JP7084022B2 - Superconductor - Google Patents
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- JP7084022B2 JP7084022B2 JP2018031880A JP2018031880A JP7084022B2 JP 7084022 B2 JP7084022 B2 JP 7084022B2 JP 2018031880 A JP2018031880 A JP 2018031880A JP 2018031880 A JP2018031880 A JP 2018031880A JP 7084022 B2 JP7084022 B2 JP 7084022B2
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- 239000002887 superconductor Substances 0.000 title claims description 77
- 125000006850 spacer group Chemical group 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- 230000001747 exhibiting effect Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910005666 SnxMy Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000000470 constituent Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000001308 synthesis method Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052787 antimony Inorganic materials 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 238000012982 x-ray structure analysis Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910012381 LiSn Inorganic materials 0.000 description 3
- 101100421767 Mus musculus Snai1 gene Proteins 0.000 description 3
- 101100421768 Xenopus laevis snai1 gene Proteins 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008520 organization Effects 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PZKRHHZKOQZHIO-UHFFFAOYSA-N [B].[B].[Mg] Chemical compound [B].[B].[Mg] PZKRHHZKOQZHIO-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- -1 MgB 2 Substances 0.000 description 1
- 229910020012 Nb—Ti Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910006913 SnSb Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Classifications
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- 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
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- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
特許法第３０条第２項適用 平成２９年１１月１７日～１８日に開催された第１１回物性科学領域横断研究会（開催場所：東京大学物性研究所６Ｆ大会議室、演題番号：Ｐ０２６＊、タイトル「ＳｎＡｓ 伝導層をもつ新規層状超伝導体ＮａＳｎ２Ａｓ２」）にてポスター発表、平成２９年１２月２２日に科学新聞（発行日：２０１７年１２月２２日、科学新聞、第３６６０号、第４頁、タイトル「ＳｎＡｓ伝導層を含む新規層状超伝導体発見」、発行所：科学新聞社）にて公表、平成２９年９月２６日にＣｏｒｎｅｌｌ Ｕｎｉｖｅｒｓｉｔｙ Ｌｉｂｒａｒｙのウェブサイト （ｈｔｔｐｓ：／／ａｒｘｉｖ．ｏｒｇ／ａｂｓ／１７０９．０８８９９）にて公表、平成２９年１１月１日に一般社団法人日本物理学会のＪｏｕｒｎａｌ ｏｆ ｔｈｅ Ｐｈｙｓｉｃａｌ Ｓｏｃｉｅｔｙ ｏｆ Ｊａｐａｎ（オンライン版）のウェブサイト （ｈｔｔｐｓ：／／ｄｏｉ．ｏｒｇ／１０．７５６６／ＪＰＳＪ．８６．１２３７０１ ｈｔｔｐ：／／ｊｏｕｒｎａｌｓ．ｊｐｓ．ｊｐ／ｄｏｉ／１０．７５６６／ＪＰＳＪ．８６．１２３７０１ ｈｔｔｐ：／／ｗｗｗ．ｊｐｓ．ｏｒ．ｊｐ／ｂｏｏｋｓ／ｊｐｓｊｓｅｌｅｃｔｆｒａｍｅ／２０１７／ｆｉｌｅｓ／１７－１２－１．