Abstract

Lead halide perovskite semiconductors providing record efficiencies of solar cells have usually mixed compositions doped in A- and X-sites to enhance the phase stability. The cubic form of formamidinium (FA) lead iodide reveals excellent opto-electronic properties but transforms at room temperature (RT) into a hexagonal structure which does not effectively absorb visible light. This metastable form and the mechanism of its stabilization by Cs+ and Br- incorporation are poorly characterized and insufficiently understood. We report here the vibrational properties of cubic FAPbI(3) investigated by DFT calculations on phonon frequencies and intensities, and micro-Raman spectroscopy. The effects of Cs+ and Br- partial substitution are discussed. We support our results with the study of FAPbBr(3) which expands the identification of vibrational modes to the previously unpublished low frequency region (500 cm(-1)). Our results show that the incorporation of Cs+ and Br- leads to the coupling of the displacement of the A-site components and weakens the bonds between FA(+) and the PbX6 octahedra. We suggest that the enhancement of alpha-FAPbI(3) stability can be a product of the release of tensile stresses in the Pb-X bond, which is reflected in a red-shift of the low frequency region of the Raman spectrum (200 cm(-1)).