The Formation of Performance Enhancing Pseudo‐Composites in the Highly Active La1–xCaxFe0.8Ni0.2O3 System for IT‐SOFC Application

The La_1–xCa_xFe_0.8Ni_0.2O_3–δ (0 ≤ x ≤ 0.9) system is investigated for potential application as a cathode material for intermediate temperature solid oxide fuel cells (IT‐SOFCs). A broad range of experimental techniques have been utilized in order to elucidate the characteristics of the entire compositional range. Low A‐site Ca content compositions (x ≤ 0.4) feature a single perovskite solid solution. Compositions with 40% Ca content (x = 0.4) exhibit the highest electrical and ionic conductivities of these single phase materials (250 and 1.9 × 10^?3 S cm^?1 at 800 °C, respectively), a level competitive with state‐of‐the‐art (La,Sr)(Fe,Co)O₃. Between 40 and 50% Ca content (0.4 > x > 0.5) a solubility limit is reached and a secondary, brownmillerite‐type phase appears for all higher Ca content compositions (0.5 ≤ x ≤ 0.9). While typically seen as detrimental to electrochemical performance in cathode materials, this phase brings with it ionic conductivity at operational temperatures. This gives rise to the effective formation of pseudo‐composite materials which feature significantly enhanced performance characteristics, while also providing the closest match in thermal expansion behavior to typical electrolyte materials. This all comes with the advantage of being produced through a simple, single‐step, low‐cost production route without the issues associated with typical composite materials. The highest performing pseudo‐composite material (x = 0.5) exhibits electronic conductivity of 300–350 S cm^?1 in the 600–800 °C temperature range while the best polarisation resistance (R_p) values of approximately 0.2 Ω cm² are found in the 0.5 ≤ x ≤ 0.7 range.     

An In Situ Formed,Dual‐Phase Cathode with a Highly Active Catalyst Coating for Protonic Ceramic Fuel Cells

Composite cathodes of solid oxide fuel cells (SOFCs) are normally fabricated by mechanical mixing of electronic‐ and ionic‐conducting phases. Here, a dual‐phase SOFC cathode, composed of perovskite PrNi_0.5Mn_0.5O₃ (PNM) and exsoluted fluorite PrO_x particles, produced in situ through a glycine–nitrate solution combustion process, is reported. When applied as the cathode for a BaZr_0.1Ce_0.7Y_0.1Yb_0.1O₃‐based protonic ceramic fuel cell, the hybrid cathode displays excellent electrocatalytic activity (area‐specific resistance of 0.052 Ω cm² at 700 °C) and remarkable long‐term stability when operated at a cell voltage of 0.7 V for ≈500 h using H₂ as fuel and ambient air as oxidant. The excellent performance is attributed to the proton‐conducting BaPrO₃‐based coating and high‐concentration oxygen vacancies of a Ba‐doped PNM surface coating, produced by the reaction between the cathode and Ba from the electrolyte (via evaporation or diffusion), as confirmed by detailed X‐ray photoelectron spectroscopy, Raman spectroscopy, and density functional theory‐based calculations.     

An Easily Sintered,Chemically Stable,Barium Zirconate‐Based Proton Conductor for High‐Performance Proton‐Conducting Solid Oxide Fuel Cells

Yttrium and indium co‐doped barium zirconate is investigated to develop a chemically stable and sintering active proton conductor for solid oxide fuel cells (SOFCs). BaZr_0.8Y_0.2‐xIn_xO_{3‐ δ} possesses a pure cubic perovskite structure. The sintering activity of BaZr_0.8Y_0.2‐xIn_xO_{3‐ δ} increases significantly with In concentration. BaZr_0.8Y_0.15In_0.05O_{3‐ δ} (BZYI5) exhibits the highest total electrical conductivity among the sintered oxides. BZYI5 also retains high chemical stability against CO₂, vapor, and reduction of H₂. The good sintering activity, high conductivity, and chemical stability of BZYI5 facilitate the fabrication of durable SOFCs based on a highly conductive BZYI5 electrolyte film by cost‐effective ceramic processes. Fully dense BZYI5 electrolyte film is successfully prepared on the anode substrate by a facile drop‐coating technique followed by co‐firing at 1400 °C for 5 h in air. The BZYI5 film exhibits one of the highest conductivity among the BaZrO₃‐based electrolyte films with various sintering aids. BZYI5‐based single cells output very encouraging and by far the highest peak power density for BaZrO₃‐based proton‐conducting SOFCs, reaching as high as 379 mW cm^?2 at 700 °C. The results demonstrate that Y and In co‐doping is an effective strategy for exploring sintering active and chemically stable BaZrO₃‐based proton conductors for high performance proton‐conducting SOFCs.     

