Direct Observation of Plasmon-Induced Interfacial Charge Separation in Metal/Semiconductor Hybrid Nanostructures by Measuring Surface Potentials

Plasmon-induced interfacial charge separation (PICS) is one of the key processes responsible for the improved conversion efficiencies of energy-harvesting devices that incorporate metal nanostructures. In this Letter, we reveal a mechanism of PICS by visualizing (with nanometer-scale resolution) and characterizing plasmonexciton coupling between p-type poly(pyrrole) (PPy) nanowires (NWs) and Ag nanoparticles (NPs) using light-irradiated Kelvin probe force microscopy (KPFM). Under blue-light irradiation, the Ag NPs are expected to donate electrons to the PPy NWs via a hot electron injection process. However, in this Letter, we observe that under blue-light irradiation the plasmonically and excitonically excited electrons in the semiconductor back-transfer to the metal. The PICS in this system can be explained by comparing it with a similar one where Au NPs are attached to n-type ZnO NWs; we observed a net electron transfer from the Au NPs to the ZnO NWs (an upward band bending is formed at the interface of the two materials, presumably obstructing electron back-transfer). Indeed, energy band matching between the metal and the semiconductor components of hybrid nanostructures influences PICS pathways. These experimental findings and our proposed mechanism consistently explain the PICS occurring in the PPy NW-Ag NP system with important implications on explaining their cooperative optoelectronic activities.