Superatom Generation and Deposition of Alkali-like Ta@Si 16 and Halogen-like Al 13 via Atomic Aggregation

Surface modification with uniform nanostructures is a promising way to fabricate functionalized surface, and the synthetic electrode functionalization can be performed by depositing atomically precise nanoclusters with a specific number of atoms and compositions. During atomic nucleation and growth in gas phase, atomic aggregates exhibit novel electronic properties, mimicking atoms at a specific number of atoms and composition, which is called superatom (SA). Tantalum-encapsulating Si 16 cage nanoclusters (Ta@Si 16 ) and aluminum 13-mer (Al 13 ) are promising SAs for designing their assembled materials with tunable properties, where one-electron-excessive Ta@Si 16 and one-electron-deficient Al 13 exhibit alkali- and halogen-like characteristics, respectively, owing to the electron shell closing. In this study, with an intense nanocluster ion source, Ta@Si 16 + and Al 13 − were generated during the formation of TaSi n + cations and Al n − anions, where Ta@Si 16 + was remarkably generated compared with the neighboring species. SA deposition provided uniformly decorated surfaces exhibiting nanofunctional properties superior to those obtained by conventional atom deposition. With mass spectrometry, Ta@Si 16 + and Al 13 − SAs were size-selectively soft-landed on the substrate surfaces predeposited with n -type fullerene (C 60 ) and p -type hexa- tert -butyl-hexa- peri -hexabenzocoronene (HB-HBC, C 66 H 66 ). The electronic states of Ta@Si 16 and Al 13 SAs immobilized on the organic substrates were characterized by X-ray photoelectron spectroscopy and oxidative reactivities under O 2 exposure.