TY - GEN A1 - Pożarowska, Emilia A1 - Pleines, Linus A1 - Ewert, Moritz A1 - Prieto, Mauricio J. A1 - Tănase, Liviu Christian A1 - Souza Caldas, Lucas de A1 - Tiwari, Aarti A1 - Schmidt, Thomas A1 - Falta, Jens A1 - Krasovskii, Eugene A1 - Morales, Carlos A1 - Flege, Jan Ingo T1 - Preparation and stability of the hexagonal phase of samarium oxide on Ru(0001) T2 - Ultramicroscopy N2 - We have used low-energy electron microscopy (LEEM), micro-illumination low-energy electron diffraction (µLEED) supported by ab initio calculations, and X-ray absorption spectroscopy (XAS) to investigate in-situ and in real-time the structural properties of Sm2O3 deposits grown on Ru(0001), a rare-earth metal oxide model catalyst. Our results show that samarium oxide grows in a hexagonal A-Sm2O3 phase on Ru(0001), exhibiting a (0001) oriented-top facet and (113) side facets. Upon annealing, a structural transition from the hexagonal to cubic phase occurs, in which the Sm cations exhibit the +3 oxidation state. The unexpected initial growth in the A-Sm2O3 hexagonal phase and its gradual transition to a mixture with cubic C-Sm2O3 showcases the complexity of the system and the critical role of the substrate in the stabilization of the hexagonal phase, which was previously reported only at high pressures and temperatures for bulk samaria. Besides, these results highlight the potential interactions that Sm could have with other catalytic compounds with respect to the here gathered insights on the preparation conditions and the specific compounds with which it interacts. KW - Samarium oxide (Sm2O3) KW - low-energy electron microscopy (LEEM) KW - X-ray photoemission electron microscopy (XPEEM) KW - Facets KW - Epitaxy KW - Hexagonal phase Y1 - 2023 U6 - https://doi.org/10.1016/j.ultramic.2023.113755 SN - 0304-3991 SN - 1879-2723 VL - 250 ER - TY - GEN A1 - Kot, Małgorzata A1 - Gawlińska‐Nęcek, Katarzyna A1 - Pożarowska, Emilia A1 - Henkel, Karsten A1 - Schmeißer, Dieter T1 - Photosensitivity and carrier densities of perovskite solar absorbers T2 - Advanced science N2 - Dark and light current–voltage characteristics of perovskite solar absorbers are analyzed in terms of their carrier densities. The analysis reveals p‐type large polarons as a dominant carrier type in the investigated perovskite solar cells. The mechanism causing photosensitivity is attributed to the dissociation (and pairing) of bipolarons to large polarons (and vice versa) that are controlled by the internal potential Γ. As an example, the polaron concept is tested for a formamidinium lead triiodide perovskite solar cell. The individual steps of the data analysis are demonstrated and determine the ionicity factor of this perovskite film, quantify the density of the large polarons, and predict the gain and loss of photo‐induced carriers. It is deduced that a reversible light‐on/off operation can only occur when the bias voltage never exceeds a critical value of the internal potential. The results gained in this study suggest that the novel analysis can be successively applied on different hybrid perovskite materials, too. KW - Bipolarons KW - Ionicity factor KW - Large polarons KW - Perovskite solar cells Y1 - 2025 UR - https://advanced.onlinelibrary.wiley.com/doi/epdf/10.1002/advs.202412711 U6 - https://doi.org/10.1002/advs.202412711 SN - 2198-3844 VL - 12 IS - 16 SP - 1 EP - 8 PB - Wiley CY - Hobken, New Jersey ER - TY - GEN A1 - Tschammer, Rudi A1 - Buß, Lars A1 - Pożarowska, Emilia A1 - Morales, Carlos A1 - Senanayake, Sanjaya D. A1 - Prieto, Mauricio J. A1 - Tănase, Liviu C. A1 - de Souza Caldas, Lucas A1 - Tiwari, Aarti A1 - Schmidt, Thomas A1 - Niño, Miguel A. A1 - Foerster, Michael A1 - Falta, Jens A1 - Flege, Jan Ingo T1 - High-temperature growth of CeOx on Au(111) and behavior under reducing and oxidizing conditions T2 - The journal of physical chemistry C N2 - Inverse oxide–metal model catalysts can show superior activity and selectivity compared with the traditional supported metal–oxide architecture, commonly attributed to the synergistic overlayer–support interaction. We have investigated the growth and redox properties of ceria nanoislands grown on Au(111) between 700 and 890 °C, which yields the CeO2–Au(111) model catalyst system. We have observed a distinct correlation between deposition temperature, structural order, and oxide composition through low-energy electron microscopy, low-energy electron diffraction, intensity–voltage curves, and X-ray absorption spectroscopy. Improved structural order and thermal stability of the oxide have been achieved by increasing the oxygen chemical potential at the substrate surface using reactive oxygen (O/O2) instead of molecular O2 during growth. In situ characterization under reducing (H2) and oxidizing atmospheres (O2, CO2) indicates an irreversible loss of structural order and redox activity at high reduction temperatures, while moderate temperatures result in partial decomposition of the ceria nanoislands (Ce3+/Ce4+) to metallic cerium (Ce0). The weak interaction between Au(111) and CeOx would facilitate its reduction to the Ce0 metallic state, especially considering the comparatively strong interaction between Ce0 and Au0. Besides, the higher reactivity of atomic oxygen promotes a stronger interaction between the gold and oxide islands during the nucleation process, explaining the improved stability. Thus, we propose that by driving the nucleation and growth of the ceria/Au system in a highly oxidizing regime, novel chemical properties can be obtained. KW - Inverse oxide-metal model catalysts KW - Ceria nanoislands KW - Growth KW - Redox properties KW - Low-energy electron microscopy (LEEM) KW - Low-energy electron diffraction (LEED) KW - Intensity–voltage curves KW - X-ray absorption spectroscopy (XAS) Y1 - 2025 U6 - https://doi.org/10.1021/acs.jpcc.4c08072 SN - 1932-7447 VL - 129 IS - 7 SP - 3583 EP - 3594 PB - American Chemical Society (ACS) CY - Washington, DC ER -