Correlating Crystallographic Orientation and Ferroic Properties of Twin Domains in Metal Halide Perovskites

Metal halide perovskite (MHP) solar cells have attracted worldwide research interest. Although it has been well established that grain, grain boundary, and grain facet affect MHPs optoelectronic properties, less is known about subgrain structures. Recently, MHP twin stripes, a subgrain feature, have stimulated extensive discussion due to the potential for both beneficial and detrimental effects of ferroelectricity on optoelectronic properties. Connecting the ferroic behavior of twin stripes in MHPs with crystal orientation will be a vital step to understand the ferroic nature and the effects of twin stripes. In this work, we studied the crystallographic orientation and ferroic properties of CH₃NH₃PbI₃ twin stripes, using electron backscatter diffraction (EBSD) and advanced piezoresponse force microscopy (PFM), respectively. Using EBSD, we discovered that the orientation relationship across the twin walls in CH₃NH₃PbI₃ is a 90° rotation about ⟨1̅1̅0⟩, with the ⟨030⟩ and ⟨111⟩ directions parallel to the direction normal to the surface. By careful inspection of CH₃NH₃PbI₃ PFM results including in-plane and out-of-plane PFM measurements, we demonstrate some nonferroelectric contributions to the PFM responses of this CH₃NH₃PbI₃ sample, suggesting that the PFM signal in this CH₃NH₃PbI₃ sample is affected by nonferroelectric and nonpiezoelectric forces. If there is piezoelectric response, it is below the detection sensitivity of our interferometric displacement sensor PFM (<0.615 pm/V). Overall, this work offers an integrated picture describing the crystallographic orientations and the origin of PFM signal of MHPs twin stripes, which is critical to understanding the ferroicity in MHPs.