Novel Au/Cu2NiSnS4 Nano-Heterostructure: Synthesis, Structure, Heterojunction Band Offset and Alignment, and Interfacial Charge Transfer Dynamics

Considering the importance of physics and chemistry at material interfaces, we have explored the coupling of multinary chalcogenide semiconductor Cu₂NiSnS₄ nanoparticles (CNTS NPs) for the first time with the noble metal (Au) to form Au-CNTS nano-heterostructures (NHSs). The Au-CNTS NHSs is synthesized by a simple facile hot injection method. Synergistic experimental and theoretical approaches are employed to characterize the structural, optical, and electrical properties of the Au-CNTS NHSs. The absorption spectra demonstrate enhanced and broadened optical absorption in the ultraviolet–visible–near-infrared (UV–Vis–NIR) region, which is corroborated by cyclic voltammetry (CV) readings. CV measurements show type II staggered band alignment, with a conduction band offset (CBO) of 0.21 and 0.23 eV at the Au-CNTS/CdS and CNTS/CdS interface, respectively. Complementary first-principles density functional theory (DFT) calculations predict the formation of a stable Au-CNTS NHSs, with the Au nanoparticle transferring its electrons to the CNTS. Moreover, our interface analysis using ultrafast transient absorption experiments demonstrate that the Au-CNTS NHSs facilitates efficient transport and separation of photoexcited charge carriers when compared to pristine CNTS. The transient measurements further reveal a plasmonic electronic transfer from the Au nanoparticle to CNTS. Our advanced analysis and findings will prompt investigations into new functional materials and their photo/electrocatalysis and optoelectronic device applications in the future.