A High Power Density Intermediate‐Temperature Solid Oxide Fuel Cell with Thin (La0.9Sr0.1)0.98(Ga0.8Mg0.2)O3‐δ Electrolyte and Nano‐Scale Anode

Solid oxide fuel cells (SOFCs) with thin (La_0.9Sr_0.1)_0.98Ga_0.8Mg_0.2O_3‐δ (LSGM) electrolytes are primary candidates for achieving high (> 1 W cm^‐2) power density at intermediate (< 650 °C) temperatures. Although high power density LSGM‐electrolyte SOFCs have been reported, it is still necessary to develop a fabrication process suitable for large‐scale manufacturing and to minimize the amount of LSGM used. Here we show that SOFCs made with a novel processing method and a Sr_0.8La_0.2TiO_{3‐ α} (SLT) oxide support can achieve high power density at intermediate temperature. The SLT support is advantageous, especially compared to LSGM supports, because of its low materials cost, electronic conductivity, and good mechanical strength. The novel process is to first co‐fire the ceramic layers – porous SLT support, porous LSGM layer, and dense LSGM layer – followed by infiltration of nano‐scale Ni into the porous layers. Low polarization resistance of 0.188 Ωcm² was achieved at 650 °C for a cell with an optimized anode functional layer (AFL) and an (La,Sr)(Fe,Co)O₃ cathode. Maximum power density reached 1.12 W cm^?2 at 650 °C, limited primarily by cathode polarization and ohmic resistances, so there is considerable potential to further improve the power density.     

Harnessing Selective Exsolution of Sn Metal to Enhance Electrical Conductivity in Oxygen-Deficient Perovskite Stannates

The versatile application of newly discovered oxide semiconductors calls for developing a simple process to generate conducting carriers. High-temperature reduction treatment leads to electrical conduction in perovskite stannate semiconductors, but carrier concentration is poorly controlled and inconsistently reported in BaSnO_3−δ films after the reduction process so far. Here, a new strategy to enhance the electrical conductivity of BaSnO_3−δ films is demonstrated by exploiting selective exsolution of Sn metals in the perovskite framework. Due to strong dependence of conductivity on initial Sn/Ba cation ratio in the reduced BaSnO_3−δ films, interestingly, only Sn-excess BaSnO_3−δ films show a dramatic increase of carrier concentration ( ∆ n_3D  = 5–7 × 10¹⁹ cm⁻³) after high-temperature reduction; exceptionally high electrical conductivity (σ  ≈  6000 S cm⁻¹) is achieved in reduced Sn-excess (La, Ba)SnO_3−δ films, which exceed full activation of La dopants in untreated (La, Ba)SnO₃. By multiple characterizations combined with theoretical calculation, it is disclosed that a small fraction of segregated β-Sn nanoparticles is likely to contribute the additional source of n_3D in the BaSnO_3−δ matrix as a result of spontaneous charge transfer from the segregated β-Sn metallic phase to BaSnO_3−δ. These original results propose a simple strategy to further increase electrical conductivity in perovskite oxide semiconductors by non-stoichiometry-driven metal exsolution.     

