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)阴离子层莫特绝缘体κ- (BEDT-TTF)ィイD22摊位ィエD2CuィイD22摊位ィエD2 (CN)ィイc15ィエD2由无限曲折聚合物链(CN-Cu)ィイD2nィエD2和无序(NC)ィイD1-1ィエD1阴离子连接无限链。将（CN- N-CN）一半的（CN- cu） D2n D2和整个无序CN基团替换为[NC-N-CN] D1-1 D1基团，得到了一个Tc =11K的超导体κ-(BEDT-TTF) D22 D2Cu(CN)[N(CN) D22 D2]。采用部分置换法制备了Tc在3K ~ 10.5K范围内的超导体。同时，部分Cu γ γ +1 γ +1 γ + D1离子被Cu γ +2 γ + D1离子取代。结果表明，该体系为κ-(BEDT-TTF) D22 D2(Cu D1+1 D1) D22-x D2(Cu D1+2 D1) D2x D2(CN) D23-2y D2[N(CN) D22 D2] D2y D2，其中y主要取0.05、0.3 ~ 0.4和0.8,x=0 ~ 1600 ppm。阴离子[N(CN) D22 D2] D1-1 D1均匀分布于阴离子层中。单晶的y = 0.3 ~ 0.4展出不同Tc的3.1,6.5,7.5 , ... 8.8和10.2 K.2)使用相同的电解质κ- (BEDT-TTF)ィイD22摊位ィエD2(铜ィイD1 + 1ィエD1)ィイD22-x-yィエD2(铜ィイD1 + 2ィエD1)ィイD2xィエD2 (CN)ィイD23-2yィエD2 [N (CN)ィイD22摊位ィエD2)ィイD2yィエD2,得到了一些晶体不同的形状和超导(Tc = 11 k)。晶体的晶格参数为θ型结构。3)四硝基双酚双离子或四氰烯丙烯基阴离子（RO-TCA）的有机阴离子（RO-TCA）在2 ~ 3 K范围内具有金属行为。Mott绝缘体的BEDT-TTF具有柔性阴离子，RO-TCA在溶剂脱除后转化为金属配合物结晶。由过渡金属和二硫代草酸盐组成的带阴离子的BEDT-TTF配合物得到了半金属配合物，在4.7 kbar（起始7 K）压力下冷却时电阻率突然下降。超导现象的发生目前正在研究中。4)为了研究配合物的带宽控制，采用bett - ttf和BEDO-TTF之间的杂化分子EOET形成配合物。利用BEDO-TTF的自组装特性，在1 wt%的BEDO-TTF薄膜和聚碳酸酯复合材料上掺杂卤素，制备了无色金属薄膜。5)对碱掺杂OMTTF·C φ φ D260 φ φ D2配合物的拉曼光谱研究表明，当原始配合物分别掺杂Rb和K时，其超导性的发生需要C φ φ D260 φ φ D12- C φ φ D1 φ φ D2和C φ φ D260 φ φ D13- C φ φ D1 φ φ D2阴离子的存在。以C γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ。6)我们已经开始研究制备由交替堆叠或D-π-A型分子组成的新类别有机超导体。制备了交替堆叠的第一个金属配合物（HMTTeF·Et D22 D2TCNQ·THFx）。此外，还测定了D γ γ +Y γ γ -π-A γ γ -Y γ γ型分子的分子内电荷转移度。少

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）。

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）

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)

H. Tsukada: "Proton Spin Relaxation due to Localization in Weekly Disordered System"J. Phys. Soc. Jpn.. 69.5. 1556-1559 (1998)

H. Tsukada：“周无序系统中局域化导致的质子自旋弛豫”J。