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Neutral-ionic phase transition in two-dimensional organic semiconductor

Research Project

Project/Area Number 13440088
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 固体物性Ⅰ(光物性・半導体・誘電体)
Research InstitutionNational Institute of Advanced Industrial Science and Technology (AIST) (2003)
Hokkaido University (2001-2002)

Principal Investigator

HASEGAWA Tatsuo  National Institute of Advanced Industrial Science and Technology (AIST), Correlated Electron Research Center (CERC), Senior Researcher, 強相関電子技術研究センター, 主任研究員 (00242016)

Co-Investigator(Kenkyū-buntansha) MIZOGUCHI Kenji  Tokyo Metropolitan University, Graduate School of Science, Professor, 理学研究科, 教授 (40087101)
NAKAMURA Takayoshi  Hokkaido University, Research Institute for Electronic Science, Professor, 電子科学研究所, 教授 (60270790)
AKUTAGAWA Tomoyuki  Hokkaido University, Research Institute for Electronic Science, Associate Professor, 電子科学研究所, 助教授 (60271631)
Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥12,600,000 (Direct Cost: ¥12,600,000)
Fiscal Year 2003: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 2002: ¥4,900,000 (Direct Cost: ¥4,900,000)
Fiscal Year 2001: ¥6,500,000 (Direct Cost: ¥6,500,000)
KeywordsOrganic Semiconductor / Valence Instability / Neutral-Ionic Phase Transition / Crystal Structure Analysis / Electron Paramagnetic Resonance / Dielectric Properties / Quantum Critical Point / High-Pressure Measurement / 電荷移動錯体 / 中性イオン性転移 / 圧力温度相図 / 熱揺らぎ / ドメイン構造 / 中性-イオン性転移 / 巨大誘導応答 / 高圧下測定 / 中性子回折 / 誘導特性 / 巨大誘電応答
Research Abstract

Valence instability or neutral-ionic (NI) phase transition in molecular semiconductor crystal, (BEDT-TTF)(ClMeTCNQ), is studied. We undertake to explore the new electronic phenomena based on the valence fluctuations around the quantum critical point, by studying the structural, magnetic, and dielectric properties of the compound under pressure and low temperature. The results of this project are summarized as follows;
1.Structure analyses:
We successfully developed the Be-based high pressure cell (application filed for a patent) for X-ray diffraction measurements under uniaxial pressure and low temperature. With use of this facility, we succeeded in the structural analyses below and above the NI transitions and observed the variation in the crystal symmetry and lattice constants.
2.ESR study:
By magnetic probe sensitive to the appearance of cation and anion radical 1/2-spins, we directly demonstrated how the NI phase transition develop in (BEDT-TTF)(ClMeTCNQ). By the analyses of the temper … More ature dependence of magnetic susceptibility under pressure, we observed the continuous evolution of the ionic domain fraction through the transition temperature. Particular finding is a presence of the thermoinduced NI meso-phase, where ionic radicals survive even at much higher temperature than the transitions. We conclude that this feature should be the origin of the drastic exponential increase of the magnetic susceptibility at room temperature with application of pressure.
3.Dielectric measurements:
Enhancement in dielectric response of (BEDT-TTF)(ClMeTCNQ) was observed around quantum critical point of the NI phase transitions. As the enhancement is temperature-and frequency-independent, we conclude that the enhancement should be ascribed to the quantum valence fluctuation between the neutral and ionic phases.
We also clarify the mechanism of magneto-lattice phase transitions in (BEDO-TTF)(Cl2TNCQ), which is an isomorphous compound with (BEDT-TTF)(ClMeTCNQ). Furthermore, the research is expanded to the new method for the valence control of molecular semiconductors with use of the FET device structures. Less