ｐｄｆ ｈｔｔｐ：／／ｗｗｗ．ｊｐｓ．ｏｒ．ｊｐ／ｂｏｏｋｓ／ｊｐｓｊｓｅｌｅｃｔｆｒａｍｅ／２０１７／２０１７＿１２．ｐｈｐ）にて公表、平成２９年１１月１日に公立大学法人首都大学東京のウェブサイト （ｈｔｔｐｓ：／／ｗｗｗ．ｔｍｕ．ａｃ．ｊｐ／ｎｅｗｓ／ｔｏｐｉｃｓ／１５６２８．ｈｔｍｌ ｈｔｔｐｓ：／／ｗｗｗ．ｔｍｕ．ａｃ．ｊｐ／ｅｘｔｒａ／ｄｏｗｎｌｏａｄ．ｈｔｍｌ？ｄ＝ａｓｓｅｔｓ／ｆｉｌｅｓ／ｄｏｗｎｌｏａｄ／ｎｅｗｓ／２０１７１１０１＿ｐｒｅｓｓ．ｐｄｆ ｈｔｔｐｓ：／／ｗｗｗ．ｈｏｕｊｉｎ－ｔｍｕ．ａｃ．ｊｐ／ｎｅｗｓ／ｐｒｅｓｓ／６３１７．ｈｔｍｌ？ｄ＝ａｓｓｅｔｓ／ｆｉｌｅｓ／ｄｏｗｎｌｏａｄ／ｐｒｅｓｓ／ｐｒｅｓｓ＿２０１７１１０１．ｐｄｆ）にて公表、Application of
特許法第３０条第２項適用 平成２９年１１月１日に日本の研究．ｃｏｍのウェブサイト （ｈｔｔｐｓ：／／ｒｅｓｅａｒｃｈ－ｅｒ．ｊｐ／ａｒｔｉｃｌｅｓ／ｖｉｅｗ／６４５１４）にて公表、平成２９年１１月５日に日本経済新聞（オンライン版）ウェブサイト （ｈｔｔｐｓ：／／ｒ．ｎｉｋｋｅｉ．ｃｏｍ／ａｒｔｉｃｌｅ／ＤＧＸＭＺＯ２３１２４２１０Ｖ０１Ｃ１７Ａ１ＴＪＭ０００）にて公表、平成２９年１１月６日に首都大学東京 総合研究推進機構のＦａｃｅｂｏｏｋページ （ｈｔｔｐｓ：／／ｗｗｗ．ｆａｃｅｂｏｏｋ．ｃｏｍ／ｔｍｕ．ｕｒａ／ｐｈｏｔｏｓ／ａ．８４２７３２２９９２２９２３６．１０７３７４１８２９．８３８３５３０２３０００４９７／８９３４９６０７４１５２８５８／？ｔｙｐｅ＝３＆ｔｈｅａｔｅｒ）にて公表、平成２９年１１月７日に首都大学東京 総合研究推進機構のウェブサイト（ｈｔｔｐｓ：／／ｔｍｕ－ｒａｏ．ｊｐ／ｉｎｆｏ／３００５／）にて公表、平成２９年１１月８日ＥｕｒｅｋＡｌａｒｔ！のウェブサイト （ｈｔｔｐｓ：／／ｗｗｗ．ｅｕｒｅｋａｌｅｒｔ．ｏｒｇ／ｐｕｂ＿ｒｅｌｅａｓｅｓ／２０１７－１１／ｔｍｕ－ｊｒｄ１１０８１７．ｐｈｐ）にて公表、平成２９年１１月１０日に首都大学東京 総合研究推進機構のＦａｃｅｂｏｏｋページ （ｈｔｔｐｓ：／／ｗｗｗ．ｆａｃｅｂｏｏｋ．ｃｏｍ／ｔｍｕ．ｕｒａ／ｐｏｓｔｓ／８９５１３０６４７３２２７３４）にて公表、平成２９年１１月２９日にａｃａｄｅｍｉｓｔ Ｊｏｕｒｎａｌのウェブサイト （ｈｔｔｐｓ：／／ａｃａｄｅｍｉｓｔ－ｃｆ．ｃｏｍ／ｊｏｕｒｎａｌ／？ｐ＝６５６６）にて公表、平成２９年１２月１２日に一般社団法人日本物理学会ＪＰＳＪ Ｎｅｗｓ ａｎｄ Ｃｏｍｍｅｎｔｓのウェブサイト （ｈｔｔｐ：／／ｊｏｕｒｎａｌｓ．ｊｐｓ．ｊｐ／ｊｏｕｒｎａｌ／ｊｐｓｊｎｃ ｈｔｔｐ：／／ｊｏｕｒｎａｌｓ．ｊｐｓ．ｊｐ／ｄｏｉ／ｆｕｌｌ／１０．７５６６／ＪＰＳＪＮＣ．１４．１３）にて公表、平成２９年１２月３１日にＳｕｐｅｒｃｏｎｄｕｃｔｏｒ Ｗｅｅｋ ｉｓｓｕｅのウェブサイト （ｈｔｔｐ：／／ｗｗｗ．ｓｕｐｅｒｃｏｎｄｕｃｔｏｒｗｅｅｋ．ｃｏｍ／ｓｔｏｒｅ）にて公表Application of
本発明は、十分な超電導を示し、低コストで加工の簡便性も有する超電導体に関する。 The present invention relates to a superconductor that exhibits sufficient superconductivity, is low in cost, and is easy to process.
現在主に実用化されている超電導体はＮｂ－Ｔｉ合金、Ｎｂ２Ｓｎであるが、更なる超電導技術の実用化のために高温で高電導を示す超電導物質が求められている。
このような要望を満足する次世代の超電導材料として、超電導転移温度が高くい、鋼酸化物高温超電導体とＭｇＢ２、鉄系超電導体等が提案されている。さらに超電導技術の発展のために、より高温・強磁場下で超電導を示し、低コスト、加工の簡便性などを備えた新しい超電導物質系の開発が求められている。
かかる要望を満足するために種々提案がなされており、例えば以下の特許文献１、２等の提案がなされている。
特許文献１：マグネシウムの酸化を引き起こしにくい緩衝膜を用いてより超電導性のよいホウ化マグネシウムの薄膜が形成できるようにするために、サファイア（酸化アルミニウム）からなり主表面がＣ面とされた基板１０１の上に例えば窒化ガリウム（ＧａＮ）などのガリウムと窒素とから構成された緩衝層１０２が形成され、緩衝層１０２の上に接してホウ化マグネシウムからなる超電導体層１０３が形成され、緩衝層１０２は、膜厚２５０ｎｍ程度に形成され、超電導体層１０３は、膜厚１００～１２０ｎｍ程度に形成されている超電導体。
特許文献２：Ｂａ－Ｉｒ－Ｇｅに代表される３元系化合物の超電導体として、化学式ＡＴＭ２Ｂ７（ＡはＣａ、ＳｒまたはＢａであり、ＴＭは遷移金属であり、ＢはＳｉ、ＧｅまたはＳｎである）で示され、上記ＴＭおよびＢからなるＴＭＢ層が積層し、斜方晶系Ａｍｍｍ結晶構造を有する超電導体。
Currently, the superconductors that are mainly put into practical use are Nb—Ti alloys and Nb2Sn, but in order to further put into practical use of superconducting technology, superconducting materials that exhibit high conductivity at high temperatures are required.
