Publication date: 17th February 2025
Understanding the atomic-scale crystallographic properties of photovoltaic semiconductor materials such as silicon, GaAs, and CdTe has been essential in their development from interesting materials to large-scale energy conversion industries. However, studying photoactive hybrid perovskites by transmission electron microscopy (TEM) has proved particularly challenging due to the large electron energies typically employed in these studies. [1,2] In particular, the very close structural relationship between a number of crystallographic orientations of the pristine perovskite and lead iodide has resulted in severe ambiguity in the interpretation of EM-derived information, severely impeding the advance of atomic resolution understanding of the materials.
In this talk, I will outline how to reliably study hybrid organic-inorganic perovskite materials using electron microscopy. With the ability to image the pristine phase of these beam-sensitive materials, we are able to obtain highly localised crystallographic information about technologically relevant materials. Using low-dose selected area electron diffraction, I will show how mixing the archetypal CH(NH2)2PbI3 (FAPbI3) and CH3NH3PbI3 (MAPbI3) improves solar cell device performance through the elimination of twin domains and stacking faults. [3]
Using a careful low-dose scanning TEM (STEM) protocol, we are also able to image these materials in their thin-film form with atomic resolution. [4] Our images enable a wide range of previously undescribed phenomena to be observed, including a remarkably highly ordered atomic arrangement of sharp grain boundaries and coherent perovskite/PbI2 interfaces, with a striking absence of long-range disorder in the crystal. These findings explain why inter-grain interfaces are not necessarily detrimental to perovskite solar cell performance, in contrast to what is commonly observed for other polycrystalline semiconductors.
Combining broad beam electron diffraction with 4D STEM (or scanning electron diffraction), I will also show why certain 2D perovskite materials are better than others at improving device performance and stability.
Our findings thus provide a significant shift in our atomic-level understanding of this technologically important class of lead-halide perovskites.