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Since its first observation in 2014, plasmoelectric potential (PEP) has drawn a great deal of research interest in all-metal optoelectronics and photochemistry. As an optical thermodynamic phenomenon induced by the electron number dependent equilibrium temperature in plasmonic nanostructures, the early theoretical model developed for calculating PEP is only applicable to Mie-resonant nanostructures, such as a gold nanosphere on a conductive indium tin oxide (ITO) substrate, where the transfer efficiency of hot electrons from gold to ITO can be analytically determined. Without the presence of the substrate, the temperature increase on the gold nanosphere induced by plasmonic absorption was calculated on the basis of thermal radiation in vacuum, which probably over-estimates the actual temperature increase in comparison to realistic experimental conditions. Here, we propose an equilibrium-thermodynamics computational method to quantify the actual efficiency of plasmon-induced electron transfer between a non-Mie-resonant metallic nanostructure and a conductive substrate and hence determine the resultant plasmoelectric potential. With a less than 2.5% relative error in predicting the steady-state temperature of a Mie-resonant nanoparticle in vacuum, and a more strict evaluation of the plasmonic local heating induced temperature increase in a single plasmonic nanostructure or an array of such structures under continuous-wave illumination (CWI), our generalized method provides a robust and accurate approach for quantifying PEP in various plasmonic-particle (array)-on-film nanocavities.

A generalized method for calculating plasmoelectric potential in non-Mie-resonant plasmonic systems