Encapsulated inorganic nanostructures: a route to sizable modulated, noncovalent, on-tube potentials in carbon nanotubes.
Encapsulated inorganic nanostructures: a route to sizable modulated, noncovalent, on-tube potentials in carbon nanotubes.
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DOI：
10.1021/nn102189w
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发表时间：
2011-04
期刊：
影响因子：
17.1
通讯作者：
A. Ilie;J. Bendall;K. Nagaoka;S. Egger;T. Nakayama;S. Crampin
中科院分区：
文献类型：
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作者：
A. Ilie;J. Bendall;K. Nagaoka;S. Egger;T. Nakayama;S. Crampin
迄今为止合成的各种各样的混合碳纳米管系统（例如，通过封装、包裹或堆叠）提供了一种相互作用的主体，通过该主体来改性主体纳米管以产生新的功能并控制它们的行为。然而，每一种都有局限性：杂交可以强烈地降低所需的纳米管性能;与分子系统的非共价相互作用通常很弱;层状纳米管中的层间相互作用强烈依赖于精确的堆叠顺序。在这里，我们表明，静电/极化相互作用提供了一个通用的路线，设计前所未有的，相当大的和高度调制（1 eV范围），非共价管电位通过封装的无机部分离子相，其中电荷各向异性最大化。专注于银碘（碘化银）纳米线内的单壁碳纳米管，我们利用碘化银的多态性，它创建了各种不同的电荷分布，因此，不同的强度和对称性的相互作用。结合从头计算，高分辨率透射电子显微镜，扫描隧道显微镜和光谱被用来证明对称性破缺的纳米管波函数和新的电子超结构的形成，我们然后与调制，非共价静电/极化电位从碘化银填充。这些管上电位明显强于那些由于其他非共价相互作用已知的碳纳米管系统，并导致显着的波函数的重新分布周围的纳米管，与概念上新的单纳米管电子器件和分子组装的影响。推导出的原理可以更广泛地转化为相关的石墨烯系统，用于设计/控制电势和超结构。
The large variety of hybrid carbon nanotube systems synthesized to date (e.g., by encapsulation, wrapping, or stacking) has provided a body of interactions with which to modify the host nanotubes to produce new functionalities and control their behavior. Each, however, has limitations: hybridization can strongly degrade desirable nanotube properties; noncovalent interactions with molecular systems are generally weak; and interlayer interactions in layered nanotubes are strongly dependent upon the precise stacking sequence. Here we show that the electrostatic/polarization interaction provides a generic route to designing unprecedented, sizable and highly modulated (1 eV range), noncovalent on-tube potentials via encapsulation of inorganic partially ionic phases where charge anisotropy is maximized. Focusing on silver iodide (AgI) nanowires inside single-walled carbon nanotubes, we exploit the polymorphism of AgI, which creates a variety of different charge distributions and, consequently, interactions of varying strength and symmetry. Combined ab initio calculations, high-resolution transmission electron microscopy, and scanning tunneling microscopy and spectroscopy are used to demonstrate symmetry breaking of the nanotube wave functions and novel electronic superstructure formation, which we then correlate with the modulated, noncovalent electrostatic/polarization potentials from the AgI filling. These on-tube potentials are markedly stronger than those due to other noncovalent interactions known in carbon nanotube systems and lead to significant redistribution of the wave function around the nanotube, with implications for conceptually new single-nanotube electronic devices and molecular assembly. Principles derived can translate more broadly to relating graphene systems, for designing/controlling potentials and superstructures.