Linking Morphology and Multi-Physical Transport in Structured Photoelectrodes

Semiconductors with complex anisotropic morphologies in solar to chemical energy conversion devices enhance light absorption and overcome limiting charge transport in the solid. However, structuring the solid-liquid interface has also implications on concentration distributions and diffusive charge transport in the electrolyte. Quantifying the link between morphology and those multi-physical transport processes remains a challenge. Here we develop a coupled experimental-numerical approach to digitalize the photoelectrodes by high resolution FIB-SEM tomography, quantitatively characterize their morphologies and calculate multi-physical transport processes on the exact geometries. We demonstrate the extraction of the specific surface, shape, orientation and dimension of the building blocks and the multi-scale pore features from the digital model. Local current densities at the solid-liquid interface and ion concentration distributions in the electrolyte have been computed by direct pore-level simulations. We have identified morphology-dependent parameters to link the incident-light-to-charge-transfer-rate-conversion to the material bulk properties. In the case of a structured lanthanum titanium oxynitride photoelectrode (Eg = 2.1 eV), with an absorptance of 77%, morphology-induced mass transport performance limitations have been found for low bulk ion concentrations and diffusion coefficients.