JPH075285B2 - Metal chalcogenide superconductor - Google Patents
Metal chalcogenide superconductorInfo
- Publication number
- JPH075285B2 JPH075285B2 JP1037218A JP3721889A JPH075285B2 JP H075285 B2 JPH075285 B2 JP H075285B2 JP 1037218 A JP1037218 A JP 1037218A JP 3721889 A JP3721889 A JP 3721889A JP H075285 B2 JPH075285 B2 JP H075285B2
- Authority
- JP
- Japan
- Prior art keywords
- superconductor
- metal chalcogenide
- temperature
- element selected
- superconductors
- 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
- 239000002887 superconductor Substances 0.000 title claims description 27
- 229910052751 metal Inorganic materials 0.000 title claims description 16
- 239000002184 metal Substances 0.000 title claims description 16
- 150000004770 chalcogenides Chemical class 0.000 title claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims 1
- 229910052745 lead Inorganic materials 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
- 239000008188 pellet Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910020658 PbSn Inorganic materials 0.000 description 1
- 101150071746 Pbsn gene Proteins 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction 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)
Description
【発明の詳細な説明】 〔技術分野〕 本発明は低温で電気抵抗が消滅する金属カルコゲナイド
超電導体に関するものである。TECHNICAL FIELD The present invention relates to a metal chalcogenide superconductor whose electric resistance disappears at low temperatures.
超電導体はエネルギー節約型の送電及び発電用の線材、
医療用等の強力な磁石、コンピューターおよび高速信号
処理及びデータ通信等において広範な用途が期待され
る。現在実用に供されているのは幾つかの金属系超電導
体である。また最近では120K程度の臨界温度を持つ酸化
物超電導体が見出されている。しかしながら、金属系超
電導体については素材としてはこれ以上新しいものが見
出される可能性は小さく、酸化物系超電導体については
臨界温度はこれ以上高くはならないであろうと予想され
ている。しかも酸化物系超電導体については粒界に絶縁
相析出に伴ってウイーク・リンクが生成し、特にバルク
材において大きい臨界電流が得にくい難点が指摘されて
いる。Superconductors are energy-saving wire rods for power transmission and power generation,
A wide range of applications are expected in powerful magnets for medical applications, computers and high-speed signal processing and data communication. Presently put into practical use are some metallic superconductors. Recently, oxide superconductors with a critical temperature of 120K have been found. However, it is unlikely that new materials will be found for metal-based superconductors, and it is expected that the critical temperature will not rise any higher for oxide-based superconductors. Moreover, it has been pointed out that weak links are generated in the grain boundaries along with the precipitation of the insulating phase in the oxide superconductors, and it is difficult to obtain a large critical current particularly in bulk materials.
実用化を考えた場合、臨界温度は更に高く、しかもウイ
ーク・リンクの生成がないことが望ましい。この点を克
服するためには、まず臨界温度は低くても良いから新し
いタイプの超電導体を開発する必要があると思われる。
特に２種以上の金属を含む多元系金属カルコゲナイド
は、いわゆる高温酸化物超電導体の発見以前は臨界温度
の高さおよび化合物の多様性においてカルコゲナイド超
電導体のほうがオキサイド超電導体よりも優れていた、
隣接組成の電導度が高く粒界にウイーク・リンクが生成
しにくい、多元系であることによって置換固溶等の展開
が容易で低臨界温度超電導体から高臨界温度超電導体へ
の発展が期待される、という背景から安定な性能を持つ
高温超電導体の有力な候補物質系として期待される。In terms of practical application, it is desirable that the critical temperature be higher and that weak links are not formed. In order to overcome this point, it is necessary to develop a new type of superconductor because the critical temperature may be low.
In particular, regarding the multi-component metal chalcogenides containing two or more metals, before the discovery of so-called high-temperature oxide superconductors, chalcogenide superconductors were superior to oxide superconductors in terms of high critical temperature and variety of compounds.
Since the conductivity of adjacent composition is high and weak links are not easily generated at grain boundaries, it is easy to develop substitution solid solution due to the multi-component system, and it is expected to develop from low critical temperature superconductors to high critical temperature superconductors. It is expected as a potential candidate material system for high temperature superconductors with stable performance.
そこで本発明は金属を２種以上含む新規な金属カルコゲ
ナイド超電導体を提供することをその課題とする。Therefore, an object of the present invention is to provide a novel metal chalcogenide superconductor containing two or more kinds of metals.
