Development of Organic Superconductors by Reduction of Intermolecular Interaction

通过减少分子间相互作用开发有机超导体

• 批准号: 14540539
• 负责人: YAMADA Jun-ichi
• 金额: $ 2.37万
• 依托单位: University of Hyogo (2004)Himeji Institute of Technology (2002-2003)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540539/
• 关键词: Organic Superconductor; Intermolecular Interaction; Non-TCF Donor; Extension of σ-Bond Framework; Reduction of π-System; Effective Cyclotron Mass; Magnetoresistance; Superconducting Hydrate; 反強磁性超伝導体; 反強磁性金属; π-d相互作用; HOMO; 結晶構造; 国際情報交換; アメリ

Tetrachalcogenafulvalene(TCF) donors are no longer essential to the production of organic superconductors, excluding fullerene superconductors. Indeed, the non-TCF-containing π-electron donor BDA-TTP [which contains the bis-fused 1,3-dithiol-2-ylidene(BDY) unit instead of the TCF unit as a π-electron system] and the 1,3-dithiol-2-ylidene (DT)-based π-donor DODHT do give superconducting salts. Our molecular design strategy for these π-donors is based on the following requirements : (i)the extension of the σ-bond framework and (ii)the reduction of the π-system. These requirements are thought to lead to a decrease of intermolecular interaction, which would be crucial in achieving superconductivity. In addition to their superconductivity, we have found the outstanding physical properties of the SbF_6 and FeCl_4 salt of BDA-TTP. β-(BDA-TTP)_2SbF_6 was proved to have the largest effective cyclotron mass (12.4±1.1 m_e) yet found in organic superconductors. This result indicates that the electron-electron interaction is probably enhanced in the BDA-TTP superconductor. Angular dependent and variable-temperature magnetoresistance(MR) measurement for β-(BDA-TTP)_2FeCl_4 under pressure showed an abrupt drop of MR. A similar anomaly in MR has been reported in κ-(BETS)_2FeBr_4 and λ-(BETS)_2FeCl_4, which exhibit magnetic-field-induced superconductivity. Similar to the superconductors β"-(DODHT)_2X (X=AsF_6 and PF_6) at 16.5 kbar, the β"-(DODHT)_2BF_4・H_2O hydrate was found to undergo an superconducting transition under an applied pressure of 15.5 kbar. The common noticeable feature of the three DODHT superconductors is that they all show a variety of pressure-induced conducting behaviors, including the insulating (or semiconducting), metallic, and superconducting phases. In this way, we succeeded in finding a series of non-TCF-based organic superconductors with notable features.

除了富勒烯超导体外，四氯醛烯（TCF）供体对有机超导体的生产不再是必需的。事实上，不含TCF的π电子给体BDA-TTP[包含双熔合的1,3-二硫醇-2-乙基（BDY）单元代替TCF单元作为π电子体系]和基于1,3-二硫醇-2-乙基（DT）的π电子给体DODHT确实能产生超导盐。我们对这些π-给体的分子设计策略是基于以下要求：(1)σ-键框架的扩展和(2)π-体系的缩减。这些要求被认为会导致分子间相互作用的减少，这对实现超导性至关重要。BDA-TTP的SbF_6和FeCl_4盐除了具有超导性外，还具有优异的物理性能。β-(BDA-TTP)_2SbF_6被证明具有有机超导体中最大的有效回旋加速器质量（12.4±1.1 m_e）。这一结果表明，BDA-TTP超导体中电子-电子相互作用可能得到增强。β-(BDA-TTP)_2FeCl_4在压力下的角相关和变温磁阻（MR）测量显示MR急剧下降，κ-(BETS)_2FeBr_4和λ-(BETS)_2FeCl_4的磁阻也有类似的异常，它们表现出磁场诱导的超导性。与超导体β"-(DODHT)_2X （X=AsF_6和PF_6）在16.5 kbar下相似，β"-(DODHT)_2BF_4·H_2O水合物在15.5 kbar的施加压力下发生超导转变。三种DODHT超导体的共同显著特征是它们都表现出各种压力诱导的导电行为，包括绝缘（或半导体）、金属和超导相。通过这种方式，我们成功地发现了一系列具有显著特征的非tcf基有机超导体。

项目成果

Hiroyuki Nishikawa: "A new organic superconductor,(DODHT)_2BF_4・H_2O"Chemical Communications. 494-495 (2003)

