Physical neural networks made of analog resistive switching processors are promising platforms for analog computing. State-of-the-art resistive switches rely on either conductive filament formation or phase change. These processes suffer from poor reproducibility or high energy consumption, respectively. Herein, we demonstrate the behavior of an alternative synapse design that relies on a deterministic charge-controlled mechanism, modulated electrochemically in solid-state. The device operates by shuffling the smallest cation, the proton, in a threeterminal configuration. It has a channel of active material, WO 3. A solid proton reservoir layer, PdH x , also serves as the gate terminal. A proton conducting solid electrolyte separates the channel and the reservoir. By protonation/deprotonation, we modulate the electronic conductivity of the channel over seven orders of magnitude, obtaining a continuum of resistance states. Proton intercalation increases the electronic conductivity of WO 3 by increasing both the carrier density and mobility. This switching mechanism offers low energy dissipation, good reversibility, and high symmetry in programming.

Segregation of aliovalent dopant cations is a common degradation pathway on perovskite oxide surfaces in energy conversion and catalysis applications. Here we focus on resolving quantitatively how dopant segregation is affected by oxygen chemical potential, which varies over a wide range in electrochemical and thermochemical energy conversion reactions. We employ electrochemical polarization to tune the oxygen chemical potential over many orders of magnitude. Altering the effective oxygen chemical potential causes the oxygen nonstoichiometry to change in the electrode. This then influences the mechanisms underlying the segregation of aliovalent dopants. These mechanisms are (i) the formation of oxygen vacancies that couples to the electrostatic energy of the dopant in the perovskite lattice and (ii) the elastic energy of the dopant due to cation size mismatch, which also promotes the reaction of the dopant with O2 from the gas phase. The present study resolves these two contributions over a wide range of effective oxygen pressures. Ca-, Sr-, and Ba-doped LaMnO3 are selected as model systems, where the dopants have the same charge but different ionic sizes. We found that there is a transition between the electrostatically and elastically dominated segregation regimes, and the transition shifted to a lower oxygen pressure with increasing cation size. This behavior is consistent with the results of our ab initio thermodynamics calculations. The present study provides quantitative insights into how the elastic energy and the electrostatic energy determine the extent of segregation for a given overpotential and atmosphere relevant to the operating conditions of perovskite oxides in energy conversion applications.

Stable composition and catalytic activity of surfaces are among the key requirements for materials employed in energy storage and conversion devices, such as solid oxide fuel cells (SOFCs). Perovskite oxides that serve as cathode in SOFCs suffer from segregation of the aliovalent substitutional cations and the formation of an inert, non-conductive phase at the surface. Here, we demonstrate that the surface of the state-of-the-art SOFC cathode material La0.8Sr0.2MnO3 (LSM) is stabilized against the segregation of Sr at high temperature by submonolayer coverages of Hf. The Hf is vapor-deposited onto the LSM thin film surface by e-beam evaporation. Using in situ near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), we analyze the surface composition of LSM thin films. Half the LSM surface was kept as-prepared, and half was Hf-modified, for a direct comparison of untreated and Hf-treated regions on the same sample. The formation of a binary SrOx surface species is quantified as descriptor for surface degradation. The onset of Sr segregation is observed at 450 °C on the bare LSM, followed by a substantial advance at 550 °C. Hf-treated regions of the same LSM surface exhibit significantly less Sr surface segregation at 450–550 °C. We interpret this stabilization imparted by Hf to arise from the suppression of the electrostatic attraction of Sr2+ cations to surface oxygen vacancies. Doping the surface layer with Hf, that has a higher affinity to oxygen, reduces this attraction by decreasing the surface oxygen vacancy concentration. In doing so, the use of physical vapor deposition highlights the direct role of the metal species in this system and excludes artifacts that could be introduced via chemical routes. The present work demonstrates this stabilizing effect of Hf on the surface of LSM, broadening the relevance of our prior findings on surface metal doping of other perovskite oxides.

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Controlling the size of Au nanoparticles (NPs) and their interaction with the oxide support is important for their catalytic performance in chemical reactions, such as CO oxidation and water-gas shift. It is known that the oxygen vacancies at the surface of support oxides form strong chemical bonding with the Au NPs and inhibit their coarsening and deactivation. The resulting Au/oxygen vacancy interface also acts as an active site for oxidation reactions. Hence, small Au NPs are needed to increase the density of the Au/oxide interface. A dynamic way to control the size of the Au NPs on an oxide support is desirable but has been missing in the field. Here, we demonstrate an electrochemical method to control the size of the Au NPs by controlling the surface oxygen vacancy concentration of the support oxide. Oxides with different reducibilities, La 0.8 Ca 0.2 MnO 3±δ and Pr 0.1 Ce 0.9 O 2−δ , are used as model support oxides. By applying the electrochemical potential, we achieve a wide range of effective oxygen pressures, pO 2 (10 −37 −10 14 atm), in the support oxides. Applying the cathodic potential creates a high concentration of oxygen vacancies and forms finely distributed Au NPs with sizes of 7−13 nm at 700−770 °C in 10 min, while the anodic potential oxidizes the surface and increases the size of the Au NPs. The onset cathodic potential required to create small Au NPs depends strongly on the reducibility of the support oxide. The Au NPs did not undergo sintering even at 700−770 °C under the cathodic potential and also were stable in catalytically relevant conditions without potential.