Massive dipoles across the metal–semiconductor cluster interface: towards chemically controlled rectification

Abstract

An interface between a metallic cluster (MgAl₁₂) and a semiconducting cluster (Re₆Se₈(PMe₃)₅) is shown to be marked by a massive dipole reminiscent of a dipolar layer leading to a Schottky barrier at metal–semiconductor interfaces. The metallic cluster MgAl₁₂ with a valence electron count of 38 electrons is two electrons short of 40 electrons needed to complete its electronic shells in a superatomic model and is marked by a significant electron affinity of 2.99 eV. On the other hand, the metal-chalcogenide semiconducting cluster Re₆Se₈(PMe₃)₅, consisting of a Re₆Se₈ core ligated with five trimethylphosphine ligands, is highly stable in the +2 charge-state owing to its electronic shell closure, and has a low ionization energy of 3.3 eV. The composite cluster Re₆Se₈(PMe₃)₅–MgAl₁₂ formed by combining the MgAl₁₂ cluster through the unligated site of Re₆Se₈(PMe₃)₅ exhibits a massive dipole moment of 28.38 D resulting from a charge flow from Re₆Se₈(PMe₃)₅ to the MgAl₁₂ cluster. The highest occupied molecular orbital (HOMO) of the composite cluster is on the MgAl₁₂ side, which is 0.53 eV below the lowest unoccupied molecular orbital (LUMO) localized on the Re₆Se₈(PMe₃)₅ cluster, reminiscent of a Schottky barrier at metal–semiconductor interfaces. Therefore, the combination can act as a rectifier, and an application of a voltage of approximately 4.1 V via a homogeneous external electric field is needed to overcome the barrier aligning the two states: the HOMO in MgAl₁₂ with the LUMO in Re₆Se₈(PMe₃)₅. Apart from the bias voltage, the barrier can also be reduced by attaching ligands to the metallic cluster, which provides chemical control over rectification. Finally, the fused cluster is shown to be capable of separating electron–hole pairs with minimal recombination, offering the potential for photovoltaic applications.