As next-generation superconducting materials that satisfy such demands, steel oxide high-temperature superconductors, MgB 2 , iron-based superconductors, etc., which have a high superconducting transition temperature, have been proposed. Furthermore, for the development of superconducting technology, it is required to develop a new superconducting material system that exhibits superconductivity under higher temperature and strong magnetic field, has low cost, and is easy to process.
Various proposals have been made in order to satisfy such a request, and for example, the following
Patent Document 1: A substrate made of sapphire (aluminum oxide) whose main surface is the C surface in order to be able to form a thin film of magnesium boride with better superconductivity by using a buffer film that does not easily cause oxidation of magnesium. A buffer layer 102 composed of gallium such as gallium nitride (GaN) and nitrogen is formed on the 101, and a superconductor layer 103 made of magnesium diboride is formed in contact with the buffer layer 102 to form a buffer layer. 102 is a superconductor having a thickness of about 250 nm, and the superconductor layer 103 is a superconductor having a thickness of about 100 to 120 nm.
Patent Document 2: As a superconductor of a ternary compound represented by Ba-Ir-Ge, the chemical formula ATM 2 B 7 (A is Ca, Sr or Ba, TM is a transition metal, and B is Si, Ge. A superconductor having an orthorhombic Ammm crystal structure in which the TMB layers composed of the above TM and B are laminated, which is indicated by (or Sn).
しかしながら、従来提案されている超電導体では、未だ十分な超電導を示すと共にコストや加工性においても十分に要求を満足するものではなかった。
従って、本発明の目的は、十分な超電導を示し、低コストで加工の簡便性も有する超電導体を提供することにある。
However, the conventionally proposed superconductors still exhibit sufficient superconductivity and do not sufficiently satisfy the requirements in terms of cost and workability.
Therefore, an object of the present invention is to provide a superconductor that exhibits sufficient superconductivity, is low in cost, and is easy to process.
本発明者らは、前記課題を解決するべく鋭意検討した結果、ＳｎＰｎ（ＰｎはＰ、Ａｓ、Ｓｂ、Ｂｉ）層を超電導層として持つ層状超電導系を発見し、更に鋭意検討した結果、本発明を完成するに至った。
本発明は、下記の発明を提供するものである。
１．構成成分Ａと、
構成成分Ｂとを具備し、
上記構成成分Ａからなる、超電導挙動を示す超電導層と、上記構成成分Ｂからなり、上記超電導層を空間的に離隔させるスペーサー層とが積層されて形成されており、
上記構成成分Ａが、化学式 ＳｎｘＭｙ（式中Ｍは、Ｐ，Ａｓ，Ｓｂ及びＢｉからなる群より選択される元素を示し、ｘ及びｙは、ｘ：ｙ＝１：０．５～１．５の関係にある）で表される化合物である
超電導体。
２．上記構成成分Ｂは、Ｎａ，Ｌｉ，Ｓｒ，Ｅｕ、Ｓｎ、Ａｓ、Ｐ、Ｓｂ及びＫからなる群より選択される１種以上を含む成分である１記載の超電導体。
As a result of diligent studies to solve the above problems, the present inventors have discovered a layered superconducting system having a SnPn (Pn is P, As, Sb, Bi) layer as a superconducting layer, and further diligently studied the present invention. Has been completed.
The present invention provides the following inventions.
1. 1. Component A and
It is equipped with the component B and
A superconducting layer composed of the component A and exhibiting superconducting behavior and a spacer layer composed of the component B and spatially separating the superconducting layer are laminated and formed.
The component A represents an element selected from the group consisting of the chemical formula SnxMy (M in the formula is P, As, Sb and Bi, and x and y are x: y = 1: 0.5 to 1.5. A superconductor which is a compound represented by).
2. 2. 1. The superconductor according to 1. The component B is a component containing at least one selected from the group consisting of Na, Li, Sr, Eu, Sn, As, P, Sb and K.
本発明の超電導体は、十分な超電導を示し、低コストで加工の簡便性も有するものである。 The superconductor of the present invention exhibits sufficient superconductivity, is low in cost, and is easy to process.
以下、本発明について、その好ましい実施形態に基づき詳細に説明する。
＜全体構成＞
本発明の超電導体（以下、「ＳｎＰｎ系超電導体」という場合もある）は、構成成分Ａと、構成成分Ｂとを具備し、
上記構成成分Ａからなる、超電導挙動を示す超電導層と、上記構成成分Ｂからなり、上記超電導層を空間的に離隔させるスペーサー層とが積層されて形成されており、
上記構成成分Ａが、化学式 ＳｎｘＭｙ（式中Ｍは、Ｐ，Ａｓ，Ｓｂ及びＢｉからなる群より選択される元素を示し、ｘ及びｙは、ｘ：ｙ＝１：０．５～１．５の関係にある）で表される化合物である。
なお、構成成分Ａと構成成分Ｂとはそれぞれが薄膜成長された状態で積層された状態でもよいが、両者は化学的に結合しているのが好ましく、この両者が結合した状態で超電導層とスペーサー層とが積層されているのが好ましい。
以下、詳述する。
Hereinafter, the present invention will be described in detail based on the preferred embodiment thereof.
