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The 21st International Conference on Microscopy of Semiconducting Materials (MSM-XXI) reports progress in the imaging, diffraction and spectroscopy of inorganic and hybrid perovskite semiconductor nanostructures used in (opto)electronic and photonic devices, as well as interfaces of thin dielectric, metal or polymer films to such semiconductors. With a focus on electron microscopy but also encompassing a wide range of related techniques, such as scanning probe microscopy and 3D atom probe, this series has now been running for 40 years.