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Issue 14, 2015
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Structural and electronic properties of organo-halide hybrid perovskites from ab initio molecular dynamics

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Abstract

The last two years have seen the unprecedentedly rapid emergence of a new class of solar cells, based on hybrid organic–inorganic halide perovskites. The success of this class of materials is due to their outstanding photoelectrochemical properties coupled to their low cost, mainly solution-based, fabrication techniques. Solution processed materials are however often characterized by an inherent flexible structure, which is hardly mapped into a single local minimum energy structure. In this perspective, we report on the interplay between structural and electronic properties of hybrid lead iodide perovskites investigated using ab initio molecular dynamics (AIMD) simulations, which allow the dynamical simulation of disordered systems at finite temperature. We compare the prototypical MAPbI3 (MA = methylammonium) perovskite in its cubic and tetragonal structure with the trigonal phase of FAPbI3 (FA = formamidinium), investigating different starting arrangements of the organic cations. Despite the relatively short time scale amenable to AIMD, typically a few tens of ps, this analysis demonstrates the sizable structural flexibility of this class of materials, showing that the instantaneous structure could significantly differ from the time and thermal averaged structure. We also highlight the importance of the organic–inorganic interactions in determining the fluxional properties of this class of materials. A peculiar spatial localization of the valence and conduction band edges is also found, with a dynamics in the range of 0.1 ps, which is associated with the positional dynamics of the organic cations within the cubo-octahedral perovskite cage. This asymmetry in the spatial localization of the band edges is expected to ease exciton dissociation and assist the initial stages of charge separation, possibly constituting one of the key factors for the impressive photovoltaic performances of hybrid lead-iodide perovskites.

Graphical abstract: Structural and electronic properties of organo-halide hybrid perovskites from ab initio molecular dynamics

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Publication details

The article was received on 30 Jan 2015, accepted on 05 Mar 2015 and first published on 05 Mar 2015


Article type: Perspective
DOI: 10.1039/C5CP00599J
Author version available: Download Author version (PDF)
Citation: Phys. Chem. Chem. Phys., 2015,17, 9394-9409
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    Structural and electronic properties of organo-halide hybrid perovskites from ab initio molecular dynamics

    C. Quarti, E. Mosconi and F. De Angelis, Phys. Chem. Chem. Phys., 2015, 17, 9394
    DOI: 10.1039/C5CP00599J

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