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In the last decade, Cu2ZnSnS4 (CZTS) has been a promising earth-abundant, nontoxic candidate material for absorption layers within thin-film solar cells. One major issue preventing this type of solar cells from achieving competitive efficiency is impurity phases and structural defects in the bulk of the absorber; as a four-element compound, the formation of CZTS is highly sensitive to synthesis conditions. The impurity phases and defects differ by the fabrication method, and thus experimental characterization is vital for the successful development of CZTS photovoltaics. In this work, we characterize CZTS nanoparticles obtained by the hot-injection method and a standard N2/S annealing procedure. Phase-pure kesterite CZTS samples in the desired compositional range were characterized by standard means, i.e., Raman spectroscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. However, using synchrotron X-ray diffraction with Rietveld refinement, we show that the as-synthesized nanoparticles consist of a mixture of the tetragonal and the fully disordered cubic sphalerite phase and transform into the tetragonal structure after heat treatment. Sn vacancies are seen in the annealed samples. X-ray total scattering with pair distribution function analysis furthermore suggests the presence of a nanostructured CZTS phase along with a bulk material. Finally, this study compares the benefits of applying synchrotron radiation instead of a standard laboratory X-ray diffraction when characterizing highly complex materials.

Ferroelectric materials offer a low-energy, high-speed alternative to conventional logic and memory circuitry. Hafnia-based films have achieved singledigit nm ferroelectricity, enabling further device miniaturization. However, they can exhibit nonideal behavior, specifically wake-up and fatigue effects, leading to unpredictable performance variation over consecutive electronic switching cycles, preventing large-scale commercialization. The origins are still under debate. Using plasmon-enhanced spectroscopy, a non-destructive technique sensitive to <1% oxygen vacancy variation, phase changes, and single switching cycle resolution, the first real-time in operando nanoscale direct tracking of oxygen vacancy migration in 5 nm hafnium zirconium oxide during a pre-wake-up stage is provided. It is shown that the pre-wake-up leads to a structural phase change from monoclinic to orthorhombic phase, which further determines the device wake-up. Further migration of oxygen ions in the phase changed material is then observed, producing device fatigue. These results provide a comprehensive explanation for the wake-up and fatigue with Raman, photoluminescence and darkfield spectroscopy, combined with density functional theory and finite-difference time-domain simulations.

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