Department of Electrical Engineering and Department of Chemistry, University of Southern California , Los Angeles, California 90089, United States.
Nano Lett. 2013 Sep 11;13(9):4416-21. doi: 10.1021/nl402259k. Epub 2013 Aug 23.
Structurally uniform and chirality-pure single-wall carbon nanotubes are highly desired for both fundamental study and many of their technological applications, such as electronics, optoelectronics, and biomedical imaging. Considerable efforts have been invested in the synthesis of nanotubes with defined chiralities by tuning the growth recipes but the approach has only limited success. Recently, we have shown that chirality-pure short nanotubes can be used as seeds for vapor-phase epitaxial cloning growth, opening up a new route toward chirality-controlled carbon nanotube synthesis. Nevertheless, the yield of vapor-phase epitaxial growth is rather limited at the present stage, due in large part to the lack of mechanistic understanding of the process. Here we report chirality-dependent growth kinetics and termination mechanism for the vapor-phase epitaxial growth of seven single-chirality nanotubes of (9, 1), (6, 5), (8, 3), (7, 6), (10, 2), (6, 6), and (7, 7), covering near zigzag, medium chiral angle, and near armchair semiconductors, as well as armchair metallic nanotubes. Our results reveal that the growth rates of nanotubes increase with their chiral angles while the active lifetimes of the growth hold opposite trend. Consequently, the chirality distribution of a nanotube ensemble is jointly determined by both growth rates and lifetimes. These results correlate nanotube structures and properties with their growth behaviors and deepen our understanding of chirality-controlled growth of nanotubes.
结构均一且手性纯的单壁碳纳米管在基础研究和许多技术应用中都备受期待,例如电子学、光电学和生物医学成像。人们已经投入了相当大的努力通过调整生长方案来合成具有确定手性的纳米管,但这种方法仅取得了有限的成功。最近,我们已经证明,手性纯的短纳米管可以用作气相外延克隆生长的种子,为手性控制的碳纳米管合成开辟了一条新途径。然而,目前气相外延生长的产率仍然相当有限,这在很大程度上是由于缺乏对该过程的机制理解。在这里,我们报告了七种单手性纳米管(9,1)、(6,5)、(8,3)、(7,6)、(10,2)、(6,6)和(7,7)的气相外延生长的手性依赖性生长动力学和终止机制,涵盖了近锯齿形、中等手性角和近扶手椅半导体以及扶手椅金属纳米管。我们的结果表明,纳米管的生长速率随其手性角的增加而增加,而生长的活性寿命则呈现相反的趋势。因此,纳米管束的手性分布由生长速率和寿命共同决定。这些结果将纳米管的结构和性能与其生长行为联系起来,并加深了我们对手性控制的纳米管生长的理解。