Enabling Quantitative IMPS Analysis of Charge Carrier Dynamics in Photoelectrochemical Systems
Alberto Piccioni a, Pierpaolo Vecchi a, Irene Carrai a, Marco Salvi a, Raffaello Mazzaro a, Luca Pasquini a
a University of Bologna, Viale Carlo Berti Pichat 6/2, Bologna, Italy
Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS Fall 2023 Conference (MATSUSFall23)
#MATSF - Advanced materials for the production of direct solar-driven fuels and chemicals
Torremolinos, Spain, 2023 October 16th - 20th
Organizers: Salvador Eslava and Sixto Gimenez Julia
Oral, Alberto Piccioni, presentation 254
DOI: https://doi.org/10.29363/nanoge.matsus.2023.254
Publication date: 18th July 2023

Intensity Modulated Photocurrent Spectroscopy (IMPS) has been largely employed in semiconductors characterization, to probe the operando behavior with widely available facilities. However, the implementation of IMPS data analysis to complex structures, such as the semiconductor-electrolyte interface or buried heterojunctions, is generally limited to qualitative evaluation of the steady-state conversion efficiency. In this work, a new algorithm for the analysis of IMPS data is developed, providing unprecedented insights into the time resolved charge transfer/recombination paths in semiconductors for solar energy conversion, from photoelectrochemical (PEC) water splitting to photovoltaics. The algorithm, based on the previously developed Distribution of Relaxation Times (DRT) analysis, here modified with Lasso regression method, is validated on different PEC systems, such as Ti modified hematite photoanode for PEC water oxidation, identified as a standard platform in the field, but also CoPi modified hematite for valorization of biomass derivated and CIGS based photocathodes for water reduction. The application of the L-DRT algorithm to IMPS data provides several advantages compared to the conventional kinetic analysis, including straightforward identification of multiple charge transfer and recombination paths, improved time resolution, providing precise and reliable description of the characteristic lifetime of each process and extension of the potential window suitable to kinetic analysis due to the deconvolution of subtle recombination peaks [1], [2].

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