A theoretical framework for the study of lead halide perovskite precursors: the case of PbI2 in γ-butyrolactone

Eros Radicchi^a^,^b, Ali Kachmar^c, Edoardo Mosconi^b, Filippo De Angelis^a^,^b

^aDepartment of Chemistry, Biology and Biotechnology, University of Perugia, Italy., Via dell' Elce di Sotto, 8, Perugia, Italy

^bIstituto CNR di Scienze e Tecnologie Chimiche “Giulio Natta” (CNR-SCITEC), Italy., Via dell' Elce di Sotto, 8, Perugia, Italy

^cQatar Environment and Energy Research Institute, Hamad Bin Khalifa University, Qatar, Qatar Foundation, Education City , Doha, 5825, Qatar

International Conference on Hybrid and Organic Photovoltaics
Proceedings of Online International Conference on Hybrid and Organic Photovoltaics (OnlineHOPV20)

Online, Spain, 2020 May 26th - 29th

Organizers: Tracey Clarke, James Durrant, Annamaria Petrozza and Trystan Watson

Poster, Eros Radicchi, 113
Publication date: 22nd May 2020

ePoster:

The choice of solvent is a crucial factor for the morphology and properties of solution-deposited perovskite films and thus for the final quality of devices, affecting the crystallization and regulating the type and quantity of defects that will be found in the crystalline material. [1-3] In this sense, high coordinative solvents such as dimethylsulfoxide (DMSO) and N,N-dimethylformamide (DMF) tends to strongly bind Pb atoms, displacing other ligands, whereas in a low coordinative solvent environment, for example acetonitrile (ACN) or γ-butyrolactone (GBL), lead complexes with higher amount of iodine (e.g. PbI₃^-, PbI₄^2-) seems preferred. [4] In the case of GBL, Fateev et al. [5] reported the formation of solid-state adducts upon evaporation of a concentrated perovskite solution, while Rahimnejad et al. [1] highlighted the formation of PbI⁺ and PbI₃^- complexes in a diluted PbI₂ solution. Nevertheless, an in-depth analysis of the structural and optical properties of different species in GBL can be useful to understand in details how this solvent affects the chemistry of perovskite precursors. For this reason, here we want to focus on the behaviour of the PbI₂ precursor salt in the GBL solvent, employing a theoretical framework that combines ab-initio molecular dynamics (AIMD) simulations of the solvated PbI₂ molecule with the evaluation of absorption spectra by means of Time-Dependent Density Functional Theory (TD-DFT) calculations. Energetic evaluations of static complexes was also carried out with DFT simulations in order to compare the stability of PbI₂(GBL)_n complexes with other solvents.

References:

[1] Rahimnejad, S., Kovalenko, A., Forés, S. M., Aranda, C. & Guerrero, A. Coordination Chemistry Dictates the Structural Defects in Lead Halide Perovskites. ChemPhysChem 2016, 17, 2795–2798.

[2] Stewart, R. J., Grieco, C., Larsen, A. V., Doucette, G. S. & Asbury, J. B. Molecular Origins of Defects in Organohalide Perovskites and Their Influence on Charge Carrier Dynamics. J. Phys. Chem. C 2016, 120, 12392–12402.

[3] Hamill, J. C., Schwartz, J. & Loo, Y.-L. Influence of Solvent Coordination on Hybrid Organic–Inorganic Perovskite Formation. ACS Energy Lett. 2018, 3, 92–97.

[4] Radicchi, E., Mosconi, E., Elisei, F., Nunzi, F. & De Angelis, F. Understanding the Solution Chemistry of Lead Halide Perovskites Precursors. ACS Appl. Energy Mater. 2019, 2, 3400–3409.

[5] Fateev, S. A., Petrov, A. A., Khrustalev, V. N., Dorovatovskii, P. V., Zubavichus, Y. V., Goodilin, E. A. & Tarasov, A. B. Solution Processing of Methylammonium Lead Iodide Perovskite from γ-Butyrolactone: Crystallization Mediated by Solvation Equilibrium. Chem. Mater. 2018, 30, 5237–5244.

Acknowledgements:

”Ministero per l’Università e la Ricerca Scientifica e Tecnologica”, MIUR (Rome, Italy).

“Dipartimenti di Eccellenza 2018-2022” (Grant AMIS), University of Perugia (Perugia, Italy).

European Union's Horizon 2020 research and innovation programme under Grant Agreement No. 764047 ESPResSo project.

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