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Layered compound, superconductor and method for producing same

外国特許コード F110003553
整理番号 BE06009WO
掲載日 2011年6月29日
出願国 アメリカ合衆国
出願番号 00314909
公報番号 20110111965
公報番号 8288321
出願日 平成21年7月9日(2009.7.9)
公報発行日 平成23年5月12日(2011.5.12)
公報発行日 平成24年10月16日(2012.10.16)
国際出願番号 JP2009062500
国際公開番号 WO2010007929
国際出願日 平成21年7月9日(2009.7.9)
国際公開日 平成22年1月21日(2010.1.21)
優先権データ
  • 特願2008-184843 (2008.7.16) JP
  • 2009JP062500 (2009.7.9) WO
発明の名称 (英語) Layered compound, superconductor and method for producing same
発明の概要(英語) Provides a new non-oxide system compound material superconductor as an alternative of the perovskite type copper oxides superconductor.
Layered compounds which are represented by chemical formula AF(TM)Pn (wherein, A is at least one selected from a group consisting of the second family elements in the long form periodic table, F is a fluorine ion, TM is at least one selected from a group of transition metal elements consisting of Fe, Ru, Os, Ni, Pd, and Pt, and Pn is at least one selected from a group consisting of the fifteenth family elements in the long form periodic table), having a crystal structure of ZrCuSiAs type (space group P4/nmm) and which become superconductors by doping trivalent cations or divalent anions.
従来技術、競合技術の概要(英語) BACKGROUND
Since the discovery of the high temperature superconductors (perovskite type copper oxides), research of materials aiming a room temperature superconductor has been actively performed.
As a result, a superconductor having a superconductive transition temperature (Tc) over 100K has been found.
There has been a progress in understanding of the formation mechanism of the superconductivity in the perovskite type copper oxides (for example, non-patent references 1 and 2.) On the other hand, compounds that include transition metal ions other than copper, or new compounds such as Sr2RuO4 (Tc=0.93 K) (Non-patent reference 3), Magnesium diboride (Tc=39 K) (Non-patent reference 4, Patent reference 1) and Na0.3CoO2.1.3H2O (Tc=5K) (Non-patent reference 5, Patent reference 2 and 3) have been newly found.
Strongly correlated electron system compounds having large interaction energy between conductive electrons compared to conduction band width, are known to have high possibilities to be superconductors having high superconductive transition temperatures.
The strongly correlated electron system has been realized by layered compounds having transition metal ions at the skeletal structure.
Most of such layered compounds belong to Mott-insulator, where antiferromagnetic interaction operates between electron spins in a way to align them antiparallel.
However, for example, in La2CuO4 which belongs to the perovskite type copper oxides, when Sr2+ ions are added at La3+ sites to form La2-xSrxCuO4, the itinerant electron state exhibiting metallic conduction is observed for x values within a range from 0.05 to 0.28, where superconductive state is observed at a low temperature and maximum Tc=40 K has been reported at x=0.15 (non-patent reference 6).
Recently, the inventors of the present application, found that a new strongly correlated electron compound having Fe as main component, LaOFeP and LaOFeAs can be superconductors, and applied as a patent (patent reference 4 and non-patent reference 7.) In the strongly correlated electron system, the itinerant electron state which exhibits metallic conduction is realized when a number of d-electrons takes a specific value, where transition to superconductive state occurs below a specific temperature (superconductivity transition temperature) when temperature is lowered.
Further, the transition temperature of this superconductor varies from 5 K to 40 K, depending on numbers of conductive carriers.
While in conventional superconductors such as Hg, Ge3Nb, the formation mechanism of the superconductivity has been attributed to the electron pair (Cooper pair) due to a thermal perturbation (BCS mechanism), in the strongly correlated electron system, the formation mechanism of the superconductivity has been attributed to the electron pair due to thermal perturbation of electron spins.
The inventors of the present application further found a superconductor comprising a strong electron correlation compound represented by LnTMOPn [here, Ln is at least one selected from a group consisting of Y and lanthanide elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), TM is at least one selected from a group consisting of transition metal elements (Fe, Ru, Os, Ni, Pd, Pt), Pn is at least one selected from a group of pnictogen elements (N, P, As, Sb)], and filed a patent application (Patent reference 5, Non-patent reference 8-10.)
The inventors of the present application also found a superconductor in compounds represented by A(TM)2(Pn)2 [here A is at least one selected from a group consisting of the second family elements in the long from periodic table, TM is at least one selected from a group of transition metal elements consisting of Fe, Ru, Os, Ni, Pd and Pt, and Pn is at least one selected from a group of the 15th family elements (pnictogen elements) in the long form periodic table], and filed a patent application (patent reference 6, non-patent reference 11.)

