Abnormal In-Plane Thermomechanical Behavior of Two-Dimensional Hybrid Organic-Inorganic Perovskites

The implementation of two-dimensional (2D) hybrid organic-inorganic perovskites (HOIPs) in semiconductor device applications will have to accommodate the co-existence of strain and temperature stressors and requires a thorough understanding of the thermomechanical behavior of 2D HOIPs. This will mitigate thermomechanical stability issues and improve the durability of the devices, especially when one considers the high susceptibility of 2D HOIPs to temperature due to their soft nature. Here, we employ atomic force microscopy (AFM) stretching of suspended membranes to measure the temperature dependence of the in-plane Young's modulus (E_∥) of model Ruddlesden-Popper 2D HOIPs with a general formula of (CH₃(CH₂)₃NH₃)₂(CH₃NH₃)PbI₃ (here, n = 1, 3, or 5). We find that E_∥ values of these 2D HOIPs exhibit a prominent non-monotonic dependence on temperature, particularly an abnormal thermal stiffening behavior (nearly 40% change in E_∥) starting around the order-disorder transition temperature of the butylammonium spacer molecules, which is significantly different from the thermomechanical behavior expected from their 3D counterpart (CH₃NH₃PbI₃) or other low-dimensional material systems. Further raising the temperature eventually reverses the trend to thermal softening. The magnitude of the thermally induced change in E_∥ is also much higher in 2D HOIPs than in their 3D analogs. Our results can shed light on the structural origin of the thermomechanical behavior and provide needed guidance to design 2D HOIPs with desired thermomechanical properties to meet the application needs.