本発明者は、前記課題を解決すべく種々研究を重ねた結
果、本発明を完成するに至った。The present inventors have completed the present invention as a result of various studies to solve the above problems.
即ち、本発明によれば、下記一般式（Ｉ）、（II）で表
わされる組成を有する新規な金属カルコゲナイド超電導
体が提供される。これらのものは基本的に同一の結晶構
造を有するものである。That is, according to the present invention, a novel metal chalcogenide superconductor having a composition represented by the following general formulas (I) and (II) is provided. These have basically the same crystal structure.
一般式（Ｉ） AxByCz （式中、ＡはBi、Sb及びAsの中から選ばれる少なくとも
１種の元素、ＢはNb及びTaの中から選ばれる少なくとも
１種の元素及びＣはＳ、Se及びTeの中から選ばれる少な
くとも１種の元素を示し、ｘは0.8≦ｘ≦1.2の数、ｙは
0.8≦ｙ≦1.2の数及びｚは2.4≦ｚ≦3.6の数を示す） 一般式（II） Ａ（１−ａ）xA′axByCz （式中、ＡはBi、Sb及びAsの中から選ばれる少なくとも
１種の元素、Ａ′はPbSn及びGeの中から選ばれる少なく
とも１種の元素、ＢはNb及びTaの中から選ばれる少なく
とも１種の元素、ＣはＳ、Se及びTeの中から選ばれる少
なくとも１種の元素を示し、ａは０≦ａ≦１の数、ｘは
0.8≦ｘ≦1.2の、ｙは0.8≦ｙ≦1.2の数、ｚは2.4≦ｚ
≦3.6の数を示す） 本発明の金属カルコゲナイド超電導体は、前記組成に対
応する成分の元素粉末あるいは金属カルコゲナイド粉末
を、その組成割合に秤取して、石英等の耐熱耐酸化性容
器中に真空封入し、400〜1200℃で加熱処理した後室温
まで冷却することによって製造することができる。General formula (I) AxByCz (In the formula, A is at least one element selected from Bi, Sb and As, B is at least one element selected from Nb and Ta, and C is S, Se and At least one element selected from Te is shown, x is a number of 0.8 ≦ x ≦ 1.2, and y is
0.8 ≦ y ≦ 1.2 and z represent 2.4 ≦ z ≦ 3.6) General formula (II) A (1-a) xA′axByCz (where A is selected from Bi, Sb and As) At least one element, A'is at least one element selected from PbSn and Ge, B is at least one element selected from Nb and Ta, C is selected from S, Se and Te At least one element is represented, a is a number 0 ≦ a ≦ 1, and x is
0.8 ≦ x ≦ 1.2, y is 0.8 ≦ y ≦ 1.2, z is 2.4 ≦ z
The metal chalcogenide superconductor of the present invention is an elemental powder or a metal chalcogenide powder of a component corresponding to the above composition, which is weighed in the composition ratio, and placed in a heat and oxidation resistant container such as quartz. It can be manufactured by sealing in a vacuum, heat-treating at 400 to 1200 ° C., and then cooling to room temperature.
このようにして得られたものは、褐色から黒色の粉末
で、粉末Ｘ線回折パターンが殆ど１つの面からの回折線
のみを示す。また条件によっては薄片状結晶が得られ、
それが容易に劈開することとあわせ、何らかの層状構造
を持つと推定される。本発明の金属カルコゲナイドの場
合、成分Ａ、Ｂ、Ｃをそれぞれ一定の範囲で複合化（固
溶化）させることが可能である。The product thus obtained is a brown to black powder, and the powder X-ray diffraction pattern shows only the diffraction line from almost one plane. Depending on the conditions, flaky crystals can be obtained,
It is presumed that it has some kind of layered structure along with the fact that it is easily cleaved. In the case of the metal chalcogenide of the present invention, the components A, B and C can be compounded (solubilized) within a certain range.
本発明の金属カルコゲナイド超電導体は、それ自身超電
導体として用いることができるが、多元系であるため置
換固溶等の展開が可能であり、高い臨界温度を持つ超電
導体合成のための出発物質として用いられると期待され
る。The metal chalcogenide superconductor of the present invention can be used as a superconductor itself, but since it is a multi-element system, it is possible to develop substitution solid solution and the like, and as a starting material for superconductor synthesis having a high critical temperature. Expected to be used.
