界電流密度が高く配向性の
良好な結晶構造を有する第１の超電導層と、成膜時間の
短いレーザ蒸着法のより形成された厚い第２の超電導層
とからなり、第２の超電導層が生成される際に第１の超
電導層を核として成長するために、全体として高い臨界
電流密度を有するとともに、十分な厚さを有する高温超
電導材を短時間で製造できる効果がある。また、本発明
によれば、厚い超電導層でも短時間で効率良く形成でき
る構造であるので、電流容量の大きな超電導材が短時間
で得られる効果がある。[Effects of the Invention] As explained above, the high temperature superconducting material of the present invention is formed by a sputtering method, and has a first superconducting layer having a high critical current density and a crystal structure with good orientation, and a first superconducting layer having a short deposition time. It consists of a thick second superconducting layer formed by laser vapor deposition, and has a high critical current density as a whole because it grows using the first superconducting layer as a nucleus when the second superconducting layer is generated. In addition, there is an effect that a high temperature superconducting material having sufficient thickness can be manufactured in a short time. Further, according to the present invention, since the structure is such that even a thick superconducting layer can be formed efficiently in a short time, there is an effect that a superconducting material with a large current capacity can be obtained in a short time.
第１図は本発明の一実施例を示す断面図、第２図は本発
明の実施に用いるレーザ蒸着装置の一例を示す構成図で
ある。
ｌ・・・基板、
２・・・高温超電導材、
２ａ・・・第１の超電導層、
２ｂ・・・第２の超電導層。FIG. 1 is a sectional view showing an embodiment of the present invention, and FIG. 2 is a configuration diagram showing an example of a laser evaporation apparatus used for carrying out the invention. l... Substrate, 2... High temperature superconducting material, 2a... First superconducting layer, 2b... Second superconducting layer.
Claims (1)
ｙ等の周期律表IIIａ族元素のうち１種以上を示し、Ｂ
はＳｒ、Ｂａ、Ｃａ等の周期律表IIａ族元素のうち１種
以上を示し、ＣはＣｕ、Ａｇ、Ａｕなどの周期律表 I
ｂ族元素とＮｂのうちＣｕあるいはＣｕを含む２種以上
を示し、ＤはＯ、Ｓ、Ｓｅ等の周期律表VIｂ族元素およ
びＦ、Ｃｌ、Ｂｒ等の周期律表VIIｂ族元素のうちＯを
含む１種以上を示す。）の高温超電導材であって、 スパッタリング法により形成されたＡ−Ｂ−Ｃ−Ｄ系の
第１の超電導層と、この第１の超電導層上にレーザ蒸着
法により形成されたＡ−Ｂ−Ｃ−Ｄ系の第２の超電導層
とからなることを特徴とする高温超電導材。[Claims] A-B-C-D system (where A is Y, Sc, La, Yb, Er, Ho, D
Indicates one or more elements of group IIIa of the periodic table such as y, B
represents one or more elements of group IIa of the periodic table such as Sr, Ba, and Ca, and C represents elements of group I of the periodic table such as Cu, Ag, and Au.
Denotes Cu or two or more of group b elements and Nb, including Cu, and D is an element of group VIb of the periodic table such as O, S, and Se, and O of group VIIb of the periodic table elements such as F, Cl, and Br. Indicates one or more types including. ), which comprises a first A-B-C-D superconducting layer formed by a sputtering method, and an A-B-C-D superconducting layer formed on the first superconducting layer by a laser evaporation method. A high-temperature superconducting material comprising a CD-based second superconducting layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62258772A JPH01100813A (en) | 1987-10-14 | 1987-10-14 | High temperature superconducting material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62258772A JPH01100813A (en) | 1987-10-14 | 1987-10-14 | High temperature superconducting material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01100813A true JPH01100813A (en) | 1989-04-19 |
Family
ID=17324869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62258772A Pending JPH01100813A (en) | 1987-10-14 | 1987-10-14 | High temperature superconducting material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01100813A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01198465A (en) * | 1988-02-04 | 1989-08-10 | Fujitsu Ltd | Superconducting coated material |
-
1987
- 1987-10-14 JP JP62258772A patent/JPH01100813A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01198465A (en) * | 1988-02-04 | 1989-08-10 | Fujitsu Ltd | Superconducting coated material |
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