Stanford Institute for Materials and Energy Sciences, Stanford, California 94305, USA.
Department of Materials Science and Engineering, Stanford, California 94305, USA.
Nat Mater. 2017 Mar;16(3):349-355. doi: 10.1038/nmat4823. Epub 2016 Dec 26.
Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal-organic frameworks and coordination polymers. However, the lack of 'solid' inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal-organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on addition of precursors for nanowire elongation. These nanowires have band-like electronic properties, low effective carrier masses and three orders-of-magnitude conductivity modulation by hole doping. This discovery highlights a previously unexplored regime of structure-directing agents compared with traditional surfactant, block copolymer or metal-organic framework linkers.
通过结构导向剂控制无机结构和维度是一种广泛应用于金属有机骨架和配位聚合物的新材料合成的通用方法。然而，缺乏“固态”无机核需要通过单原子链和/或有机基团进行电荷传输，限制了它们的电子性质。在这里，我们报告说，强相互作用的类金刚石结构导向剂引导具有固态无机核的混合金属-有机硫属化物纳米线的生长，这些无机核具有三原子横截面，代表了可能的最小纳米线。类金刚石之间的强范德华吸引力克服了空间排斥，导致在活性生长前沿形成顺式构型，从而能够在纳米线伸长过程中进行前体的面对面添加。这些纳米线具有带型电子性质、低有效载流子质量和通过空穴掺杂调制三个数量级的电导率。这一发现突出了与传统表面活性剂、嵌段共聚物或金属有机骨架连接剂相比，结构导向剂的一个以前未被探索的领域。