<Overall configuration>
The superconductor of the present invention (hereinafter, may be referred to as “SnPn-based superconductor”) comprises a constituent component A and a constituent component B.
A superconducting layer composed of the component A and exhibiting superconducting behavior and a spacer layer composed of the component B and spatially separating the superconducting layer are laminated and formed.
The component A represents an element selected from the group consisting of the chemical formula SnxMy (M in the formula is P, As, Sb and Bi, and x and y are x: y = 1: 0.5 to 1.5. It is a compound represented by).
The constituent component A and the constituent component B may be laminated in a thin film-grown state, but it is preferable that the constituent components A and the constituent component B are chemically bonded to each other, and the superconducting layer and the constituent component B are bonded to each other. It is preferable that the spacer layer is laminated.
The details will be described below.
＜超電導層＞
上記超電導層は、化学式 ＳｎｘＭｙで表される構成成分Ａからなる。
なお、「超電導挙動を示す」とは、本明細書においては、温度の限定はなく、超電導温度が存在することを意味し、「超電導挙動を示さない」超電導温度が存在しないことを意味する。
上記化学式におけるＭは、Ｐ，Ａｓ，Ｓｂ及びＢｉからなる群より選択される元素を示す。
また、ｘ及びｙは、ｘ：ｙ＝１：０．５～１．５の関係にある。
このような関係を示す具体的な成分としては、以下に示す成分等を挙げることができる。
ＳｎＰ
ＳｎＡｓ
ＳｎＳｂ
ＳｎＢｉ
Ｓｎ２Ｐ２
Ｓｎ２Ａｓ２
Ｓｎ２Ｓｂ２
Ｓｎ２Ｂｉ２
<Superconducting layer>
The superconducting layer is composed of a constituent component A represented by the chemical formula SnxMy.
In addition, "exhibiting superconducting behavior" means that there is no limitation on the temperature in the present specification and that a superconducting temperature exists, and that there is no superconducting temperature that "does not exhibit superconducting behavior".
M in the above chemical formula indicates an element selected from the group consisting of P, As, Sb and Bi.
Further, x and y have a relationship of x: y = 1: 0.5 to 1.5.
Specific components showing such a relationship include the following components and the like.
SnP
SnAs
SnSb
SnBi
Sn 2 P 2
Sn 2 As 2
Sn 2 Sb 2
Sn 2 Bi 2
＜スペーサー層＞
上記スペーサー層を構成する構成成分Ｂとしては、Ｎａ，Ｌｉ，Ｓｒ，Ｅｕ、Ｓｎ、Ａｓ、Ｐ、Ｓｂ及びＫからなる群より選択される１種以上を含む成分が挙げられる。
上記スペーサー層を構成する構成成分Ｂの具体例としては、下記の成分等が挙げられる。
Ｎａ、
Ｌｉ、
Ｓｒ、
Ｅｕ、
Ｋ、
またはこれらの欠損ＮａｘやＳｒｘ、
またはこれらの固溶Ｎａ１－ｘＬｉｘやＮａ１－ｘＳｒｘ（ただし、これらのｘは０より大きく１より小さい数を示す）、
化合物成分として、Ｓｎ2ＰやＳｎ2Ａｓ等
<Spacer layer>
Examples of the component B constituting the spacer layer include a component containing at least one selected from the group consisting of Na, Li, Sr, Eu, Sn, As, P, Sb and K.
Specific examples of the component B constituting the spacer layer include the following components and the like.
Na,
Li,
Sr,
Eu,
K,
Or these deficient Na x or Sr x ,
Or these solid-dissolved Na 1-x Li x and Na 1-x Sr x (where these x indicate numbers greater than 0 and less than 1),
As compound components, Sn 2 P, Sn 2 As, etc.
