Structural characterization of bulk and nanoparticle lead halide perovskite thin films by (S)TEM techniques

Lead halide (APbX₃) perovskites, in polycrystalline thin films but also perovskite nanoparticles (NPs) has demonstrated excellent performance to implement a new generation of photovoltaic and photonic devices. The structural characterization of APbX₃ thin films using (scanning) transmission electron microscopy ((S)TEM) techniques can provide valuable information that can be used to understand and model their optoelectronic performance and device properties. However, since APbX₃ perovskites are soft materials, their characterization using (S)TEM is challenging. Here, we study and compare the structural properties of two different metal halide APbX₃ perovskite thin films: bulk CH₃NH₃PbI₃ prepared by spin-coating of the precursors in solution and CsPbBr₃ colloidal NPs synthetized and deposited by doctor blading. Both specimen preparation methods and working conditions for analysis by (S)TEM are properly optimized. We show that CH₃NH₃PbI₃ thin films grown by a one-step method are composed of independent grains with random orientations. The growth method results in the formation of tetragonal perovskite thin films with good adherence to an underlying TiO₂ layer, which is characterized by a photoluminescence (PL) emission band centered at 775 nm. The perovskite thin films based on CsPbBr₃ colloidal NPs, which are used as the building blocks of the film, are preserved by the deposition process, even if small gaps are observed between adjacent NPs. The crystal structure of CsPbBr₃ NPs is cubic, which is beneficial for optical properties due to its optimal band gap. The absorption and PL spectra measured in both the thin film and the colloidal solution of CsPbBr₃ NPs are very similar, indicating a good homogeneity of the thin films and the absence of aggregation of NPs. However, a particular care was required to avoid long electron irradiation times during our structural studies, even at a low voltage of 80 kV, as the material was observed to decompose through Pb segregation.