Electrical Conduction of Superatom Thin Films Composed of Group-V-Metal-Encapsulating Silicon-Cage Nanoclusters

Nanocluster assembled films have attracted great interest for designing nanostructured materials with unique electromagnetic properties through a bottom-up approach. Superatoms of group-5 metals (MV = V, Nb, and Ta) encapsulating silicon (Si) cage nanoclusters (MV@Si16), which are synthesized by high-power impulse magnetron sputtering technique, can be efficiently generated to form assembled films. Temperature-dependent current-voltage (I-V) characteristics of the MV@Si16 assembled films revealed that the electrical conduction mechanism is not band transport but hopping transport with Efros-Shklovskii variable range hopping for all central MV atoms. The results show that electrons involved in conduction are strongly correlated to localized electronic states; this correlation arises because of not only the geometrical disordering in noncrystalline assembled films but also the electronic nature of a superatomic 1H orbital with multiple nodes. The localization length depends on the specific MV and is several times the radius of MV@Si16 (0.45 nm); it is the largest for Ta (2.2 nm) and the smallest for Nb (0.8 nm), revealing a periodicity of superatoms.