＜超電導体の構造＞
本発明の超電導体１は、図１に示すように、超電導層１０、即ち超電導挙動を示す層と、スペーサー層２０、即ち超電導層１０を空間的に隔て、超電導挙動を示さない層とを積層してなる。ここで「積層」とは、超電導層１０とスペーサー層２０とが交互に存在する状態、超電導層１０が複数積層されて積層された層（積層層）が形成されており、この積層層間にスペーサー層２０が存在する状態（図１に示す形態）、スペーサー層２０が複数積層されて積層された層（積層層）が形成されており、この積層層間に超電導層１０が存在する状態、及びこれらの状態が組み合わされた状態を意味する。
図１はＮａＳｎ２Ａｓ２で示される超電導体の構造を模式的に示す図であり、図１に示す例においては、超電導層１０が、層状に連なった構成成分Ａ（Ｓｎ２Ａｓ２）からなり、かかる構成成分Ａの層が２層重なって超電導層１０を形成している。なお、これは一例を示したものであり、種々形態の超電導層１０があってよく、上記構成成分Ａの層が３層以上重なっていてもよく、また１層のみで形成されていてもよい。
また超電導層１０において小さい球体１１はＳｎを示し、大きい球体１２はＭとしてのＡｓを示す。また両者をつなぐ線１３は便宜上入れているものであり、化学結合または分子間力による結合など種々の強い結合ならびに弱い結合を示す。
層２０はスペーサー層であり、球２１は上記物質としてのＮａを示す。
なお、超電導体を組成式ＮａＳｎ２Ａｓ２で表すのは、構成成分Ａ及び構成成分Ｂを総合して表すためであり、図中の枠線で示す単位格子中の原子数に基づいて原子数をカウントした場合の組成に基づいて上記の組成式で表される。
図１に示す形態をとる超電導体としては、上述の組成式で表されるもののほかにＬｉＳｎ２Ａｓ２、ＮａＳｎ2Ｐ2, Ｓｎ4Ａｓ3, Ｓｎ4Ｐ3等が挙げられる。
各層の厚みは各原子の結合状態及び結晶構造に起因し、特に制限されるものではない。また超電導層１０及びスペーサー層２０の間隔は、超電導層１０を構成する成分とスペーサー層２０を構成する成分分子のイオン半径やそれらの間の化学結合力により決定される。
また、超電導層１０及びスペーサー層２０の平面視面積（図１の矢印Ａ方向に矢視した際の面積）は、どの程度の分子を結合させるかに応じて任意である。
超電導層１０とスペーサー層２０との積層数も任意である。
<Structure of superconductor>
As shown in FIG. 1, in the
FIG. 1 is a diagram schematically showing the structure of a superconductor represented by NaSn 2 As 2. In the example shown in FIG. 1, the
Further, in the
The
The superconductor is represented by the composition formula NaSn 2 As 2 in order to collectively represent the constituent components A and B, and the number of atoms is based on the number of atoms in the unit cell shown by the frame line in the figure. Is expressed by the above composition formula based on the composition when counting.
Examples of the superconductor having the form shown in FIG. 1 include LiSn 2 As 2 , NaSn 2 P 2 , Sn 4 As 3 , Sn 4 P 3 , and the like, in addition to those represented by the above-mentioned composition formula.
The thickness of each layer depends on the bonding state of each atom and the crystal structure, and is not particularly limited. The distance between the
Further, the area of the
The number of layers of the
＜製造方法＞
本発明の超電導体は、以下の製法に準じて得ることができる。
すなわち、原料成分を３００～１０００℃で１～３０時間焼成する焼成工程を行うことで得ることができる（以下、この方法を「合成方法１」という）。
また、更にこの焼成工程の後、得られた焼成物を徐々に冷却することで５０～２００時間かけて冷却を行い、室温まで冷却する冷却工程を行うことで得ることもできる（以下、この方法を「合成方法２」という）。
また、上記の冷却工程に代えて、焼成工程の後、得られた焼成物を水中に投入し、水中にて急速に冷却する急冷工程を行うことで得ることもできる（以下、この方法を「合成方法３」という）。なお、この際の冷却時間は好ましくは１～１０秒であり、好ましくは１０～２５℃の水を用い、室温まで冷却するのが好ましい。
<Manufacturing method>
The superconductor of the present invention can be obtained according to the following production method.
That is, it can be obtained by performing a firing step of firing the raw material component at 300 to 1000 ° C. for 1 to 30 hours (hereinafter, this method is referred to as "
Further, after this firing step, it can also be obtained by performing a cooling step of gradually cooling the obtained fired product to cool it for 50 to 200 hours and then cooling it to room temperature (hereinafter, this method). Is called "
Further, instead of the above cooling step, it can also be obtained by putting the obtained fired product into water and performing a quenching step of rapidly cooling in water after the firing step (hereinafter, this method is referred to as "this method".
本発明は上述した実施形態に何ら制限されるものではなく、本発明の趣旨を逸脱しない範囲で種々変形可能である。 The present invention is not limited to the above-described embodiment, and can be variously modified without departing from the spirit of the present invention.
以下、本発明について実施例を示してさらに具体的に説明するが、本発明はこれらに何ら制限されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
〔実施例１〕
実施例１に係るＳｎＰｎ系超電導体は、超電導層の構成成分ＡがＳｎ2Ａｓ2であり、スペーサー層の構成成分ＢがＮａである超電導体である。
実施例１に係るＮａＳｎ2Ａｓ2超電導体は以下のようにして製造した。すなわち、出発原料にＮａ（シグマ－アルドリッチ社製、Ｎａキューブ、９９．９％）、Ｓｎ（高純度化学社製、Ｓｎ粉末、９９．９％）、Ａｓ（高純度化学社製、９９．９９９９％）を用い、Ａｒ雰囲気のグローブボックス中で組成比がＮａＳｎ2Ａｓ2になるように秤量した。
[Example 1]
The SnPn-based superconductor according to the first embodiment is a superconductor in which the component A of the superconducting layer is Sn 2 As 2 and the component B of the spacer layer is Na.