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] T.Hasegawa et al.: "Neutral-ionic phase transition of (BEDT-TTF)(ClMeTCNQ) under pressure"Physical Review B. 64. 85106-1-85106-7 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Sakamoto et al.: "Magnetic properties of (BEDT-TTF)(ClMeTCNQ) studied by ESR under pressure : an N-I crossover and thermoinduced mesophase"Physical Review Letters. (投稿中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Y.Takahashi et al.: "Enhanced dielectric response is (BEDT-TTF)(ClMeTCNQ) at the Neutral-Ionic Phase Transitions"Journal de Physique IV. (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] T.Hasegawa et al.: "Novel magneto-lattice transition is the mined-stack charge-transfer complexes with intercolumnar networks"Synthetic Metals. 133-134. 623-625 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Hasegawa et al.: "Ambipolar field-effect carrier injections in organic Mott insulators"Physical Review 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] T.Sato et al.: "2kF transitions is a series of(DMET)2(X1X2TCNQ)[X1,X2 Br,Cl,F,CH3,H] ; subsidiary lattice effect by the anion radicals"Physical Review B. 69. 075103-1-075103-5 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Hasegawa et al.: "Neutral-ionic phase transition of (BEDT-TTF)(ClMeTCNQ) under pressure"Phys.Rev. B. Vol.64. 85106 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Sakamoto et al.: "Magnetic properties of (BEDT-TTF)(ClMeTCNQ) studied by ESR under pressure : an N-I crossover and thermoinduced mesophase"Phys.Rev.Lett.. (submitted).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Y.Takahashi et al.: "Enhanced dielectric response in (BEDT-TTF)(ClMeTCNQ) at the Neutral-Ionic Phase Transitions"Journal de Physique IV. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Hasegawa et al.: "Novel magneto-lattice transition in the mixed-stack charge-transfer complexes with intercolumnar networks"Synthetic Metals. vol.133-134. 623 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Hasegawa et al.: "Ambipolar field-effect carrier injections in organic Mott insulator"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] T.Sato et al.: "2kF transitions in a series of (DMET)2(X1X2TCNQ) [X1,X2= Br, Cl, F, CH3,H]; subsidiary lattice effect by the anion radicals"Phys.Rev. B.. vol.69. 075103 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Hasegawa, T.Akutagawa, T.Nakamura: "Novel magneto-lattice phase transition in the mixed-stack charge-transfer complexes with inter-columnar networks"Synthetic Metals. 133-134. 623-625 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Sakamoto, K.Mizoguchi, T.Hasegawa: "ESR studies of (BEDT-TTF) (ClMeTCNQ) under pressure"Synthetic Metals. 133-134. 627-628 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Sato, T.Hasegawa, T.Akutagawa, T.Nakamura, R.Kondo: "2kF transitions in a series of (DMET)2(X1X2TCNQ) [X1,X2 = Br,Cl,F,CH3,H] ; subsidiary lattice effect by the anion radicals"Physical Review B. 69. 075103-1-075103-5 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Akutagawa, T.Uchimaru, K.Sakai, T.Hasegawa, T.Nakamura: "Bidentated Hydrogen-bond from [O-H 〜 N-N 〜 H-O] to [O- +H-N-N-H+ 〜-O] Structures in Solid"Journal of Physical Chemistry B. 107. 6248-6251 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Sakai, T.Akutagawa, T.Hasegiawa, T.Nakamura: "Thed-L(p)-ptype of charge-transfer salt [Cu(Me-tri)2][Ni(dmit)2]2 : Interaction between copper(II)d- and Ni(dmit)2p-electronsviap-conjugated macrocyclic ligand"Physical Chemistry Chemical Physics. 5. 2469-2475 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Nishihara, T.Akutagawa, T.Hasegawa, T.Nakamura: "Crystal Structure and Magnetic Properties of Gd2([18] crown-6)2(OH)2(CH3CN)2[Ni(dmit)2]4 Complex Having f- and II-spins"Inorganic Chemistry. 42. 2480-2482 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T. Hasegawa: "Neutral-ionic phase transition of (BEDT-TTF)(ClMeTCNQ) under pressure"PHYSICAL REVIEW B. 64. 085106 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] K. Hiraki: "Electronic states of novel donor/acceptor type of organic superconductor, (BETS)_2(Cl_2TCNQ)"JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS. 62. 401-403 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] R. Kondo: "Superconductivity and metal-insulator transition in twin-columnar organic superconductor, (BETS)_2(Cl_2TCNQ) [X=Cl, Br]"JOURNAL OF THE PHYSICAL SOCIETY OF JAPAN. 70. 3023-3030 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] T. Hasegawa: "Donor-acceptor-type complexes of (BEDT-TTF)(TCNQ) analogues : Peculiar magnetic transition in (BEDO-TTF)(Cl_2TCNQ)"SYNTHETIC METALS. 120. 991-992 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] R. Kondo: "Metal-insulator transition in donor-acceptor type superconductor, (BETS)_2(Cl_2TCNQ)"SYNTHETIC METALS. 120. 995-996 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] K. Hiraki: "Electronic properties of novel donor-acceptor type charge transfer complexes, (BETS)_2(Cl_2TCNQ) (X=Cl, Br) : H-1, Se-77 and C-13-NMR"SYNTHETIC METALS. 120. 917-918 (2001)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2020-05-15  

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