次に本発明を実施例によりさらに詳細に説明する。 Next, the present invention will be described in more detail with reference to Examples.
実施例１ 前記一般式（Ｉ）の組成に対応する金属カルコゲナイド
超電導体BiNbSe3を次のようにして合成した。Example 1 A metal chalcogenide superconductor BiNbSe 3 corresponding to the composition of the general formula (I) was synthesized as follows.
Bi、Nb、Seをモル比で1:1:3に秤取し石英管中に真空封
入した後400〜1200℃の温度に加熱し、次いで室温まで
冷却した。石英管を開けて生成物を粉砕混合し、約1ton
/cm2の圧力でプレスしてペレットとした。このペレット
を石英管中に真空封入し300°〜800℃の温度で24時間ア
ニールした。ペレットは、粉末Ｘ線回折において粉末と
同様１つの軸に垂直な面からの回折線のみを示した。Bi, Nb, and Se were weighed at a molar ratio of 1: 1: 3, vacuum-sealed in a quartz tube, heated to a temperature of 400 to 1200 ° C., and then cooled to room temperature. Open the quartz tube, crush and mix the product, about 1 ton
The pellets were pressed with a pressure of / cm 2 . The pellet was vacuum sealed in a quartz tube and annealed at a temperature of 300 ° to 800 ° C. for 24 hours. The pellet showed only the diffraction line from the plane perpendicular to one axis in the same manner as the powder in the powder X-ray diffraction.
四端子法を用いた電気抵抗測定により試料の超電導転移
温度を調べた結果、本試料は2.5Kにおいて超電導転移を
起こして電気抵抗が下がり始め1.3K以下では完全に電気
抵抗が消滅した状態が実現していることが判明し、本試
料は超電導体であることが確認された。この様子を第１
図に示す。As a result of investigating the superconducting transition temperature of the sample by the electrical resistance measurement using the four-terminal method, this sample caused the superconducting transition at 2.5K and the electrical resistance began to drop, and the state in which the electrical resistance disappeared completely at 1.3K or less was realized. It was confirmed that the sample was a superconductor. This is the first
Shown in the figure.
なお、本発明の金属カルコゲナイドにおいては、その成
分ＡとＢとＣの組成は、通常1:1:3と表示されるが、Ｃ
成分にはノンストイキオトリーがあるので正確な３の値
ではなく、2.4〜3.6の範囲にある。また、成分Ａ及びＢ
も同様に、その値は正確な１ではなく、0.8〜1.2の範囲
にあるものと考えられる。In addition, in the metal chalcogenide of the present invention, the composition of the components A, B and C is usually expressed as 1: 1: 3.
The component has non-stoichiometry, so it is in the range of 2.4 to 3.6, not the exact value of 3. In addition, components A and B
Similarly, the value is not exactly 1, but is considered to be in the range of 0.8 to 1.2.
実施例２ 実施例１と同様の方法で一般式（Ｉ）の組成を持つBiTa
Se3ペレットを調製した。ペレットは粉末Ｘ線回折にお
いて粉末と同様１つの軸に垂直な面からの回折線のみを
示した。電気抵抗率の温度依存性を第２図に示す。該図
より超電導転移開始温度が2.5Kであり、1.3Kで電気抵抗
が零となり、本試料は超電導体であることが確認され
た。Example 2 In the same manner as in Example 1, BiTa having the composition of general formula (I)
Se 3 pellets were prepared. The pellet showed only the diffraction line from the plane perpendicular to one axis in the same manner as the powder in the powder X-ray diffraction. The temperature dependence of the electrical resistivity is shown in FIG. From the figure, it was confirmed that the superconducting transition start temperature was 2.5 K and the electric resistance became zero at 1.3 K, indicating that this sample was a superconductor.
実施例３ 実施例１と同様の方法で一般式（II）の組成を持つBi
0.5Pb0.5NbS3ペレットを調製した。ペレットは粉末Ｘ線
回折において粉末と同様１つの軸に垂直な面からの回折
線のみを示した。電気抵抗率の温度依存性を第３図に示
す。該図より超電導転移開始温度が2.2Kであり、1.2Kで
電気抵抗が零となり、本試料が超電導体であることが確
認された。Example 3 Bi having the composition of the general formula (II) was prepared in the same manner as in Example 1.