The NaSn 2 As 2 superconductor according to Example 1 was manufactured as follows. That is, the starting materials are Na (Sigma-Aldrich, Na Cube, 99.9%), Sn (High Purity Chemicals, Sn Powder, 99.9%), As (High Purity Chemicals, 99.99999). %) Was used and weighed so that the composition ratio was NaSn 2 As 2 in a glove box in an Ar atmosphere.
次に、秤量して得られた各原料を石英ガラス管に真空封入し、電気炉にて７５０℃で２０時間焼成した。これにより、実施例１に係るＳｎＰｎ系超電導体としてＮａＳｎ2Ａｓ2が得られた。なお、実施例１に係るＮａＳｎ2Ａｓ2超電導体の合成方法を以下、「合成方法１」という。
Next, each raw material obtained by weighing was vacuum-sealed in a quartz glass tube and fired at 750 ° C. for 20 hours in an electric furnace. As a result, NaSn 2 As 2 was obtained as the SnPn-based superconductor according to Example 1. The method for synthesizing the NaSn 2 As 2 superconductor according to Example 1 is hereinafter referred to as "
〔実施例２〕
実施例２に係るＳｎＰｎ系超電導体は、構成成分ＡがＳｎ2Ａｓ2であり、構成成分ＢがＬｉである超電導体である。すなわち、実施例２に係るＳｎＰｎ系超電導体は、組成式がＬｉＳｎ2Ａｓ2で表される超電導体である。
[Example 2]
The SnPn-based superconductor according to the second embodiment is a superconductor in which the component A is Sn 2 As 2 and the component B is Li. That is, the SnPn-based superconductor according to Example 2 is a superconductor whose composition formula is represented by LiSn 2 As 2 .
実施例２に係るＬｉＳｎ2Ａｓ2超電導体は以下のようにして製造した。すなわち、出発原料にＬｉ（高純度化学社製、Ｌｉインゴット、９９．９％）、Ｓｎ（高純度化学社製、Ｓｎ粉末、９９、９％）、Ａｓ（高純度化学社製、９９．９９９９％）を用い、Ａｒ雰囲気のグローブボックス中で組成比がＬｉ０．７Ｓｎ２．３Ａｓ2になるように秤量した。 The LiSn 2 As 2 superconductor according to Example 2 was manufactured as follows. That is, the starting materials are Li (manufactured by High Purity Chemical Co., Ltd., Li ingot, 99.9%), Sn (manufactured by High Purity Chemical Co., Ltd., Sn powder, 99, 9%), As (manufactured by High Purity Chemical Co., Ltd., 99.99999). %) Was used and weighed so that the composition ratio was Li 0.7 Sn 2.3 As 2 in a glove box in an Ar atmosphere.
次に、秤量して得られた各原料を石英ガラス管に真空封入し、電気炉にて７００℃で２時間焼成し、室温まで１００時間かけて冷却した。これにより、実施例１に係るＳｎＰｎ系超電導体としてＬｉ０．７Ｓｎ２．３Ａｓ2が得られた。なお、実施例２に係るＬｉ０．７Ｓｎ２．３Ａｓ2超電導体の合成方法を以下、「合成方法２」という。
〔実施例３〕
Next, each raw material obtained by weighing was vacuum-sealed in a quartz glass tube, fired in an electric furnace at 700 ° C. for 2 hours, and cooled to room temperature over 100 hours. As a result, Li 0.7 Sn 2.3 As 2 was obtained as the SnPn-based superconductor according to Example 1. The method for synthesizing the Li 0.7 Sn 2.3 As 2 superconductor according to Example 2 is hereinafter referred to as “
[Example 3]
実施例３に係るＳｎＰｎ系超電導体は、構成成分ＡがＳｎ2Ａｓ2であり、構成成分ＢがＳｎ2Ａｓである超電導体である。すなわち、実施例２に係るＳｎＰｎ系超電導体は、組成式がＳｎ４Ａｓ3で表される超電導体である。 The SnPn-based superconductor according to the third embodiment is a superconductor in which the component A is Sn 2 As 2 and the component B is Sn 2 As 2. That is, the SnPn-based superconductor according to the second embodiment is a superconductor whose composition formula is represented by Sn 4 As 3 .
実施例２に係るＳｎ４Ａｓ3超電導体は以下のようにして製造した。すなわち、出発原料にＳｎ（高純度化学社製、Ｓｎ粉末、９９、９％）、Ａｓ（高純度化学社製、９９．９９９９％）を用い、Ａｒ雰囲気のグローブボックス中で組成比がＳｎ４Ａｓ3になるように秤量した。 The Sn 4 As 3 superconductor according to Example 2 was manufactured as follows. That is, Sn (manufactured by High Purity Chemical Co., Ltd., Sn powder, 99, 9%) and As (manufactured by High Purity Chemical Co., Ltd., 99.99999%) are used as starting materials, and the composition ratio is Sn 4 in an Ar atmosphere glove box. Weighed to As 3 .
