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Development and Application of Layer Structured Nitride Superconductors

Research Project

Project/Area Number 14350461
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 無機工業化学
Research InstitutionHIROSHIMA UNIVERSITY

Principal Investigator

YAMANAKA Shoji  Hiroshima University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (90081314)

Co-Investigator(Kenkyū-buntansha) INUMARU Kei  Hiroshima University, Graduate School of Engineering, Associate Professor, 大学院・工学研究科, 助教授 (80270891)
陳 学安  広島大学, 大学院・工学研究科, 助手 (30343289)
Project Period (FY) 2002 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥15,000,000 (Direct Cost: ¥15,000,000)
Fiscal Year 2003: ¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 2002: ¥11,000,000 (Direct Cost: ¥11,000,000)
KeywordsLeyered Nitride / Superconductor / Intercalation / High pressure synthesis / Structural analysis / Thin film synthesis / Superconducting mechanism / 超伝導 / 層状物質 / 窒化物 / 薄膜
Research Abstract

We have reported that layer structured nitride halides β-MNX (M = Zr, Hf ; X = Cl, Br, I) electron-doped by intercalation of alkali metals became superconductors. In particular, the compound cointercalated with Li and THF (tetrahydrofuran), Lio_<48>(THF)_yHfNCl, showed a high critical temperature of Tc = 25.5 K. In this study, we have collaborated with solid state physicists to investigate the superconducting mechanism, and new types of layer structured nitrides have been developed. The main results obtained are the followings;
1. Single crystals of β-MNX were successfully prepared using ammonium halides as fluxes under high-pressure conditions, and their structures were determined by the single crystal X-ray analysis.
2. A new electron-doping method was developed by partial deintercalation of chlorine atoms to form β-ZrNCl_<1-x> and β-HfNCl_<1-x>, which were stable in air for pretty long time. The deintercalated samples showed similar superconductivity with those electron doped by alkali metal intercalation.
3. Isotope substituted β-Hf^<15>NCl was prepared, and its superconductors were derived by electron doping.
4. ^<15>N NMR study revealed that the layer structured nitride superconductors were two-dimensional ones with very low carrier densities and weak phonon enhancement. The mechanism of the new superconductors cannot be interpreted in the conventional BCS theory.
5. The superconducting gap was successfully measured by a break-junction method.
6. Layer structured Sr_2N oriented films were prepared by MBE method in a high vacuum chamber with a nitrogen radical source.

Report

(3 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • Research Products

    (71 results)

All Other

All Publications (71 results)

