Framing excitons in halide perovskite materials from symmetry analysis and simulations

Claudio Quarti^a

^aLaboratory for Chemistry of Novel Materials, University of Mons, Belgium, Place du Parc, 20, Mons, Belgium

Materials for Sustainable Development Conference (MATSUS)
Proceedings of nanoGe Spring Meeting 2022 (NSM22)

#PhotoPero22. Photophysics of Halide Perovskites and Related Materials - from Bulk to Nano

Online, Spain, 2022 March 7th - 11th

Organizers: Sascha Feldmann, Annamaria Petrozza and Ajay Ram Srimath Kandada

Invited Speaker, Claudio Quarti, presentation 158
DOI: https://doi.org/10.29363/nanoge.nsm.2022.158
Publication date: 7th February 2022

On the wave of their success in strategic fields of application, as energy conversion and light-emission, great effort was devoted to better understand and clarify the native semiconducting properties of halide perovskite materials. As a result, the electronic properties of these systems are nowadays well understood, with clear identification of the influence of quantum confinement and chemical tuning on the corresponding band structure, as relevant in the case of dimensionally tailored materials,[1] and in mixed halide or double perovskites,[2] respectively. The situation however becomes more complex when one goes beyond the single particle picture. The Coulomb interaction between the photogenerated electron-hole pairs in fact may result in the formation of stable excitons, with distinct properties (energetics, polarization, degeneracy, etc.) with respect to the corresponding single particle transitions.

Here, we aim to provide a general frame for the discussion of the exciton properties of metal halide perovskite frames, which encompasses effects like quantum confinement and chemical composition. Symmetry-based, group theory analysis will provide a sounded ground for the discussion, with clear indication about the expected splitting of the excitonic features in the materials, when going from 3D, to 2D and to other systems of practical relevance.[3] These results will be then referred to recent spectroscopic experiments[4-6] and to cutting edge first-principle calculations,[7] so demonstrating the possibilities of modern first-principle simulations tools in supporting experimental investigations and predicting the excitonic properties of halide perovskite materials. Excitons dominate the optical response of two-dimensional layered perovskite materials, where quantum and dielectric confinement enhance the electron-hole interactions;[1] still, they are shown to play a fundamental role also for double perovskites,[8] with serious impact on the relative role of dimensional confinement.[9] In addition, also for 3D lead-based halide perovskites, featuring exciton binding as small as 14-25 meV at room temperature,[10] the clear understanding and assignment of the spectral signatures must rely on an excitonic picture.[4-5]

References:

[1] Katan, C.; Mercier, N.; Even, J. Quantum and Dielectric Confinement Effects in Lower-Dimensional Hybrid Perovskite Semiconductors, Chem. Rev. 2019, 119, 3140–3192

[2] Filip M.R., Volonakis G., Giustino F. (2018) Hybrid Halide Perovskites: Fundamental Theory and Materials Design. In: Andreoni W., Yip S. (eds) Handbook of Materials Modeling. Springer, Cham.

[3] Quarti, C.; Katan, K.; Even, J. Physical properties of bulk, defective, 2D and 0D metal halide perovskite semiconductors from a symmetry perspective, J Phys.: Mater., 2020, 3, 042001

[4] Becker, M. A.; Vaxenburg, R.; Nedelcu, G.; Sercel, P. C.; Shabaev, A.; Mehl, M. J.; Michopoulos, J. G.; Lambrakos, S. G.; Bernstein, N.; Lyons, J. L.; Stöferle, T.; Mahrt, R. F.; Kovalenko, M. V.; Norris, D. J.; Rainò, G.; Efros, A. L. Bright triplet excitons in caesium lead halide perovskites, Nature 2018, 553, 189–193

[5] Tamarat, P.; Bodnarchuk, M. I.; Trebbia, J.-B.; Rolf, E.; Kovalenko, M. V.; Even, J.; Lounis, B. The ground exciton state of formamidinium lead bromide perovskite nanocrystals is a singlet dark state Nat. Mater. 2019, 18 717–724

[6] Dyksik, M.; Duim, H. ; Maude, D. K.; Baranowski, M.; Loi, M. A.; Plochocka, P. Brightening of dark excitons in 2D perovskites Sci. Adv. 2021, 7, eabk0904

[7] Giorgi, G.; Yamashita, K.; Palummo, M. Nature of the Electronic and Optical Excitations of Ruddlesden-Popper Hybrid Organic-Inorganic Perovskites: The Role of the Many-Body Interactions. J. Phys. Chem. Lett. 2018, 9, 5891–5896

[8] Biega, R. I.; Filip, M. R.; Leppert, L.; Neaton, J. B. Chemically Localized Resonant Excitons in Silver–Pnictogen Halide Double Perovskites, J. Phys. Chem. Lett., 2021, 12, 2057–2063.

[9] Pantaler, M.; Diez-Cabanes, V.; Queloz, V. I. E.; Sutanto, A.; Schouwink, P. A.; Pastore, M.; García-Benito, I.; Nazeeruddin, M. K.; Beljonne, D.; Lupascu, D. C.; Quarti, C.; Grancini, G. Revealing Weak Dimensional Confinement Effects in Excitonic Silver/Bismuth Double Perovskites, Jacs Au, accepted manuscript.

[10] Galkowski, K.; Mitioglu, A.; Miyata, A.; Plochocka, P.; Portugall, O. ; Eperon, G. E.; Wang, J. T.-W.; Stergiopoulos, T.; Stranks, S. D.; Snaith H. J.; Nicholas, R. J. Determination of the exciton binding energy and effective masses for methylammonium and formamidinium lead tri-halide perovskite semiconductors, Energy Environ. Sci., 2016, 9, 962-970

Acknowledgements:

The results from this work are partially funded by the Agence Nationale pour la Recherche (MORELESS project). Computational resources were provided by the Zenobe/CENAERO (Walloon region Grant Agreement 1117545) clusters. C. Q. is a FNRS Research Associate

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