次に、秤量して得られた各原料を混合した後にペレット状に成形することで原料ペレットを得た。続いて、得られた原料ペレットを石英ガラス管に真空封入し、電気炉にて４５０℃で２０時間焼成し、水中にて急冷した。この際、室温（２５℃）の水を用い、数秒（１０秒以内）で室温まで冷却した。これにより、実施例３に係るＳｎＰｎ系超電導体としてＳｎ４Ａｓ3が得られた。なお、実施例３に係るＳｎ４Ａｓ3超電導体の合成方法を以下、「合成方法３」という。
Next, raw material pellets were obtained by mixing the raw materials obtained by weighing and then molding into pellets. Subsequently, the obtained raw material pellets were vacuum-sealed in a quartz glass tube, fired in an electric furnace at 450 ° C. for 20 hours, and rapidly cooled in water. At this time, water at room temperature (25 ° C.) was used, and the mixture was cooled to room temperature within a few seconds (within 10 seconds). As a result, Sn 4 As 3 was obtained as the SnPn-based superconductor according to Example 3. The method for synthesizing the Sn 4 As 3 superconductor according to the third embodiment is hereinafter referred to as "
〔実施例４〕
実施例４に係るＳｎＰｎ系超電導体は、構成成分ＡがＳｎ2Ｐ2であり、構成成分ＢがＳｎ2Ｐである超電導体である。すなわち、実施例２に係るＳｎＰｎ系超電導体は、組成式がＳｎ４Ｐ3で表される超電導体である。
[Example 4]
The SnPn-based superconductor according to the fourth embodiment is a superconductor in which the component A is Sn 2 P 2 and the component B is Sn 2 P. That is, the SnPn-based superconductor according to the second embodiment is a superconductor whose composition formula is represented by Sn 4 P 3 .
実施例４に係るＳｎ４Ｐ3超電導体は以下のようにして製造した。すなわち、出発原料にＳｎ（高純度化学社製、Ｓｎ粉末、９９、９％）、Ｐ（高純度化学社製、９９．９９９９％）を用い、Ａｒ雰囲気のグローブボックス中で組成比がＳｎ４Ｐ3になるように秤量した。 The Sn 4 P 3 superconductor according to Example 4 was manufactured as follows. That is, Sn (manufactured by High Purity Chemical Co., Ltd., Sn powder, 99, 9%) and P (manufactured by High Purity Chemical Co., Ltd., 99.99999%) were used as starting materials, and the composition ratio was Sn 4 in an Ar atmosphere glove box. Weighed to P3.
次に、秤量して得られた各原料を混合した後にペレット状に成形することで原料ペレットを得た。続いて、得られた原料ペレットを石英ガラス管に真空封入し、電気炉にて４５０℃で２０時間焼成し、水中にて急冷した。この際、室温（２５℃）の水を用い、数秒（１０秒以内）で室温まで冷却した。これにより、実施例４に係るＳｎＰｎ系超電導体としてＳｎ４Ｐ3が得られた。なお、実施例４に係るＳｎ４Ｐ3超電導体の合成方法を以下、「合成方法４」という。
Next, raw material pellets were obtained by mixing the raw materials obtained by weighing and then molding into pellets. Subsequently, the obtained raw material pellets were vacuum-sealed in a quartz glass tube, fired in an electric furnace at 450 ° C. for 20 hours, and rapidly cooled in water. At this time, water at room temperature (25 ° C.) was used, and the mixture was cooled to room temperature within a few seconds (within 10 seconds). As a result, Sn 4 P 3 was obtained as the SnPn-based superconductor according to Example 4. The method for synthesizing the Sn 4 P 3 superconductor according to the fourth embodiment is hereinafter referred to as “
〔実施例５〕
実施例５に係るＳｎＰｎ系超電導体は、超電導層の構成成分ＡがＳｎ2Ｐ2であり、スペーサー層の構成成分ＢがＮａである超電導体である。
実施例５に係るＮａＳｎ2Ｐ2超電導体は以下のようにして製造した。すなわち、出発原料にＮａ3Ｐ、Ｓｎ（高純度化学社製、Ｓｎ粉末、９９．９％）、P（高純度化学社製、９９．９９９９％）を用い、Ａｒ雰囲気のグローブボックス中で組成比がＮａＳｎ2P2になるように秤量した。ここで、Ｎａ3ＰはＮａ（シグマ－アルドリッチ社製、Ｎａキューブ、９９．９％）とＰを石英ガラス管に真空封入し、電気炉にて３００～４００℃で２０時間焼成することで得た。
[Example 5]
The SnPn-based superconductor according to the fifth embodiment is a superconductor in which the component A of the superconducting layer is Sn 2 P 2 and the component B of the spacer layer is Na.
The NaSn 2 P 2 superconductor according to Example 5 was manufactured as follows. That is, Na 3P , Sn (manufactured by High Purity Chemical Co., Ltd., Sn powder, 99.9%) and P (manufactured by High Purity Chemical Co., Ltd., 99.99999%) were used as starting materials, and the composition was made in an Ar atmosphere glove box. Weighed so that the ratio was NaSn 2 P 2 . Here, Na 3 P can be obtained by vacuum-sealing Na (Na cube, 99.9% manufactured by Sigma-Aldrich) and P in a quartz glass tube and firing at 300 to 400 ° C. for 20 hours in an electric furnace. rice field.
