Development of Molecular Superconductors Having New Structures

新结构分子超导体的研制

• 批准号: 09304065
• 负责人: SAITO Gunzi
• 金额: $ 26.3万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09304065/
• 关键词: Molecular Superconductor; Organic Superconductor; CィイD260ィエD2 Superconductor; Superconducting Critical Temperature; Two-dimensional Layered Structure; One-dimensional Stacking; Doping; Anion Layer; ド-ピング; ラマン散乱

1) The anion layer of a Mott insulator κ-(BEDT-TTF)ィイD22ィエD2CuィイD22ィエD2(CN)ィイD23ィエD2 is composed of infinite zigzag polymer chains of (CN-Cu)ィイD2nィエD2 and disordered [NC]ィイD1-1ィエD1 anion which connects the infinite chains. A replacement of the half of (CN-Cu)ィイD2nィエD2 and whole disordered CN groups by [NC-N-CN]ィイD1-1ィエD1 groups of it provided a superconductor κ-(BEDT-TTF)ィイD22ィエD2Cu(CN)[N(CN)ィイD22ィエD2] with Tc =11K. Numbers of superconductors having Tc in the range of 3K〜10.5K were prepared by the partial replacement. At the same time, some CuィイD1+1ィエD1 ions were substituted by CuィイD1+2ィエD1 ions. Consequently the system was found to be formulated as κ-(BEDT-TTF)ィイD22ィエD2(CuィイD1+1ィエD1)ィイD22-x-yィエD2(CuィイD1+2ィエD1)ィイD2xィエD2(CN)ィイD23-2yィエD2[N(CN)ィイD22ィエD2]ィイD2yィエD2, where y took mainly 0.05, 0.3〜0.4 and 0.8 and x=0〜1600 ppm. The anion [N(CN)ィイD22ィエD2]ィイD1-1ィエD1 was found to distribute homogeneously in the anion layer. The single crystal of y = 0.3〜0.4 exhibited varied Tc's of 3.1, 6.5, 7.5, … More 8.8 and 10.2 K.2) Using the same electrolyte for κ-(BEDT-TTF)ィイD22ィエD2(CuィイD1+1ィエD1)ィイD22-x-yィエD2(CuィイD1+2ィエD1)ィイD2xィエD2(CN)ィイD23-2yィエD2[N(CN)ィイD22ィエD2]ィイD2yィエD2, some crystals with different shape were obtained and showed the superconductivity (Tc=11K). The lattice parameters of the crystals indicated θ-type structure.3) The metallic behavior down to 2〜3 K was observed in the BEDT-TTF salts the organic anions of tetranitrobiphenol dianion or tetracyanoallylide anions(RO-TCAィイD1-ィエD1). The Mott insulators of BEDT-TTF with the flexible anion, RO-TCAィイD1-ィエD1 transformed into the metallic complexes on the removal of the solvent of crystallization. The BEDT-TTF complex with the anion consists of a transition metal and dithiooxalate gave a semimetallic complex which shows the abrupt decrease of the resistivity on cooling under the pressure of 4.7 kbar (onset 7 K). The occurrence of the superconductivity is now being examined.4) To examine the controlling of the bandwidth of the complexes, EOET, which is the hybrid molecule between BEDT-TTF and BEDO-TTF, was employed for complex formation. As the application of the self-assembling property of BEDO-TTF, the colorless metallic films were prepared by doping halogens to the films of 1 wt% of BEDO-TTF and polycarbonate composite.5) The Raman spectroscopic study of alkali doped OMTTF・CィイD260ィエD2 complexes revealed that the occurrences of their superconductivities require the anion species of CィイD260ィイD12-ィエD1ィエD2 and CィイD260ィイD13-ィエD1ィエD2 when the pristine complex is doped with Rb and K, respectively. With the CィイD260ィエD2CIィイD26ィエD2, CィイD260ィエD2BrィイD2xィエD2(x=6, 8) which are stronger electron acceptors than CィイD260ィエD2, the preparation of the complexes of organic donor molecules were examined.6) We have started the investigations to prepare organic superconductors of new categories, which consist of the alternating stack or D-π-A type molecule. The first metallic complex of the alternating stack was prepared (HMTTeF・EtィイD22ィエD2TCNQ・THFx). Also, the degrees of intramolecular charge-transfer(γ) were examined on the series of DィイD1+YィエD1-π-AィイD1-YィエD1 type molecules. Less

