Solution-Phase Growth of Cu Nanowires with Aspect Ratios Greater Than 1000: Multiscale Theory
Solution-Phase Growth of Cu Nanowires with Aspect Ratios Greater Than 1000: Multiscale Theory
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DOI：
10.1021/acsnano.1c07425
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发表时间：
2021-11-23
期刊：
影响因子：
17.1
通讯作者：
Fichthorn, Kristen A.
中科院分区：
文献类型：
--
作者：
Kim, Junseok;Cui, Jianming;Fichthorn, Kristen A.
五孪晶金属纳米线在现有和新兴技术中得到了广泛的应用。然而，人们对其生长机制知之甚少。我们探测的起源氯化物和烷基胺介导的，溶液相生长的五孪晶铜纳米线从第一性原理使用多尺度理论。采用量子密度泛函理论（DFT）方法，研究了Cu原子在氯覆盖的Cu（100）和Cu（111）表面的键合和表面扩散.我们发现氯化Cu（111）上的Cu原子比氯化Cu（100）上的Cu原子具有更强的结合力和更慢的扩散速度，这与裸Cu表面的趋势相反。我们还探测了面间扩散，发现从Cu（100）到Cu（111）的扩散速度比相反的速度快。使用DFT率在埃尺度的各个站点之间的跳跃，我们计算粗粒度，interfacet率为纳米线的各种长度-高达数百微米-和直径在10纳米范围内。我们预测纳米线的纵横比类似于100，仅基于表面扩散。我们还考虑了自组装的烷基胺层的影响，该层覆盖了大部分{100}面，但在{111}面和{100}/{111}边界附近的“端区”中不存在或薄且无序。随着端区，我们预测在实验范围内的纳米线的纵横比范围很广。我们的工作揭示了卤化物-氯化物促进高纵横比纳米线生长的机制。
Penta-twinned metal nanowires are finding widespread application in existing and emerging technologies. However, little is known about their growth mechanisms. We probe the origins of chloride- and alkylamine-mediated, solution-phase growth of penta-twinned Cu nanowires from first-principles using multiscale theory. Using quantum density functional theory (DFT) calculations, we characterize the binding and surface diffusion of Cu atoms on chlorine-covered Cu(100) and Cu(111) surfaces. We find stronger binding and slower diffusion of Cu atoms on chlorinated Cu(111) than on chlorinated Cu(100), which is a reversal of the trend for bare Cu surfaces. We also probe interfacet diffusion and find that this proceeds faster from Cu(100) to Cu(111) than the reverse. Using the DFT rates for hopping between individual sites at Angstrom scales, we calculate coarse-grained, interfacet rates for nanowires of various lengths-up to hundreds of micrometers-and diameters in the 10 nm range. We predict nanowires with aspect ratios of similar to 100, based on surface diffusion alone. We also account for the influence of a self-assembled alkylamine layer that covers most of the {100} facets, but is absent or thin and disordered on the {111} facets and in an "end zone" near the {100}/{111} boundary. With an end zone, we predict a wide range of nanowire aspect ratios in the experimental ranges. Our work reveals the mechanisms by which a halide-chloride-promotes the growth of high-aspect-ratio nanowires.