Integrating β-Pb_0.33V₂O₅ nanowires with cdse quantum dots: Toward nanoscale heterostructures with tunable interfacial energetic offsets for charge transfer

Achieving directional charge transfer across semiconductor interfaces requires careful consideration of relative band alignments. Here, we demonstrate a promising tunable platform for light harvesting and excited-state charge transfer based on interfacing β-Pb_xV₂O₅ nanowires with CdSe quantum dots. Two distinct routes are developed for assembling the heterostructures: linker-assisted assembly mediated by a bifunctional ligand and successive ionic layer adsorption and reaction (SILAR). In the former case, the thiol end of a molecular linker is found to bind to the quantum dot surfaces, whereas a protonated amine moiety interacts electrostatically with the negatively charged nanowire surfaces. In the alternative SILAR route, the surface coverage of CdSe nanostructures on the β-Pb_xV₂O₅ nanowires is tuned by varying the number of successive precipitation cycles. High-energy valence band X-ray photoelectron spectroscopy measurements indicate that "mid-gap" states of the β-Pb_xV₂O₅ nanowires derived from the stereoactive lone pairs on the intercalated lead cations are closely overlapped in energy with the valence band edges of CdSe quantum dots that are primarily Se 4p in origin. Both the midgap states and the valence-band levels are in principle tunable by variation of cation stoichiometry and particle size, respectively, providing a means to modulate the thermodynamic driving force for charge transfer. Steady-state and time-resolved photoluminescence measurements reveal dynamic quenching of the trap-state emission of CdSe quantum dots upon exposure to β-Pb_xV₂O₅ nanowires. This result is consistent with a mechanism involving the transfer of photogenerated holes from CdSe quantum dots to the midgap states of β-Pb_xV₂O₅ nanowires.