Interfacial N→Sb Nonbonded Interaction Enhances the Photoelectronic Performance of PVP‐Capped Sb₂S₃ Amorphous Colloids

Abstract The bonded or nonbonded interactions at the interface of ligands and surface atoms are a core issue in engineering the surface chemistry and (photo)electronic properties of semiconductor colloidal solids. Herein, we demonstrate the interfacial Lewis acid‐base N→Sb nonbonded interaction: N atoms in polyvinylpyrrolidone (PVP) molecules acting as an electron donor to enhance the photoconductivity and ‐responsivity of PVP‐capped Sb₂S₃ amorphous semiconductor colloids. The electron donation effect of PVP N atoms in the N→Sb interaction is backed by the upper shift of N 1s binding energy in the X‐ray photoelectron spectra (XPS) and the relevant literature. The repulsion of lone pair electrons (LPEs) of N atoms is thought to make 5 s² LPEs of Sb atoms retract from Sb nuclei with an increased orbital volume, giving rise to high probability for the overlap and coupling of 5 s² LPEs among neighboring Sb atoms on the surface of Sb₂S₃ amorphous colloids. Such a spatially and energetically matched electron‐electron coupling greatly contributes to the photoelectronic performance enhancement of amorphous Sb₂S₃. We believe that the electron coupling and improved (photo)electronics can be generalized in many semiconductors containing ns² LPE metal cations by the surface/interface Lewis acid‐base interactions with suitable ligands.