Modeling Enhanced Performances by Optical Nanostructures in Water-Splitting Photoelectrodes

Material nanostructuring and optical phenomena on a nanoscale such as plasmonic effects and light scattering have been widely studied for improving the solar-to-hydrogen efficiency of photoelectrochemical (PEC) water-splitting electrodes. In this work, we report a method for analyzing the contributions of optical effects from nanostructures for enhancing the PEC performances. Electromagnetic simulations are performed for the precise calculation of generated power density in a semiconductor material. In addition, the transport and transfer of photogenerated charges to the electrolyte are modeled by using the conservation of minority carriers. The surface loss parameter, diffusion length, and doping density of the semiconductor material are determined by fitting the model to an incident photon to current efficiency (IPCE) curve experimentally measured on the bare reference photoelectrode. These parameters are then used to compute the IPCE spectra of the photoelectrode for which an optical enhancement strategy is used, such as nanostructuring or plasmonics. The method is validated using published experimental data. The calculated IPCE enhancement ratio originating from optical effects is in quantitative agreement with experimental observations for both periodic and random optical structures. The model can be used to study in detail the key enhancement mechanisms for the IPCE from optical nanostructures and, in particular, discriminate between optical and nonoptical (e.g., catalytic) enhancement.

Automated summary

This work presents a method for analyzing the contributions of optical effects from nanostructures to enhance the performance of PEC water-splitting electrodes. Electromagnetic simulations and modeling of photogenerated charges transport are used to calculate the power density in semiconductor materials. Parameters of the semiconductor material are determined by fitting the model to experimentally measured IPCE curve, and then used to compute the IPCE spectra of the photoelectrode with optical enhancement strategies. The calculated IPCE enhancement ratio is in agreement with experimental observations, indicating the effectiveness of optical nanostructures in improving IPCE.