  • [Publications] K.Inumaru: "Preparation of superconducting Epitaxial Thin Films of Tansition Metal Nitrides on Silicon Wafers by Molecular Beam Epitaxy"J.Crystal Growth. 237-9. 2050-2054 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] X.Chen: "High-Pressure Synthesis and Crystal Structures of β-MNX (M=Zr, Hf ; X=Br, I)"J.Solid State Chem.. 163. 77-83 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] L.Zhu: "Preparation of TiN fine powders using ammonium chloride,"Mater.Res.Bull.. 37. 155-156 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Tou: "DC-magnetization and ^1H-NMR studies of layered superconductor Li_<0.48>(THF)_<0.3>HfNCl"Physica B. 312-313. 155-156 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] X.Chen: "High-Pressure Synthesis and Crystal Structures of β-MNX (M=Zr, Hf ; X=Cl, Br, I)"J.Phys.Condens.Matter,. 14. 11209-11212 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] L.Zhu: "Zirconium Nitride Derived from Layer Structured β-ZrNCl by deintercalation of chlorine layers"Chem.Mater.. 14. 4517-4521 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Sakamoto: "Pulsed laser deposition of novel nitride solid solution films Ni_xTi_<1-x>N_y on MgO(001)"Appl.Surface Sci.. 199. 303-306 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] X.Chen: "The first single-crystal X-ray structural refinement of the superconducting phase Li_<0.2(1)>ZrNCl derived by intercalation"J.Solid State Chem.. 169. 149-154 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] L.Zhu: "Preparation and superconductivity of Chlorine-Deintercalated Crystals β-MNCl_<1-x>(M=Zr, Hf)"Chem.Mater.. 15. 1897-1902 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Yamanaka: "Electron-doping and superconductivity in layer-structured nitride chlorides,β-MNCl (M=Zr, Hf)"Physica B. 328. 6-9 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Ekino: "Tunneling spectroscopy of MgB_2 and Li_<0.5>(THF)_yHfNCl"Physica B. 328. 23-25 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Tou: "NMR studies of the electron-doped hafnium nitride superconductor"Physica B. 329-333. 1323-1324 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Ekino: "Tunneling spectroscopy of the electron-doped layered superconductor Li_<0.48>(THF)_<0.3>HfNCl"Physica C. 388-389. 573-574 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Inumaru: "Preparation and transport properties of Nb_<1-x>Cr_xN epitaxial thin films on silicon wafers"Physica B. 328. 123-124 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Tou: "Superconducting characteristics in electron-doped layered hafnium nitride:^<15>N isotope effect studies"Phys.Rev.B. 67. 100509/1-100509/4 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Z.Liu: "Preparation and properties of the ternary ZrNF"Solid State Commun.. 130. 227-230 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Ito: "Superfluid density of layered superconductors LixHfNCl and LixZrNCl with/without co-intercalation of THF (tetrahydrofuran):muon spin relaxation and magnetization measurements"Phys.Rev.B. (印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Inumaru: "Synthesis and High Metallic Conductivity of Layer-Structured Sr_2N Thin Film Deposited onto MgO(001) Substrate."J.Alloys Compd.. 372. L1-L3 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Inumaru: "Layer-by-Layer Deposition of Epitaxial TiN - CrN Multilayers on MgO(001) by Pulsed Laser Ablation"Appl.Surface Sci.. (印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Yamanaka: "Synthesis and Properties of New Superconductors with Cage and Layered Structures"Jpn.J.Appl.Phys.Chem.. 41. 5008-5012 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Yamanaka: "Alkali Metal Intercalation in Layer Structured α-HfNBr"J.Phys.Chem.Solid. 65. 565-569 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Yamanaka: "Superconductivity of Layer Structured TiNCl Intercalated with Pyridine"Molecular Crystals and Liquid Crystals. (印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Shamoto: "Structural Study on Na_xHfNCl System"Physica C. 402. 283-292 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 山中昭司 分担執筆: "先端化学シリーズII、電気化学、光化学、無機固体、環境ケミカルサイエンス日本化学会編"丸善. 338 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Inumaru et al.: "Preparation of superconducting Epitaxial Thin Films of Tansition Metal Nitrides on Silicon Wafers by Molecular Beam Epitaxy"J.Crystal Growth. 237-239. 2050-2054 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] X.Chen et al.: "High-Pressure Synthesis and Crystal Structures of β-MNX (M = Zr, Hf ; X = Br, I)"J.Solid State Chem.. 163. 77-83 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] L.Zhu et al.: "Preparation of TiN fine powders using ammonium chloride"Mater.Res.Bull.. 37. 475-483 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Tou et al.: "DC-magnetization and ^1H-NMR studies of layered superconductor Li_<0.48>(THF)_<0.3>HfNCl"Physica B. 312-313. 155-156 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] X.Chen et al.: "High-Pressure Synthesis and Crystal Structures of β-MNX (M = Zr, Hf ; X = Cl, Br, I)"J.Phys.Condens.Matter.. 14. 11209-11212 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] L.Zhu et al.: "Zirconium Nitride Derived from Layer Structured β-ZrNCl by deintercalation of chlorine layers"Chem.Mater.. 14. 4517-4521 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Sakamoto et al.: "Pulsed laser deposition of novel nitride solid solution films Ni_xTi_<1-x>N_y on MgO(001)"Appl.Surface Sci.. 199. 303-306 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] X.Chen et al.: "The first single-crystal X-ray structural refinement of the superconducting phase Li_<0.2(1)>ZrNCl derived by intercalation"J.Solid State Chem.. 169. 149-154 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] L.Zhu et al.: "Preparation and superconductivity of Chlorine-Deintercalated Crystals β-MNCl_<1-x> (M = Zr, Hf)"Chem.Mater.. 15. 1897-1902 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Yamanaka et al.: "Electron-doping and superconductivity in layer-structured nitride chlorides, β-MNCl (M = Zr, Hf)"Physica B. 328. 6-9 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Ekino et al.: "Tunneling spectroscopy of MgB_2 and Li_<0.5>(THF)_yHfNCl"Physica B. 328. 23-25 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Tou et al.: "NMR studies of the electron-doped hafnium nitride superconductor"Physica B. 329-333. 