Structural and Optical Characterization of Solution Processed Lead Iodide Ruddlesden-Popper Perovskite Thin Films

Highly efficient LEDs and photovoltaic cells based on spin coated films of layered Ruddlesden-Popper hybrid perovskites (RPP) have been recently reported. The electronic structure and phase composition of these films remains an open question, with diverse explanations offered accounting for the excellent device performance. Here we report x-ray and optical characterization of hot cast RPP thin films, emphasizing the distribution of structural and electronic properties through the film depth. Our results indicate an at least 70% phase pure n=3 film results from casting a stoichiometric solution of precursors, with minor contributions from n=2 and n=4 phases. We observe a strong correspondence between the predicted single-crystal RPP reciprocal lattice and measured RPP film wide angle scattering pattern, indicating a highly ordered [101] oriented film. This correspondence is broken at the air-film interface where new scattering peaks indicate the existence of a long wavelength structural distortion localized near the films surface. Using transient absorption spectroscopy, we show that the previously detected luminescent mid-gap states are localized on the films surface. Investigating films of varying thickness, we determine the photo-excited carrier dynamics are dominated by diffusion to this interface state, and extract an excitonic diffusivity of 0.18cm2s-1. We suggest that the observed surface distortion is responsible for the creation of luminescent mid-gap states.