Diffuse Scattering as a Probe of Static and Dynamic Local Structure

Local atomic structure often differs from the global average structure as measured with diffraction and yet the local structure has a profound impact on properties. This structure-function relationship applies in many materials classes, ranging from organics to Li-ion battery cathodes to perovskites. Accurately characterizing this local structure has proven challenging but recent advances in diffuse scattering (“between” Bragg peaks) has enabled local structure determination.<br/><br/>In this talk, I will discuss the importance of local structure and how this can be quantified and will demonstrate this for organic-inorganic hybrid halide perovskites [1,2]. These materials are a recently re-invigorated class of semiconductor that have demonstrated very high efficiencies for solar cells after just over a decade of research. While the importance of lattice dynamics and dynamical (dis)order has been recognized in these materials, their nature is only poorly known and understood. We used X-ray and neutron diffuse scattering coupled with molecular dynamics to quantify the nature, size, and time scale associated with dynamical local order in CH₃NH₃PbI₃ and CH₃NH₃PbBr₃ perovskites. We observe that the nominally cubic perovskite consists of dynamical, two-dimensional sheets of lower symmetry tetragonal regions of about 3 nm diameter with several picosecond lifetimes. The implications on halide perovskite properties will be discussed.<br/>[1] NJ Weadock et al., Joule <b>7</b>, 5, 1051-1066 (2023)<br/>[2] DM Ladd, unpublished.