Controlling Phase Transitions in Two-Dimensional Perovskites through Organic Cation Alloying

We demonstrate control over the phase transition temperature of Ruddlesden-Popper two-dimensional (2D) perovskites by alloying alkyl organic cations of varying lengths. By blending hexylammonium with pentylammonium or heptylammonium cations in different ratios, we continuously tune the phase transition temperature of 2D perovskites from approximately 40 to -80 °C in both crystalline powders and thin films. Correlating temperature-dependent grazing incidence wide-angle X-ray scattering and photoluminescence spectroscopy, we also demonstrate that the phase transition in the organic layer couples to the inorganic lattice, impacting PL intensity and wavelength. We take advantage of changes in PL intensity to image the dynamics of this phase transition and show asymmetric phase growth at the microscale. Our findings provide the necessary design principles to precisely control phase transitions in 2D perovskites for applications such as solid-solid phase change materials and barocaloric cooling.