Revealing the impact of organic spacers and cavity cations on quasi-2D perovskites via computational simulations.

Autor: Guedes-Sobrinho D; Chemistry Department, Federal University of Paraná, Curitiba, 81531-980, Brazil., Neves Silveira D; Chemistry Department, Federal University of Paraná, Curitiba, 81531-980, Brazil., de Araujo LO; Chemistry Department, Federal University of Paraná, Curitiba, 81531-980, Brazil., Favotto Dalmedico J; Department of Physics, Federal University of Pelotas, PO Box 354, Pelotas, RS, 96010-900, Brazil., Wenzel W; Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz, 76344, Eggenstein-Leopoldshafen, Germany., Pramudya Y; Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz, 76344, Eggenstein-Leopoldshafen, Germany., Piotrowski MJ; Department of Physics, Federal University of Pelotas, PO Box 354, Pelotas, RS, 96010-900, Brazil., Rêgo CRC; Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz, 76344, Eggenstein-Leopoldshafen, Germany. celso.rego@kit.edu.
Jazyk: angličtina
Zdroj: Scientific reports [Sci Rep] 2023 Mar 17; Vol. 13 (1), pp. 4446. Date of Electronic Publication: 2023 Mar 17.
DOI: 10.1038/s41598-023-31220-8
Abstrakt: Two-dimensional hybrid lead iodide perovskites based on methylammonium (MA) cation and butylammonium (BA) organic spacer-such as [Formula: see text]-are one of the most explored 2D hybrid perovskites in recent years. Correlating the atomistic profile of these systems with their optoelectronic properties is a challenge for theoretical approaches. Here, we employed first-principles calculations via density functional theory to show how the cation partially canceled dipole moments through the [Formula: see text] terminal impact the structural/electronic properties of the [Formula: see text] sublattices. Even though it is known that at high temperatures, the organic cation assumes a spherical-like configuration due to the rotation of the cations inside the cage, our results discuss the correct relative orientation according to the dipole moments for ab initio simulations at 0 K, correlating well structural and electronic properties with experiments. Based on the combination of relativistic quasiparticle correction and spin-orbit coupling, we found that the MA horizontal-like configuration concerning the inorganic sublattice surface leads to the best relationship between calculated and experimental gap energy throughout n = 1, 2, 3, 4, and 5 number of layers. Conversely, the dipole moments cancellation (as in BA-MA aligned-like configuration) promotes the closing of the gap energies through an electron depletion mechanism. We found that the anisotropy [Formula: see text] isotropy optical absorption conversion (as a bulk convergence) is achieved only for the MA horizontal-like configuration, which suggests that this configuration contribution is the majority in a scenario under temperature effects.
(© 2023. The Author(s).)
Databáze: MEDLINE
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