REFERENCES

Non-Patent References
Non-patent reference 1: Tadao Tsuda, Keiichiro Nasu, Atsushi Fujimori, Norikazu Shiratori, "Electric conductive oxides," pp. 350-452, Shokabo, 1993,
Non-patent reference 2: Sadamichi Maekawa, Oyo Butsuri, vol. 75, No. 1, pp. 17-25, 2006,
Non-patent reference 3, Y. Maeno, H. Hashimoto, K. Yoshida, S. Nishizaki, T. Fujita, J. G. Bednorz, F. Lichtenberg, Nature, 372, pp. 532-534 (1994),
Non-patent reference 4: J. Nagamatsu, N. Nakagawa, T. Muranaka, Y. Zenitani, J. Akimitsu, Nature, 410 pp. 63-64, (2001),
Non-patent reference 5: K. Takada, H. Sakurai, E. Takayama-Muromachi, F. Izumi, R. A. Dilanian, T. Sasaki, Nature, 422, pp. 53-55, (2003),
Non-patent reference 6: J. B. Torrance et al., Phys. Rev., B40, pp. 8872-8877, (1989),
Non-patent reference 7: Y. Kamihara et al., J. Am. Chem. Soc., 128 (31), pp. 10012-10013, (2006),
Non-patent reference 8: T. Watanabe et al., Inorg. Chem., 46 (19), pp. 7719-7721, (2007),
Non-patent reference 9: Y. Kamihara et al., J. Am. Chem. Soc., 130 (11), pp. 3296-329'7, (2008)
Non-patent reference 10: H. Takahashi et al., Nature, 453, pp. 376-378, (2008),
Non-patent reference 11: Hiroshi Yanagi et al., Proceedings of the 55th Joint Conferences of Japan Society of Applied Physics, 2008 SPRING, p. 288, March 27, (2008).

Patent References
Patent references 1: Japanese laid-open patent publication No. 2002-211916,
Patent references 2: Japanese laid-open patent publication No. 2004-262675,
Patent references 3: Japanese laid-open patent publication No. 2005-350331,
Patent references 4: Japanese laid-open patent publication No. 2007-320829,
Patent references 5: Japanese patent application No. 2008-035977,
Patent references 6: Japanese patent application No. 2008-082386.

特許請求の範囲(英語) [claim1]
1. A layered compound represented by chemical formula:
AF(TM)Pn
wherein A is at least one selected from a group consisting of the 2nd family elements in the long form periodic table, F is a fluorine ion,
TM is at least one selected from a group of transition metal elements consisting of Fe, Ru, Os, Ni, Pd, and Pt, and
Pn is at least one selected from a group consisting of the 15th family elements in the long form periodic table, and
wherein the layered compound has a crystal structure of ZrCuSiAs type (space group P4/nmm) and that the layered compound becomes superconductive by doping trivalent cations or divalent anions.
[claim2]
2. The layered compound of claim 1, wherein A is at least one selected from a group consisting of Ca and Sr, TM is either Ni or Fe, and Pn is at least one selected from a group consisting of P, As, and Sb.
[claim3]
3. The layered compound of claim 1, wherein the layered compound is doped with a trivalent cation of an element selected from a group consisting of Sc, Y, La, Nd, and Gd.
[claim4]
4. The layered compound of claim 1, wherein the layered compound is doped with a divalent anion of an element selected from a group consisting of O, S, and Se.
[claim5]
5. A method of manufacturing a layered compound represented by chemical formula: AF(TM)Pn, wherein A is at least one selected from a group consisting of the 2nd family elements in the long form periodic table, F is a fluorine ion, TM is at least one selected from a group of transition metal elements consisting of Fe, Ru, Os, Ni, Pd, and Pt, and Pn is at least one selected from a group consisting of the 15th family elements in the long form periodic table, and wherein the layered compound has a crystal structure of ZrCuSiAs type (space group P4/nmm) and that the layered compound becomes superconductive by doping trivalent cations or divalent anions, the method comprising: mixing powders of element A, TM element, Pn element, and at least one fluorine compound selected from a group consisting of fluorine compounds of element A, fluorine compounds of TM element, and fluorine compounds of Pn element, and
sintering the mixed powders at 900 to 1200 deg C. in an inert gas ambient or in a vacuum.
[claim6]
6. The method according to claim 5, wherein the layered compound is doped with a trivalent cation of an element selected from a group consisting of Sc, Y, La, Nd, and Gd, and
in the mixing step, the powders include powder of element of the trivalent cations cation or powder of fluorine compound of element of the trivalent cation.
[claim7]
7. The method according to claim 5, wherein the layered compound is doped with a divalent anion of an element selected from a group consisting of O, S, and Se, and
in the mixing step, the powders include at least one powder of oxide of A element, sulfide of A element, selenide of A element, sulfur, and selenium.
[claim8]
8. A super conductor comprised of the layered compound according to claim 3.
[claim9]
9. A super conductor comprised of the layered compound according to claim 4.
  • 発明者/出願人(英語)
  • HOSONO HIDEO
  • YANAGI HIROSHI
  • KAMIYA TOSHIO
  • MATSUISHI SATORU
  • KIM SUNGWNG
  • YOON SEOK GYU
  • HIRAMATSU HIDENORI
  • HIRANO MASAHIRO
  • NOMURA TAKATOSHI
  • KAMIHARA YOICHI
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
国際特許分類(IPC)
米国特許分類/主・副
  • 505/123
  • 505/461
参考情報 (研究プロジェクト等) ERATO/SORST Exploring and developing applications for active functions utilizing nanostructure embedded in transparent oxides AREA
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