Proceedings of MATSUS Fall 2023 Conference (MATSUSFall23)
DOI: https://doi.org/10.29363/nanoge.matsus.2023.057
Publication date: 18th July 2023
Halide perovskites have been established as one of the most promising semiconductors for a myriad of optoelectronic applications. Besides their exceptional optical properties, perovskites have been demonstrated to behave as mixed ionic-electronic conductors. While ion migration is typically detrimental for conventional perovskite applications (such as solar cells or LEDs), this particular property has proven useful in devices such as memristors, electrochemical transistors, or bolometers. Therefore, it is essential to develop a deep fundamental understanding of the mixed ionic-electronic conduction properties in this class of materials to enable further advances in multiple perovskite-based technologies.
Amongst the vast number of perovskite compositions, Sn-based perovskites have received great attention due to their reduced toxicity and narrow bandgaps compatible with NIR absorption. However, mixed conduction in this class of materials has been underexplored relative to their Pb-based analogues. While a few reports have recently unveiled a smaller degree of ion migration in a limited number of Sn-based compositions, the use of standard electrical characterization techniques to quantify this phenomenon in a wider range of Sn perovskites is still required.
In this work, we used the galvanostatic polarization technique to obtain the ionic and electronic conductivities of various Sn-based perovskite compositions (ASnxPb1-xI3, where A=methylammonium and formamidinium). This technique has been established as one of the most standardized methods to measure the mixed conduction properties of several semiconducting materials. In particular, we shed light on the role of the Sn content (x=0, 0.25, 0.5, 0.75, and 1), the A-site composition, and the concentration of Sn vacancies (tuned by adjusting the content of SnF2 vacancy modulator additive) on the ionic and electronic conductivities. We found ionic conductivity to be intimately correlated to electronic conductivity, suggesting that the electronic carrier concentration is proportional to the number of mobile ions in the perovskite and/or their ionic mobility. These findings provide key design rules to harness ion migration in Sn-based perovskites via compositional engineering.
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