1323-1324 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Ekino et al.: "Tunneling spectroscopy of the electron-doped layered superconductor Li_<0.48>(THF)_<0.3>HfNCl"Physica C. 388-389. 573-574 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Inumaru et al.: "Preparation and transport properties of Nb_<1-x>Cr_xN epitaxial thin films on silicon wafers"Physica B. 328. 123-124 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Tou et al.: "Superconducting characteristics in electron-doped layered hafnium nitride : ^<15>N isotope effect studies"Phys.Rev B. 67. 100509-1-100509-4 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] L.Zhu et al.: "Preparation and properties of the ternary ZrNF"Solid State Commun.. 130. 227-230 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Ito et al.: "Superfluid density of layered superconductors LixHfNCl and LixZrNCl with/without co-intercalation of THF (tetrahydrofuran) : muon spin relaxation and magnetization measurements"Phys.Rev.B. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Inumaru et al.: "Synthesis and High Metallic Conductivity of Layer-Structured Sr_2N Thin Film Deposited onto MgO(001) Substrate"Appl.Surface Sci.. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Yamanaka et al.: "Synthesis and Properties of New Superconductors with Cage and Layered Structures"Jpn.J.Appl.Phys.. 41. 5008-5012 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Yamanaka et al.: "Alkali Metal Intercalation in Layer Structured α-HfNBr"J.Phys.Chem.Solid. 65. 565-569 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Yamanaka et al.: "Superconductivity of Layer Structured TiNCl Intercalated with Pyridine"Molecular Crystals and Liquid Crystals. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Shamoto et al.: "Structural Study on Na_xHfNCl System"Physica C. 402. 283-292 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] L.Zhu: "Preparation and superconductivity of Chlorine-Deintercalated Crystals β-M NCl_<1-x> (M=Zr, Hf)"Chem.Mater.. 15. 1897-1902 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Yamamaka: "Electron-doping and superconductivity in layer-structured nitride chlorides, β-MNCL (M=Zr, Hf)"Physica B. 328. 6-9 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Ekino: "Tunneling spectroscopy of MgB_2 and Li_x(THF)_yHfNCl"Physica B. 328. 23-25 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Ekino: "Tunneling spectroscopy of the electron-doped layered superconductor Li_<0.48>(THF)_<0.3>HfNCl"Physica B. 388-389. 1323-1324 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Tou: "Superconducting characteristics in electron-doped layered hafnium nitride : ^<15>N isotope effect studies"Phys.Rev.B. 67. 100509/1-100509/4 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Yamanaka: "Alkali Metal Intercalation in Layer Structured α-HfNBr"J.Phys.Chem.Solids. 65. 565-569 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Shamoto: "Structural Study on Na_xHfNCl System"Physica C. 402. 283-292 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Itoh: "Superfluid density of layered tH superconductors Li_xHfNCl and Li_xZrNCl with/ without co-intercalation of THF (tetrahydrofuran) : muon spin relaxation and magnetization measurements"Phys.Rev.B. (印刷中). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] L.Zhu: "Preparation and Properties of the ternary nitride ZrNF"Solid State Commun.. 130. 227-230 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Inumaru: "Preparation and transport properties of Nbl-xCrxN epitaxial thin films on silicon wafers"Physica B. 328. 123-124 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Inumaru: "Layer-by-Layer Deposition of Epitaxial TiN-CrN Multilayers on MgO (001) by Pulsed Laser Ablation"Appl.Surface Sci.. (印刷中). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Inumaru: "Preparation of Superconducting Epitaxial Thin Films of Tansition Metal Nitrides on Silicon Wafers by Molecular Beam Epitaxy"J. Crystal Growth. 237-239. 2050-2054 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] X.Chen: "High-Pressure Synthesis and Crystal Structures of β-MNX(M=Zr, Hf ; X=Br, I)"J. Solid State Chem.. 163. 77-83 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] L.Zhu: "Novel synthesis of TiN fine powders by nitridation with ammonium chloride"Mater. Res. Bull.. 37. 475-483 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Tou: "Dc-magnetization and ^1H-NMR studies of layered superconductor Li_<0.48>(THF)_<0.3>HfNCl"Physica B. 312-313. 155-156 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] X.Chen: "High-Pressure Synthesis and Crystal Structures of β-MNX(M=Zr, Hf ; X=Cl, Br, I)"J. Phys. Condens. Matter. 14. 11209-11212 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] L.Zhu: "Zirconium Nitride Derived from Layer Structured β-ZrNCl by Deintercalation of Chlorine Layers"Chem. Mater.. 14. 4517-4521 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Sakamoto: "Pulsed laser deposition of novel nitride solid solution films Ni_xTi_<1-x>N_y on MgO(001)"Appl. Surface Sci.. 199. 303-306 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] X.Chen: "The first single-crystal X-ray structural refinement of the superconducting phase Li_<0.2(1)>ZrNCl derived by intercalation"J. Solid State Chem.. 169. 149-154 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Yamanaka: "Synthesis and Properties of New Superconductors with Cage and Layered Structures"Jpn. J. Appl. Phys.. 41. 5008-5012 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Yamanaka: "Electron-doping and superconductivity in layer-structured nitride chlorides, β-MNCl(M=Zr, Hf)"Physica B. (印刷中). (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Ekino: "Tunneling spectroscopy of MgB_2 and Li_<0.5>(THF)_yHfNCl"Physica B. (印刷中). (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] L.Zhu: "Preparation and Superconductivity of Chlorine-Deintercalated Crystals β-MNCl_<1-x>(M=Zr, Hf)"Chem. Mater.. (印刷中). (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Tou: "Unusual ^<15>N isotope effect in the electron-doped superconductor Li_<0.48>(THF)_<0.3>HfNCl"Phys. Rev. B. (印刷中). (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] 日本化学会編(山中昭司他共著): "先端化学シリーズII、電気化学、光化学、無機化学、環境ケミカルサイエンス"丸善株式会社. 330 (2002)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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