Realizing nearly-free-electron like conduction band in a molecular film through mediating intermolecular van der Waals interactions.

Cui, Xingxia; Han, Ding; Guo, Hongli; Zhou, Linwei; Qiao, Jingsi; Liu, Qing; Cui, Zhihao; Li, Yafei et al. · Nat Commun · 2019

basic_science · Level V

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Abstract

Collective molecular physical properties can be enhanced from their intrinsic characteristics by templating at material interfaces. Here we report how a black phosphorous (BP) substrate concatenates a nearly-free-electron (NFE) like conduction band of a C<sub>60</sub> monolayer. Scanning tunneling microscopy reveals the C<sub>60</sub> lowest unoccupied molecular orbital (LUMO) band is strongly delocalized in two-dimensions, which is unprecedented for a molecular semiconductor. Experiment and theory show van der Waals forces between C<sub>60</sub> and BP reduce the inter-C<sub>60</sub> distance and cause mutual orientation, thereby optimizing the π-π wave function overlap and forming the NFE-like band. Electronic structure and carrier mobility calculations predict that the NFE band of C<sub>60</sub> acquires an effective mass of 0.53-0.70 m<sub>e</sub> (m<sub>e</sub> is the mass of free electrons), and has carrier mobility of ~200 to 440 cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup>. The substrate-mediated intermolecular van der Waals interactions provide a route to enhance charge delocalization in fullerenes and other organic semiconductors.