Coherent Nanotwins and Dynamic Disorder in Cesium Lead Halide Perovskite Nanocrystals

Abstract Crystal defects in highy luminescent colloidal nanocrystals (NCs) of CsPbX3 perovskites (X = Cl, Br, I) are investigated. Here, using X-ray total scattering techniques and the Debye scattering equation (DSE), we provide evidence that the local structure of these NCs always exhibits orthorhombic tilting of PbX6 octahedra within locally ordered subdomains. These subdomains are hinged through a two-/three-dimensional (2D/3D) network of twin boundaries through which the coherent arrangement of the Pb ions throughout the whole NC is preserved. The density of these twin boundaries determines the size of the subdomains and results in an apparent higher-symmetry structure on average in the high-temperature modification. Dynamic cooperative rotations of PbX6 octahedra are likely at work at the twin boundaries, causing the rearrangement of the 2D or 3D network, particularly effective in the pseudocubic phases. An orthorhombic, 3D γ-phase, isostructural to that of CsPbBr3 is found here in as-synthesized CsPbI3 NCs.