Hiroyuki Nishikawa：“一种新的有机超导体，(DODHT)_2BF_4・H_2O”化学通讯494-495 (2003)。

A Novel BEDT-TTF-based Organic Conducting Salt with a Ferrocene-containing Dianion, a-(BEDT-TTF)_4(Fe(Cp-CONHCH_2SO_3)_2)・4H_2O

一种新型BEDT-TTF基二茂铁二价阴离子有机导电盐a-(BEDT-TTF)_4(Fe(Cp-CONHCH_2SO_3)_2)·4H_2O

• 发表时间: 2004
• 期刊: Chem.Lett. 33
• 作者: R.Shibaeva;H.Nishikawa;J.Yamada;J.Yamada;T.Amano;E.S.Choi;K.Furuta
• 通讯作者: K.Furuta

Effect of the gap due to anion ordering in deuterated (TMTSF)_2ClO_4 at high magnetic fields

高磁场下氘化 (TMTSF)_2ClO_4 中阴离子排序引起的间隙效应

• 发表时间: 2003
• 期刊: Synth.Met. 133-134
• 作者: R.Shibaeva;H.Nishikawa;J.Yamada;J.Yamada;T.Amano;E.S.Choi;K.Furuta;J.Yamada;J.Yamada;E.S.Choi;H.Nishikawa;J.Yamada;Hiroki Akutsu;Irina Shevyakova;Jun-ichi Yamada;Eun S.Choi;Jun-ichi Yamada;Jun-ichi Yamada;H.Nishikawa;S.Nakatsuji;E.S.Choi;S.Nakatsuji;T.Kaneko;H.Akutsu;J.Yamada;H.Akutsu;H.Akutsu;Y.Ogawa;J.Yamada;K.Nomura;A.Hoshikawa;N.Matsunaga
• 通讯作者: N.Matsunaga

Upper critical fields of pressurized organic superconductors κ-(BEDT-TTF)_2X in the magnetic fields parallel to the layer

平行于层的磁场中加压有机超导体κ-(BEDT-TTF)_2X的上临界场

• 发表时间: 2003
• 期刊: Synth.Met. 133-134
• 作者: R.Shibaeva;H.Nishikawa;J.Yamada;J.Yamada;T.Amano;E.S.Choi;K.Furuta;J.Yamada;J.Yamada;E.S.Choi;H.Nishikawa;J.Yamada;Hiroki Akutsu;Irina Shevyakova;Jun-ichi Yamada;Eun S.Choi;Jun-ichi Yamada;Jun-ichi Yamada;H.Nishikawa;S.Nakatsuji;E.S.Choi;S.Nakatsuji;T.Kaneko;H.Akutsu;J.Yamada;H.Akutsu;H.Akutsu;Y.Ogawa;J.Yamada;K.Nomura;A.Hoshikawa;N.Matsunaga;K.Yamashita;J.Yamada;H.Nishikawa;Y.Shimojo
• 通讯作者: Y.Shimojo

Field-induced SDW phase diagram of (TMTSF)_2PF_6 at high magnetic fields

(TMTSF)_2PF_6 在高磁场下的场感 SDW 相图

• 发表时间: 2003
• 期刊: Physica B 329-333
• 作者: R.Shibaeva;H.Nishikawa;J.Yamada;J.Yamada;T.Amano;E.S.Choi;K.Furuta;J.Yamada;J.Yamada;E.S.Choi;H.Nishikawa;J.Yamada;Hiroki Akutsu;Irina Shevyakova;Jun-ichi Yamada;Eun S.Choi;Jun-ichi Yamada;Jun-ichi Yamada;H.Nishikawa;S.Nakatsuji;E.S.Choi;S.Nakatsuji;T.Kaneko;H.Akutsu;J.Yamada;H.Akutsu;H.Akutsu;Y.Ogawa;J.Yamada;K.Nomura;A.Hoshikawa;N.Matsunaga;K.Yamashita;J.Yamada;H.Nishikawa;Y.Shimojo;T.Arai;T.Mizutani;H.Ito;E.Ohmichi;J.YAMADA;N.Matsunaga;K.Yokoyama;Y.Shimojo;F.Setifi;A.Miyazaki;K.Kikuchi;H.Ito;H.Nishikawa;E.Ohmichi;M.A.Tanatar;A.Miyazaki;N.Matsunaga
• 通讯作者: N.Matsunaga