次に、秤量して得られた各原料を石英ガラス管に真空封入し、電気炉にて４００℃で２０時間焼成した。これにより、実施例５に係るＳｎＰｎ系超電導体としてＮａＳｎ2Ｐ2が得られた。なお、実施例５に係るＮａＳｎ2Ｐ2超電導体の合成方法を以下、「合成方法５」という。
Next, each raw material obtained by weighing was vacuum-sealed in a quartz glass tube and fired at 400 ° C. for 20 hours in an electric furnace. As a result, NaSn 2 P 2 was obtained as the SnPn-based superconductor according to Example 5. The method for synthesizing the NaSn 2 P 2 superconductor according to Example 5 is hereinafter referred to as “
（実施例で得られた超電導体の評価結果）
実施例１～５で得られたＳｎＰｎ系超電導体の超電導転移温度（Ｔｃ）電気抵抗率の温度依存性により決定した。電気抵抗率は４端子法を用いて測定した。その結果を図２～６に示す。
また、実施例１～５で得られたＳｎＰｎ系超電導体について、Ｘ線構造解析を実施した。その結果を図７～１１に示す。この結果から明らかなように、すべての超電導体について空間群Ｒ－３ｍ構造に特徴的なピークが観測された。したがって、各超電導体が、空間群がＲ－３ｍである三方晶の層状構造をしていることが示された。
実施例１～５に係るＳｎＰｎ系超電導体の製造に用いた出発原料の混合比と、得られた超電導体の超電導転移温度（Ｔｃ）の値を表１に示す。
It was determined by the temperature dependence of the superconducting transition temperature (Tc) electrical resistivity of the SnPn-based superconductors obtained in Examples 1 to 5. The electrical resistivity was measured using the 4-terminal method. The results are shown in FIGS. 2 to 6.
In addition, X-ray structure analysis was performed on the SnPn-based superconductors obtained in Examples 1 to 5. The results are shown in FIGS. 7 to 11. As is clear from this result, peaks characteristic of the space group R-3m structure were observed for all superconductors. Therefore, it was shown that each superconductor has a trigonal layered structure in which the space group is R-3 m.
Table 1 shows the mixing ratio of the starting raw materials used for producing the SnPn-based superconductors according to Examples 1 to 5 and the values of the superconducting transition temperature (Tc) of the obtained superconductors.
Claims (1)
上記構成成分Ａが、化学式 ＳｎｘＭｙ（式中Ｍは、ＰまたはＡｓであり、ｘ及びｙは、ｘ：ｙ＝１：０．５～１．５の関係にある）で表される化合物であり、
上記構成成分Ｂが、Ｎａ，Ｌｉ，Ｓｎ 2 Ｐ、またはＳｎ 2 Ａｓであり、
上記構成成分Ａと上記構成成分Ｂとのモル比は、上記構成成分Ａ：上記構成成分Ｂ＝１：１である
超電導体。 A superconducting layer having a component A and a component B and exhibiting superconducting behavior, which is composed of the component A, and a spacer layer composed of the component B and spatially separating the superconducting layer are laminated. Is formed and
The component A is a compound represented by the chemical formula SnxMy (M in the formula is P or As, and x and y have a relationship of x: y = 1: 0.5 to 1.5). ,
The component B is Na, Li, Sn 2 P, or Sn 2 As.
The molar ratio of the component A to the component B is the component A: the component B = 1: 1.
Superconductor.
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| JP2009234847A (en) | 2008-03-27 | 2009-10-15 | Japan Science & Technology Agency | Superconductor comprising lamellar compound and method of producing the same |
| CN101814344A (en) | 2010-03-10 | 2010-08-25 | 中国科学院电工研究所 | Method for preparing iron-based superconductor |
| JP2011026176A (en) | 2009-07-28 | 2011-02-10 | Sumitomo Electric Ind Ltd | Method for production of groups iii-v compound crystal |
| JP2012199234A (en) | 2011-03-10 | 2012-10-18 | Osaka Prefecture Univ | Lithium ion battery, and negative electrode material therefor |
| JP2015127280A (en) | 2013-12-27 | 2015-07-09 | 国立研究開発法人産業技術総合研究所 | Phosphorus compound and use thereof |
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| JP2009234847A (en) | 2008-03-27 | 2009-10-15 | Japan Science & Technology Agency | Superconductor comprising lamellar compound and method of producing the same |
| JP2011026176A (en) | 2009-07-28 | 2011-02-10 | Sumitomo Electric Ind Ltd | Method for production of groups iii-v compound crystal |
| CN101814344A (en) | 2010-03-10 | 2010-08-25 | 中国科学院电工研究所 | Method for preparing iron-based superconductor |
| JP2012199234A (en) | 2011-03-10 | 2012-10-18 | Osaka Prefecture Univ | Lithium ion battery, and negative electrode material therefor |
| JP2015127280A (en) | 2013-12-27 | 2015-07-09 | 国立研究開発法人産業技術総合研究所 | Phosphorus compound and use thereof |
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