Intrinsic glassy-metallic transport in an amorphous coordination polymer
Intrinsic glassy-metallic transport in an amorphous coordination polymer
复制标题
DOI：
10.1038/s41586-022-05261-4
复制
发表时间：
2022-10-26
期刊：
影响因子：
64.8
通讯作者：
Anderson, John S.
中科院分区：
文献类型：
--
作者：
Xie, Jiaze;Ewing, Simon;Anderson, John S.
导电有机材料，如掺杂有机聚合物(1)，分子导体（2,3）和新兴的配位聚合物(4)，支撑着从显示器到柔性电子(5)的技术。在传统的绝缘有机材料中实现高导电性需要通过化学掺杂调整其电子结构(6)。此外，即使是具有内在导电性的有机材料，如单组分分子导体（7,8），也需要结晶度来实现金属行为。然而，导电聚合物通常是无定形的，以帮助耐用性和加工性(9)。利用分子设计在未掺杂的非晶材料中产生高导电性，将在许多应用中实现可调和稳健的导电性（10），但是没有内在导电性的有机材料在无序时保持高导电性。在这里，我们报道了一种无定形配位聚合物，镍四硫代戊烯四硫酸盐，它显示出明显的高电子导电性（高达1200 S cm(-1)）和固有的玻璃金属行为。理论表明，这些特性是由分子重叠实现的，这种分子重叠对结构扰动具有鲁棒性。这组不寻常的特征导致高导电性，在潮湿空气中稳定数周，pH值为0-14，温度高达140摄氏度。这些发现表明，分子设计即使在严重无序的材料中也可以实现金属导电性，提出了关于金属运输如何在没有周期性结构的情况下存在的基本问题，并指出了这些材料令人兴奋的新应用。
Conducting organic materials, such as doped organic polymers(1), molecular conductors(2,3) and emerging coordination polymers(4), underpin technologies ranging from displays to flexible electronics(5). Realizing high electrical conductivity in traditionally insulating organic materials necessitates tuning their electronic structure through chemical doping(6). Furthermore, even organic materials that are intrinsically conductive, such as single-component molecular conductors(7,8), require crystallinity for metallic behaviour. However, conducting polymers are often amorphous to aid durability and processability(9). Using molecular design to produce high conductivity in undoped amorphous materials would enable tunable and robust conductivity in many applications(10), but there are no intrinsically conducting organic materials that maintain high conductivity when disordered. Here we report an amorphous coordination polymer, Ni tetrathiafulvalene tetrathiolate, which displays markedly high electronic conductivity (up to 1,200 S cm(-1)) and intrinsic glassy-metallic behaviour. Theory shows that these properties are enabled by molecular overlap that is robust to structural perturbations. This unusual set of features results in high conductivity that is stable to humid air for weeks, pH 0-14 and temperatures up to 140 degrees C. These findings demonstrate that molecular design can enable metallic conductivity even in heavily disordered materials, raising fundamental questions about how metallic transport can exist without periodic structure and indicating exciting new applications for these materials.