Orientation and Grain Size in MAPbI₃ Thin Films: Influence on Phase Transition, Disorder, and Defects

In recent years, record efficiencies of halide perovskite-based devices have been achieved by processing high-quality thin films, where small morphology differences seem to be relevant for optimized optoelectronic functionality. However, a detailed understanding on how small morphological changes in perovskite films affect their structural and optoelectronic properties is still missing. Here, we investigate the influence of small morphology differences (i.e., increased grain size and crystallographic orientation), which are induced by hot-pressing methylammonium lead iodide (MAPbI 3 ) thin films, on the structural properties, phase transition behavior, energetic disorder, and defects. To this end, detailed temperature-dependent photoluminescence (PL) and absorption analyses from 300 K down to 5 K are performed. The morphology differences, confirmed by scanning electron microscopy and X-ray diffractometry analyses, result in an increased phase transition temperature for hot-pressed (HP) films, which we attribute to less strain. Moreover, fluence-dependent and transient PL measurements reveal a lower defect density in HP films. Here, besides grain size, also the degree of orientation appears to enhance the charge carrier lifetimes. The identified interdependence of strain and defect properties with film morphology suggests small differences in the perovskite’s energetic disorder. Our work thus emphasizes the importance that even small structural differences in halide perovskites have on their optoelectronic functionality, spurring their further optimization.