Cation Dynamics and Structural Stabilization in Formamidinium Lead Iodide Perovskites
Journal article, 2021

The vibrational dynamics of pure and methylammonium-doped formamidinium lead iodide perovskites (FAPbI3) has been investigated by high-resolution neutron spectroscopy. For the first time, we provide an exhaustive and accurate analysis of the cation vibrations and underlying local structure around the organic moiety in these materials using first-principles electronic-structure calculations validated by the neutron data. Inelastic neutron scattering experiments on FAPbI3 provide direct evidence of the formation of a low-temperature orientational glass, unveiling the physicochemical origin of phase metastability in the tetragonal structure. Further analysis of these data provides a suitable starting point to explore and understand the stabilization of the perovskite framework via doping with small amounts of organic cations. In particular, we find that the hydrogen-bonding interactions around the formamidinium cations are strengthened as a result of cage deformation. This synergistic effect across perovskite cages is accompanied by a concomitant weakening of the methylammonium interactions with the surrounding framework.

Author

Kacper Drużbicki

Polish Academy of Sciences

University of the Basque Country (UPV/EHU)

Rasmus Lavén

Chalmers, Chemistry and Chemical Engineering, Energy and Material, Environmental Inorganic Chemistry 2

Jeff Armstrong

STFC Rutherford Appleton Laboratory

Lorenzo Malavasi

Universita degli studi di Pavia

F. Fernandez-Alonso

University of the Basque Country (UPV/EHU)

University College London (UCL)

Donostia International Physics Center

Basque Foundation for Science (Ikerbasque)

Maths Karlsson

Chalmers, Chemistry and Chemical Engineering, Energy and Material, Environmental Inorganic Chemistry 2

Journal of Physical Chemistry Letters

1948-7185 (eISSN)

Vol. 12 14 3503-3508

Subject Categories

Inorganic Chemistry

Physical Chemistry

Condensed Matter Physics

DOI

10.1021/acs.jpclett.1c00616

PubMed

33792334

More information

Latest update

5/20/2021