Modulating the Growth Rate, Aspect Ratio, and Yield of Copper Nanowires with Alkylamines,Chemistry of Materials

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Modulating the Growth Rate, Aspect Ratio, and Yield of Copper Nanowires with Alkylamines
Chemistry of Materials ( IF 7.2 ) Pub Date : 2018-04-07 00:00:00 , DOI: 10.1021/acs.chemmater.8b00760
Myung Jun Kim ₁ , Samuel Alvarez ₁ , Tianyu Yan ₂ , Vaibhav Tadepalli ₁ , Kristen A. Fichthorn ₂ , Benjamin J. Wiley ₁

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This article shows how the chain length of alkylamine capping agents and the corresponding stability of their self-assembled monolayers on a Cu surface determines the growth rate, yield, and dimensions of Cu nanowires produced in a solution-phase synthesis. Of the 10 linear alkylamines that were tested, only those with 12 or more carbon atoms induced growth of nanowires. The length, yield, and growth rate of nanowires were larger for shorter alkylamines. As the Cu nanowire growth rates were up to 1050 times smaller than the calculated diffusion-limited growth rates—and the alkylamine chain length had no significant effect on the in situ generation of the reducing agent—we conclude the rate of alkylamine-mediated Cu nanowire growth is limited by charge transfer. Electrochemical measurements indicate longer alkylamines form more effective passivation layers that greatly decrease the rate at which Cu–alkylamine complexes are reduced onto a Cu surface. Molecular dynamics simulations show that the energy required for removal of octadecylamine from a self-assembled monolayer on the Cu surface is much larger (3.59 eV) than for removal of tetradecylamine (2.06 eV). Thus, the more stable self-assembled monolayer formed by longer-chain alkylamines leads to greater inhibition of Cu addition, slower growth, reduced yield, and reduced nanowire aspect ratio.

中文翻译：

用烷基胺调节铜纳米线的生长速率，纵横比和产率

本文显示了烷基胺封端剂的链长以及在铜表面上其自组装单层的相应稳定性如何决定溶液相合成中生产的铜纳米线的生长速率，产率和尺寸。在测试的10种直链烷基胺中，只有具有12个或更多碳原子的那些才会诱导纳米线的生长。对于较短的烷基胺，纳米线的长度，产率和生长速率较大。由于Cu纳米线的生长速率比计算的扩散极限生长速率小1050倍，并且烷基胺链长对还原剂的原位生成没有显着影响，因此我们得出了烷基胺介导的Cu纳米线的生长速率的结论。增长受到电荷转移的限制。电化学测量表明，更长的烷基胺会形成更有效的钝化层，从而大大降低铜-烷基胺络合物在铜表面上的还原速率。分子动力学模拟表明，从铜表面自组装单层去除十八烷基胺所需的能量（3.59 eV）比去除十四烷基胺（2.06 eV）所需的能量大得多。因此，由更长链的烷基胺形成的更稳定的自组装单层导致对Cu添加的更大抑制，更慢的生长，降低的产率和降低的纳米线长宽比。59 eV）比去除十四烷基胺（2.06 eV）。因此，由更长链的烷基胺形成的更稳定的自组装单层导致对Cu添加的更大抑制，更慢的生长，降低的产率和降低的纳米线长宽比。59 eV）比去除十四烷基胺（2.06 eV）。因此，由更长链的烷基胺形成的更稳定的自组装单层导致对Cu添加的更大抑制，更慢的生长，降低的产率和降低的纳米线长宽比。

更新日期：2018-04-07

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