0.5 Pb 0.5 NbS 3 pellets were prepared. The pellet showed only the diffraction line from the plane perpendicular to one axis in the same manner as the powder in the powder X-ray diffraction. The temperature dependence of the electrical resistivity is shown in FIG. From the figure, it was confirmed that the superconducting transition start temperature was 2.2K and the electric resistance became zero at 1.2K, and that this sample was a superconductor.
第１図、第２図及び第３図は、直流四端子法によって測
定した電気抵抗率の温度変化を表わす特性曲線。 たて軸：電気抵抗率／μΩ・cm、横軸：絶対温度/K。FIG. 1, FIG. 2 and FIG. 3 are characteristic curves showing the temperature change of the electrical resistivity measured by the DC four-terminal method. Vertical axis: electrical resistivity / μΩ · cm, horizontal axis: absolute temperature / K.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０１Ｇ 30/00 ＺＡＡ 33/00 ＺＡＡ Ｂ 35/00 ＺＡＡ Ｚ Ｈ０１Ｂ 12/00 ＺＡＡ 7244−5Ｇ Ｈ０１Ｌ 39/12 ＺＡＡ Ａ 9276−4Ｍ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C01G 30/00 ZAA 33/00 ZAA B 35/00 ZAA Z H01B 12/00 ZAA 7244-5G H01L 39 / 12 ZAA A 9276-4M
Claims (2)
１種の元素、ＢはNb及びTaの中から選ばれる少なくとも
１種の元素及びＣはＳ、Se及びTeの中から選ばれる少な
くとも１種の元素を示し、ｘは0.8≦ｘ≦1.2の数、ｙは
0.8≦ｙ≦1.2の数及びｚは2.4≦ｚ≦3.6の数を示す） で表わされる組成を有することを特徴とする金属カルコ
ゲナイド超電導体。1. General formula (I) AxByCz (wherein A is at least one element selected from Bi, Sb and As, B is at least one element selected from Nb and Ta, and C). Represents at least one element selected from S, Se and Te, x is a number of 0.8 ≦ x ≦ 1.2, and y is
A metal chalcogenide superconductor having a composition represented by the following formula: 0.8 ≦ y ≦ 1.2 and z represents a number of 2.4 ≦ z ≦ 3.6.
１種の元素、Ａ′はPb、Sn及びGeの中から選ばれる少な
くとも１種の元素、ＢはNb及びTaの中から選ばれる少な
くとも１種の元素、ＣはＳ、Se及びTeの中から選ばれる
少なくとも１種の元素を示し、ａは０≦ａ≦１の数、ｘ
は0.8≦ｘ≦1.2の、ｙは0.8≦ｙ≦1.2の数、ｚは2.4≦
ｚ≦3.6の数を示す） で表わされる組成を有することを特徴とする金属カルコ
ゲナイド超電導体。2. A compound represented by the general formula (II): A (1-a) xA'axByCz (wherein A is at least one element selected from Bi, Sb and As, A'is Pb, Sn and Ge). At least one element selected from among B, at least one element selected from Nb and Ta, C represents at least one element selected from S, Se and Te, and a is 0 ≦ Number of a ≦ 1, x
Is 0.8 ≦ x ≦ 1.2, y is 0.8 ≦ y ≦ 1.2, and z is 2.4 ≦
A metal chalcogenide superconductor having a composition represented by the formula: z ≦ 3.6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1037218A JPH075285B2 (en) | 1989-02-16 | 1989-02-16 | Metal chalcogenide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1037218A JPH075285B2 (en) | 1989-02-16 | 1989-02-16 | Metal chalcogenide superconductor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02217315A JPH02217315A (en) | 1990-08-30 |
| JPH075285B2 true JPH075285B2 (en) | 1995-01-25 |
Family
ID=12491451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1037218A Expired - Lifetime JPH075285B2 (en) | 1989-02-16 | 1989-02-16 | Metal chalcogenide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH075285B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102188719B1 (en) * | 2014-05-27 | 2020-12-08 | 삼성전자주식회사 | Conductive material and electrical device including the same |
-
1989
- 1989-02-16 JP JP1037218A patent/JPH075285B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| Ｊ．ＳｏｌｉｄＳｔａｔｅＣｈｅｍ．１２（１−２）Ｐ．８０〜８３（１９７５） |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02217315A (en) | 1990-08-30 |
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