Microstructure of Methylammonium Lead iodide Perovskite Thin Films: A Comprehensive Study of the Strain and Texture

Abstract Controlling the microstructure of hybrid halide perovskite thin films is essential for optimizing their performance in optoelectronic devices. It is well established that the strain state of the perovskite layer affects its stability. Likewise, the orientation of the perovskite lattice is a determining parameter as these materials have shown pronounced anisotropies in their physical and mechanical properties. In this work, the authors focus on the understanding of the mechanisms that govern the strain and texture observed in MAPbI 3 thin films deposited on various oxide substrates. A thorough study of the evolution of the strain of the perovskite layer upon cooling down to room temperature from the crystallization temperature (100 °C) shows an essentially relaxed behavior of the perovskite layers. This result contradicts the commonly accepted hypothesis according to which MAPbI 3 layers synthesized above ambient temperature are strained due to the large mismatch in the thermal expansion coefficients of the perovskite and its substrate. The texture in MAPbI 3 layers is investigated by means of synchrotron full‐field diffraction X‐ray microscopy. This technique allows the direct observation of the [hh0] and [00l]‐oriented domains at the origin of the observed textures, demonstrating both their twin and ferroelastic nature. The stability of the different domain orientations is investigated by DFT calculations, illustrating the determining role of the chemical environment at the film‐substrate interface. PbI 2 ‐ terminated surfaces are found to favor the [hh0] orientations while for MAI‐terminated ones, both [hh0] and [00l] domains are equally stabilized. The different results constitute an important step of clarification and understanding from the perspective of controlling the microstructure of perovskite layers.