Intrinsic formamidinium tin iodide nanocrystals by suppressing the Sn(IV) impurities

Dmitry Dirin^a^,^b, Anna Vivani^c, Marios Zacharias^d, Taras Sekh^a^,^b, Ihor Cherniukh^a^,^b, Sergii Yakunin^a^,^b, Federica Bertolotti^c, Marcel Aebli^a^,^b, Richard Schaller^e^,^f, Alexander Wieczorek^b, Sebastian Siol^b, Claudia Cancellieri^b, Lars Jeurgens^b, Norberto Masciocchi^c, Antonietta Guagliardi^g, Laurent Pedesseau^d, Jacky Even^d, Maksym Kovalenko^a^,^b, Maryna Bodnarchuk^a^,^b

^aETH Zürich, Department of Chemistry and Applied Biosciences, CH-8093, Zurich, Switzerland

^bEmpa-Swiss Federal Laboratories for Materials Science and Technology, CH-8600, Dübendorf, Switzerland

^cDepartment of Science and High Technology and To.Sca.Lab., University of Insubria, via Valleggio 11, 22100 Como, Italy, Via Valleggio, 11, Como, Italy

^dUniv Rennes, INSA Rennes, CNRS, Institut FOTON - UMR 6082, F-35000 Rennes, France

^eArgonne National Lab

^fNorthwestern University

^gIstituto di Cristallografia and To.Sca.Lab, Consiglio Nazionale delle Ricerche, Via Valleggio, 11, Como, Italy

Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS23 & Sustainable Technology Forum València (STECH23) (MATSUS23)

#ChemNano23 - Chemistry of Nanomaterials

VALÈNCIA, Spain, 2023 March 6th - 10th

Organizers: Loredana Protesescu and Maksym Yarema

Oral, Dmitry Dirin, presentation 246
DOI: https://doi.org/10.29363/nanoge.matsus.2023.246
Publication date: 22nd December 2022

Lead halide perovskites successfully advance towards applications in solar cells, light-emitting devices, and high-energy radiation detectors. Recent progress in understanding their uniqueness highlights the role of optoelectronic tolerance to intrinsic defects, particularly long diffusion lengths of carriers, and highly dynamic 3d inorganic framework. This picture indicates that finding an analogous material among non-group-14 metal halides can be very challenging, if possible at all. On the other hand, a judicious choice of chemistry made it possible to noticeably increase the performance of formamidinium tin iodide perovskites when integrated into thin-film photovoltaic devices. The main challenge with this material originates from the easiness of the trap states generation, which are typically ascribed to the oxidation of Sn(II) to Sn(IV). In this work, we describe the synthesis of colloidal monodisperse FASnI₃ NCs, whereby thorough control of the purity and redox chemistry of the precursors allows the concentration of Sn(IV) to be reduced to an insignificant level, to probe the intrinsic structural and optical properties of these NCs. Intrinsic FASnI₃ NCs exhibit unusually low absorption coefficients of 4•10³ cm^-1 at the first excitonic transition, a 190 meV increase of the bandgap as compared to the bulk material, and a lack of excitonic resonances. These features are attributed to a highly disordered lattice, distinct from the bulk FASnI₃ as supported by structural characterizations and first-principles calculations.

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