Evidence for ferroelectric polarons in lead halide perovskites

Lead halide perovskites are characterized by dielectric responses and phonon dynamics resembling those of liquids. We show that the dielectric function in the THz region in this class of materials may lead to dynamic and local ordering of polar nano domains by an extra electron or hole, resulting a quasiparticle which we call a ferroelectric large polaron, a concept similar to solvation in chemistry. Compared to a conventional large polaron, the collective nature of polarization in a ferroelectric large polaron may give rise to order(s)-of-magnitude larger reduction in the Coulomb potential. We show that the shape of a ferroelectric polaron resemble that of a Belgian waffle. Using two-dimensional coherent phonon spectroscopy, we directly probe the energetics and local phonon responses of the ferroelectric large polarons. We find that that electric field from a nascent e-h pair drives the local transition to a hidden ferroelectric order on picosecond time scale. The ferroelectric or Belgian waffle polarons may explain the defect tolerance and low recombination rates of charge carriers in lead halide perovskites, as well as providing a design principle of the “perfect” semiconductor for optoelectronics.