Dielectric function of hybrid perovskites at finite temperature investigated by classical molecular dynamics

A Mattoni and C Caddeo, JOURNAL OF CHEMICAL PHYSICS, 152, 104705 (2020).

DOI: 10.1063/1.5133064

Ionic polarization and dielectric function play a fundamental role in the optoelectronic properties of hybrid perovskites, currently one of the most studied materials for next generation photovoltaics. The hybrid nature of the crystal, with molecular dipoles that can reorient within the inorganic lattice, gives rise to a complex dielectric response in the bulk material that has been largely studied and debated. Here, we investigate the nature and the relaxation properties of the dielectric polarization of hybrid perovskites at finite temperature by means of classical molecular dynamics. We provide evidence that a simple ionic model of classical interatomic forces is able to explain qualitatively the temperature and frequency dependence of the dielectric constant providing a picture that is fully consistent with experimental data. The constant dielectric function in the low-temperature phase is controlled by ionic displacements, while the temperature-dependent paraelectric behavior of the tetragonal phase is due to reorientation of dipoles that are responsible for the discontinuity at the orthorhombic-to-tetragonal transition. In the frequency domain, the molecular reorientations give rise to a broad band that is located in the 0.1 THz timescale at room temperature and that shifts down to the GHz timescale when cooling the system toward the tetragonal-to-orthorhombic phase transition. The relation between relaxation time and maximum absorption frequency is also clarified.

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