Department of Materials Science and Engineering, Yonsei University, 134 Shinchon-dong, Seoul, Korea.
ACS Nano. 2010 Apr 27;4(4):2307-19. doi: 10.1021/nn9018575.
We have studied the chemical transformations in ultrathin chalcogenide nanowires with an aim to understand the parameters that control the morphology and crystal structure of the product. Ultrathin Te nanowires were transformed into Ag2Te nanowires with preservation of the single crystallinity. The Ag2Te nanowires were then converted into CdTe, ZnTe, and PbTe using cation-exchange reactions, and the CdTe nanowires were further transformed into PtTe2 nanotubes. On the basis of the solubility products of the ionic solids, the crystal structures of the involved solids, the reaction kinetics, and the reaction conditions for transformations, we were able to reach the following conclusions: (i) The solubility products of ionic solids can be used as a rough criterion to predict if the transformation is thermodynamically favorable or not. (ii) The morphological preservation of reactant nanowires is more sensitive to the change in length rather than the total volume in addition to the lattice matching between the reactant and product nanowires. (iii) The crystal structure resulting from a transformation should be determined by the free energy of formation and the stability of the products. (iv) The transformation involving small volume change or topotactic lattice matching is considered homogeneous along the entire length of the nanowires, preserving both the single crystallinity and the morphology of the reactant nanowires.
我们研究了超薄碲化物纳米线中的化学转化,旨在了解控制产物形态和晶体结构的参数。通过保留其单晶性,将超薄碲纳米线转化为 Ag2Te 纳米线。然后,通过阳离子交换反应将 Ag2Te 纳米线转化为 CdTe、ZnTe 和 PbTe,并且将 CdTe 纳米线进一步转化为 PtTe2 纳米管。基于离子固体的溶度积、所涉及固体的晶体结构、反应动力学以及转化的反应条件,我们得出以下结论:(i)离子固体的溶度积可用作预测转化是否热力学有利的粗略标准。(ii)反应物纳米线的形态保留对长度的变化比对总体积更为敏感,除了反应物和产物纳米线之间的晶格匹配之外。(iii)转化产生的晶体结构应由形成自由能和产物的稳定性决定。(iv)涉及小体积变化或拓扑位错晶格匹配的转化被认为在整个纳米线长度上是均匀的,保留反应物纳米线的单晶性和形态。