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）Mott绝缘子κ-（BEDT-TTF）II D22CUI D22（CN）II D23D2的阴离层由（CN-CU）II D2NI D2的无限ZIGZAG聚合物链组成，并混乱[NC] II D1-1II D1 antion，它连接了Infrinite Chains。 [NC-N-CN] II D1 D1-1II D1组的一半（CN-CU）II D2NI D2和全部无序CN组的替换提供了超导体κ-（BEDTTTTF）II D22CU（cn）[N（CN）II D22CU（D2]）II D22CU（D2]，TC = 11K。通过部分替代品。 D2（CN）D23-2YE D2 [N（CN）D2 D2] D2YE D2，其中Y主要在0.05、0.3至0.4和0.4和0.4和X = 0到1600 ppm的情况下[n（cn）d22e d2 d2] d1 d1 d1 d1 d1。用于3.1、6.5、7.5，…更多8.8和10.2 k.2）使用相同的电解质进行κ-（bedt-ttf）D22-x-x-Y D2（CUI D1+1 D1）D22-X-X-Y D2（CUI D1+2 D1+2 D1+2 D1）D2X（CN）D23-2Y D2 D2 [n（CUI D1+2 D1）d2 d2 [n（cn）d222]超导性（TC = 11K）。晶体的晶格参数表示θ型结构。3）在BEDT-TTF盐中观察到金属行为降至2-3 K，四硝基苯酚dianion dianion dianion或Tetracyanoallyalyallide Anions的有机阴离子（RO-TCAII D1-IE D1 D1）。带有柔性阴离子的BEDT-TTF的Mott绝缘子Ro-Tcaii D1-EID1在去除结晶溶液后转变为金属络合物。带有阴离子的BEDT-TTF复合物由过渡金属和二硫代氧化物组成，产生了半金属络合物，显示在4.7 kbar（Onset 7 K）的压力下，冷却时的电阻突然降低。现在正在检查超导性的发生。4）检查复合物的带宽EOET（EOET），即BedT-TTF和Bedo-TTF之间的杂交分子，以进行复杂的形成。随着Bedo-TTF的自组合特性的应用，通过将卤素掺杂到1 wt％的贝托-TTF和多碳酸盐复合材料的膜来制备无色金属膜。5）拉曼光谱研究的碱性研究，对碱性化的Omttf omttf omttf cii d260e d2复合物却揭示了该物种，以表明该物种的疾病，以使这些疾病既有事件，使得出现了这些事件。当原始复合物分别用RB和K掺杂时，CII D260E D12-E D12和CII D260E D13-E D12。使用CII D260E D2CII D26E D2，CII D260E D2BRII D2XE D2（X = 6，8），它们比CII D260E D2更强的电子受体，比CII D260E D2更强，研究了有机分子的复合物的制备。或D-π-A型分子。制备了替代堆栈的第一个金属络合物（HMTTEF・ETIE D22IE D2TCNQ ・THFX）。同样，在一系列Dyy D1+YIE D1-yii D1-yie D1 D1分子上检查了分子内电荷转移（γ）的程度。较少的

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）

G.Saito: "Organic Molecular Solids…Properties and Application, Chapter 10"CRC Press. 309-340 (1997)

G.Saito：“有机分子固体……特性和应用，第 10 章”CRC Press 309-340 (1997)。