Polarons, the combined motion of electrons in a cloth of their lattice distortions, are a key transport feature in doped manganites. To develop a profound understanding of the colossal resistance effects induced by external fields, the study of polaron correlations and the resulting collective polaron behavior, i.e., polaron ordering and transition from polaronic transport to metallic transport is essential. We show that static long-range ordering of Jahn–Teller polarons forms a polaron solid which represents a new type of charge and orbital ordered state. The related noncentrosymmetric lattice distortions establish a connection between colossal resistance effects and multiferroic properties, i.e., the coexistence of ferroelectric and antiferromagnetic ordering. Colossal resistance effects due to an electrically induced polaron solid–liquid transition are directly observed in a transmission electron microscope with local electric stimulus applied in situ using a piezo-controlled tip. Our results shed light onto the colossal resistance effects in magnetic field and have a strong impact on the development of correlated electron-device applications such as resistive random access memory (RRAM).

${\mathrm{Pr}}_{1-x}{\mathrm{Ca}}_x{\mathrm{MnO}}_3$ in the doping range between $0.3<x<0.5$ represent an extremely interesting manganite system for the study of the interplay of different kinds of ordering (charge, orbital, lattice, and spin). While there is consensus that a charge- and orbital-ordered state develops below a transition temperature $T_{\mathrm{co}}\approx 230\mathrm{K}$, recent controversial structural refinements resulting from neutron and x-ray diffraction studies challenged our understanding of the particular type of charge ordering (CO) and orbital ordering (OO), and consequently, the underlying mechanism of the colossal resistance effects. Here, we present a detailed high-resolution transmission electron microscopy and electron-diffraction study that, based on extinction rules, resolves the current controversy and confirms the existence of the Zener-polaron (ZP)-type CO and/or OO in ${\mathrm{Pr}}_{1-x}{\mathrm{Ca}}_x{\mathrm{MnO}}_3$. The ZP-type ordering is further verified by atomic-column-resolved electron energy-loss spectroscopy revealing strong charge ordering of the in-plane oxygen-Mn bonds, while valence disproportionation at the Mn sites is less than expected. Over wide doping and temperature ranges, we observed structural phase coexistence between the $\mathrm{ZP}\text{−}\mathrm{CO}∕\mathrm{OO}$ $P{2}_{1}nm$ and the disordered Pbnm structure.

Studying catalysts in situ is of high interest for understanding their surface structure and electronic states in operation. Herein, we present a study of epitaxial manganite perovskite thin films (Pr_1−xCa_xMnO₃) active for the oxygen evolution reaction (OER) from electro-catalytic water splitting. X-ray absorption near-edge spectroscopy (XANES) at the Mn L- and O K-edges, as well as X-ray photoemission spectroscopy (XPS) of the O 1s and Ca 2p states have been performed in ultra-high vacuum and in water vapor under positive applied bias at room temperature. It is shown that under the oxidizing conditions of the OER a reduced Mn²⁺ species is generated at the catalyst surface. The Mn valence shift is accompanied by the formation of surface oxygen vacancies. Annealing of the catalysts in O₂ atmosphere at 120 °C restores the virgin surfaces.

An improved understanding of the correlation between the electronic properties of Mn-O bonds, activity and stability of electro-catalysts for the oxygen evolution reaction (OER) is of great importance for an improved catalyst design. Here, an in-depth study of the relation between lattice structure, electronic properties and catalyst performance of the perovskite Ca_1−xPr_xMnO₃ and the first-order RP-system Ca_2−xPr_xMnO₄ at doping levels of x = 0, 0.25 and 0.5 is presented. Lattice structure is determined by X-ray powder diffraction and Rietveld refinement. X-ray absorption spectroscopy of Mn-L and O-K edges gives access to Mn valence and covalency of the Mn-O bond. Oxygen evolution activity and stability is measured by rotating ring disc electrode studies. We demonstrate that the highest activity and stability coincidences for systems with a Mn-valence state of +3.7, though also requiring that the covalency of the Mn-O bond has a relative minimum. This observation points to an oxygen evolution mechanism with high redox activity of Mn. Covalency should be large enough for facile electron transfer from adsorbed oxygen species to the MnO₆ network; however, it should not be hampered by oxidation of the lattice oxygen, which might cause a crossover to material degradation. Since valence and covalency changes are not entirely independent, the introduction of the energy position of the e_g^↑ pre-edge peak in the O-K spectra as a new descriptor for oxygen evolution is suggested, leading to a volcano-like representation of the OER activity.

Improving the activity of catalysts for the oxygen evolution reaction (OER) requires a detailed understanding of the surface chemistry and structure to deduce structure-function relationships (descriptors) for fundamental insight. We chose epitaxial (100)-oriented La_0.6Sr_0.4Mn_1−δO₃ (LSMO) thin films as a model system with high electrochemical activity comparable to (110)-oriented IrO₂ to investigate the effect of Mn off-stoichiometry on both catalytic activity and stability. Extensive structural characterization was performed by microscopic and spectroscopic methods before and after electrochemical characterization using rotating ring-disk studies. Stoichiometric LSMO had the highest activity, while both Mn deficiency and excess reduced the catalytic activity. Furthermore, all samples preserved the crystal structure up to the very surface. Mn excess improved the long-term activity, and we hypothesize that excess Mn stabilizes the surface chemistry during catalysis. Our data show that the defect chemistry should be considered when designing catalysts with enhanced activity and rugged stability.