Oxidative reactivity of alkali-like superatoms of group 5 metal-encapsulating Si16 cage nanoclusters

Abstract It is crucial to control the reactivity of surface silicon atoms for applications in miniaturized silicon-based nanodevices. Here we demonstrate that reactive silicon atoms are made unreactive by forming a Si16 cage that encapsulates a metal atom. Specifically, group 5 metal-encapsulating Si16 nanoclusters (M@Si16: M = V, Nb, and Ta) exhibit alkali-like superatomic behavior on n-type C60 substrates, where charge transfer between M@Si16 and C60 satisfies the 68-electron shell closure as M@Si16+. The oxidation properties of M@Si16+ are investigated by X-ray photoelectron spectroscopy, revealing that the chemical stability of the caged silicon surface towards oxygen is enhanced by a factor of 104 compared to a crystalline silicon surface, and that M@Si16 are oxidized stepwise from the outer Si16 cage to the central metal atom. While the nanoclusters share a common Si16 cage, their chemical robustness depends on a superatomic “periodicity” (Ta@Si16 > V@Si16 > Nb@Si16) which is explained by the electron density distributions of M@Si16 investigated by DFT calculations.