Entropy-driven structural transition and kinetic trapping in formamidinium lead iodide perovskite

See allHide authors and affiliations

Science Advances  21 Oct 2016:
Vol. 2, no. 10, e1601650
DOI: 10.1126/sciadv.1601650


A challenge of hybrid perovskite solar cells is device instability, which calls for an understanding of the perovskite structural stability and phase transitions. Using neutron diffraction and first-principles calculations on formamidinium lead iodide (FAPbI3), we show that the entropy contribution to the Gibbs free energy caused by isotropic rotations of the FA+ cation plays a crucial role in the cubic-to-hexagonal structural phase transition. Furthermore, we observe that the cubic-to-hexagonal phase transition exhibits a large thermal hysteresis. Our first-principles calculations confirm the existence of a potential barrier between the cubic and hexagonal structures, which provides an explanation for the observed thermal hysteresis. By exploiting the potential barrier, we demonstrate kinetic trapping of the cubic phase, desirable for solar cells, even at 8.2 K by thermal quenching.

  • Organic-inorganic perovskite
  • neutron scattering
  • photovoltaic perovskite

This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license, which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited.

View Full Text