1）莫特绝缘体κ-(BEDT-TTF)D22D2CuD22D2(CN)D23D2的阴离子层由(CN-Cu)D2nD2的无限锯齿形聚合物链和连接无限链的无序[NC]D1-1D1阴离子组成。更换一半(CN-Cu)D2nD2 和由 [NC-N-CN]D1-1D1 基团组成的整个无序 CN 基团提供了超导体 κ-(BEDT-TTF)D22 D2Cu(CN)[N(CN)iiD22ieD2]，Tc = Tc在3K〜10.5K范围内的超导体的数量为11K。同时，一些CuD1+1D1离子被CuiD1+2D1离子取代，发现该系统被配制为。 κ-(BEDT-TTF)D22D2(CuD1+1D1)D22-x-yD2(CuD1+2D1)D2xD2( CN)D23-2D2[N(CN)D22D2]D2D2，其中主要取0.05， 0.3～0.4和0.8，x=0～1600 ppm，阴离子[N(CN)D22D2]D1-1D1均匀分布在阴离子层中，y=0.3～0.4的单晶表现出3.1的不同Tc， 6.5、7.5、……更多 8.8 和 10.2 K.2) 对 κ-(BEDT-TTF)D22D2(CuD1+1D1)D22-x-yD2(CuD1+2D1) D1) D2x D2(CN) D23-2 D2[N(CN) D22 D2 使用相同的电解质] D2 D2,得到了一些不同形状的晶体，并表现出超导性(Tc=11K)，晶体的晶格参数呈θ型结构。3)在BEDT-TTF有机盐中观察到了低至2〜3K的金属行为。四硝基联苯二阴离子或四氰基烯丙基阴离子(RO-TCA-D1-D1) 具有柔性的BEDT-TTF莫特绝缘体。阴离子，RO-TCA-D1-D1在除去结晶溶剂后转化为金属络合物，与阴离子的BEDT-TTF络合物由过渡金属和二硫代草酸盐组成，得到半金属络合物，其显示出电阻率的突然降低。 4.7 kbar 压力下的冷却（起始温度 7 K）目前正在研究超导性的发生。4）研究对带宽的控制。配合物EOET是BEDT-TTF和BEDO-TTF之间的杂化分子，利用BEDO-TTF的自组装特性，通过在薄膜中掺杂卤素来制备无色金属薄膜。 1 wt% 的 BEDO-TTF 和聚碳酸酯复合材料。5) 碱掺杂 OMTTF·CiD260D2 复合物的拉曼光谱研究揭示当原始络合物分别掺杂 Rb 和 K 时，它们的超导性的出现需要 C260D12-D1D1 和 C260D13-D1D1 的阴离子物种， C260D2BrD2xD2(x=6, 8)是比C260D2更强的电子受体，对有机给体分子配合物的制备进行了研究。6)我们已经开始研究制备新类别的有机超导体，这些超导体由交替堆叠或制备了第一个交替叠层金属络合物。 (HMTTeF·EtD22D2TCNQ·THFx) 另外，对D1+YD1-π-AD1-Y D1型分子系列的分子内电荷转移(γ)的程度进行了研究。

项目成果

A.Otsuka: "Superconductivity in Charge Transfer Complexes of CィイD260ィエD2"Synthetic Metals. 85.1. 1459-1460 (1997)

A.Otsuka：“C260D2 电荷转移配合物的超导性”合成金属 85.1（1997）。

田沼 静一 編集: "高温超伝導体とエキゾチック超伝導体"共立出版. 316 (1999)

田沼精一编辑：“高温超导体和奇异超导体”Kyoritsu Shuppan 316 (1999)。

T.Ishiguro: "Organic Superconductors,2nd Edition" Springer, 522 (1998)

T.Ishiguro：“有机超导体，第二版”Springer，522 (1998)

K.Nishimura: "Preparation of Metallic BEDT-TTF Charge Transfer Complex of 3,3'5,5'-Tetranitro-4,4'-biphenyldiol Dianion (TNBPィイD12-ィエD1) having Flexible Molecular Shape"J. Mat. Chem.. 10.4. 911-919 (2000)

K. Nishimura：“具有柔性分子形状的 3,35,5-四硝基-4,​​4-联苯二阴离子 (TNBP-D12-D1) 的金属 BEDT-TTF 电荷转移络合物的制备”J. ..10.4。911-919（2000）

S.Horiuchi: "Highly Oriented BEDO-TTF Molecules in Metallic Polymer Composites" Molecular Crystals and Liquid Crystals. 296. 365-382 (1997)

S.Horiuchi：“金属聚合物复合材料中的高度取向 BEDO-TTF 分子”分子晶体和液晶。