A highly selective non-radical diazo coupling provides low cost semi-conducting carbon nanotubes
A highly selective non-radical diazo coupling provides low cost semi-conducting carbon nanotubes
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DOI：
10.1016/j.carbon.2013.08.064
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发表时间：
2014-01-01
期刊：
影响因子：
10.9
通讯作者：
Chenevier, Pascale
中科院分区：
文献类型：
--
作者：
Darchy, Lea;Hanifi, Nassim;Chenevier, Pascale
尽管半导体碳纳米管（sc-CNT）在低成本、柔性和高频电子和光伏方面具有公认的潜力，但由于它们是与金属碳纳米管（m-CNT）混合合成的，因此尚未导致工业发展。分类已被广泛研究，但成本仍然很高。在这里，所提出的CNT化学处理以前所未有的选择性使用重氮醚，避免m-CNT和sc-CNT分离。实际上，与常规重氮偶联（对m-CNT部分选择性）一样，重氮醚偶联诱导纳米管导电性的消失。通过发光、拉曼光谱和电导率证明，重氮醚的选择性比重氮盐高50倍。将含有非活性m-CNT和高度保存的sc-CNT的经处理的CNT溶液用于具有高度增加的开/关比的晶体管中。此外，重氮醚/CNT反应被发现遵循一个意想不到的耦合机制：化学计量的，自由基的反应，而不是自由基的重氮链反应。这种机理上的剧烈变化，加上对反应动力学和热力学的完整描述，使得对反应的调节和精细控制变得容易。作为一种通用的处理剂，重氮醚提供了一种廉价的sc-CNT材料，可用于印刷电子产品的大规模使用。(C)2013爱思唯尔有限公司保留所有权利。
Despite their recognized potential for low cost, flexible and high frequency electronics and photovoltaic, semi-conducting carbon nanotubes (sc-CNTs) did not lead to industrial development yet because they are synthesized as a mixture with metallic carbon nanotubes (m-CNTs). Sorting has been widely studied but cost remains high. Here, the proposed CNT chemical treatment uses diazoether with unprecedented selectivity, avoiding m-CNT and sc-CNT separation. Indeed like conventional diazonium coupling, partly selective for m-CNTs, diazoether coupling induces extinction of nanotube conductivity. The diazoether proved 50 times more selective than diazonium as shown by luminescence, Raman spectroscopy and electrical conductivity. Treated CNT solutions containing inactive m-CNTs and highly preserved sc-CNTs were used in transistors with highly increased ON/OFF ratio. Furthermore, the diazoether/CNT reaction was found to follow an unexpected coupling mechanism: a stoichiometric, radical-free reaction instead of a radical chain reaction for diazonium. This drastic change in mechanism, together with a complete description of the reaction kinetics and thermodynamics, brought easy tuning and fine control on the reaction. As a versatile treatment diazoether provides a cheap sc-CNT material for large scale use in printed electronics. (C) 2013 Elsevier Ltd. All rights reserved.