A Three Component Self‐Assembled Epitaxial Nanocomposite Thin Film

A self‐assembled three phase epitaxial nanocomposite film is grown consisting of ≈3 nm diameter fcc metallic Cu nanorods within square prismatic SrO rocksalt nanopillars in a Sr(Ti,Cu)O_3‐δ perovskite matrix. Each phase has an epitaxial relation to the others. The core–shell‐matrix structures are grown on SrTiO₃ substrates and can also be integrated onto Si using a thin SrTiO₃ buffer. The structure is made by pulsed laser deposition in vacuum from a SrTi_0.75Cu_0.25O₃ target, and formed as a result of the limited solubility of Cu in the perovskite matrix. Wet etching removes the 3 nm diameter Cu nanowires leaving porous SrO pillars. The three‐phase nanocomposite film is used as a substrate for growing a second epitaxial nanocomposite consisting of CoFe₂O₄ spinel pillars in a BiFeO₃ perovskite matrix, producing dramatic effects on the structure and magnetic properties of the CoFe₂O₄. This three‐phase vertical nanocomposite provides a complement to the well‐known two‐phase nanocomposites, and may offer a combination of properties of three different materials as well as additional avenues for strain‐mediated coupling within a single film.     

(Magic Dopant) Amphoteric Behavior of a Redox‐Active Transition Metal Ion in a Perovskite Lattice: New Insights on the Lattice Site Occupation of Manganese in SrTiO3

It is demonstrated that a transition metal redox‐active ion can exhibit amphoteric dopant substitution in the SrTiO₃ perovskite lattice. In stoichiometric SrTiO₃, the manganese dopant is preferably accommodated through isovalent substitution as Mn²⁺ on the strontium site and as Mn⁴⁺ on the titanium site. Previous studies have suggested that either type of substitution is possible for compositions with tailored Sr/Ti stoichiometry. Using electron paramagnetic resonance (EPR) spectroscopy, the site occupancy of dilute concentrations of manganese is investigated in SrTiO₃ as a function of the Sr/Ti ratio. The tuned Sr/Ti ratio can be used to manipulate the nature of the manganese substitution, and it is shown that Sr‐rich compositions (Sr/Ti > 1.001) processed in air result in B‐site isovalent doping. For B‐site substituted manganese ions, a new EPR signal for aliovalent Mn²⁺ is observed in compositions annealed under reducing atmosphere. The concentration of oxygen vacancies observed with EPR is also shown to depend on the Sr/Ti stoichiometry. With improved control over the site of substitution and valence state, doping with a transition metal redox‐active ion may facilitate the ability to engineer new electronic functionality into the perovskite lattice.     

Nanophase ZnCo2O4 as a High Performance Anode Material for Li‐Ion Batteries

ZnCo₂O₄ has been synthesized by the low‐temperature and cost‐effective urea combustion method. X‐ray diffraction (XRD), HR‐TEM and selected area electron diffraction (SAED) studies confirmed its formation in pure and nano‐phase form with particle size ～ 15–20 nm. Galvanostatic cycling of nano‐ZnCo₂O₄ in the voltage range 0.005–3.0 V versus Li at 60 mA g^–1 gave reversible capacities of 900 and 960 mA h g^–1, when cycled at 25 °C and 55 °C, respectively. These values correspond to ～ 8.3 and ～ 8.8 mol of recyclable Li per mole of ZnCo₂O₄. Almost stable cycling performance was exhibited in the range 5–60 cycles at 60 mA g^–1 and at 25 °C with ～ 98 % coulombic efficiency. A similar cycling stability at 55 °C, and good rate‐capability both at 25 and 55 °C were found. The average discharge‐ and charge‐potentials were ～ 1.2 V and ～ 1.9 V, respectively. The ex‐situ‐XRD, ‐HRTEM, ‐SAED and galvanostatic cycling data are consistent with a reaction mechanism for Li‐recyclability involving both de‐alloying‐alloying of Zn and displacement reactions, viz., LiZn ? Zn ? ZnO and Co ? CoO ? Co₃O₄. For the first time we have shown that both Zn‐ and Co‐ions act as mutual beneficial matrices and reversible capacity contribution of Zn through both alloy formation and displacement reaction takes place to yield stable and high capacities. Thus, nano‐ZnCo₂O₄ ranks among the best oxide materials with regard to Li‐recyclability.     

The Excellence of Both Worlds: Developing Effective Double Perovskite Oxide Catalyst of Oxygen Reduction Reaction for Room and Elevated Temperature Applications

The efficiencies of a number of electrochemical devices (e.g., fuel cells and metal‐air batteries) are mainly governed by the kinetics of the oxygen reduction reaction (ORR). Among all the good ORR catalysts, the partially substituted double perovskite oxide (AA′B₂O_5+δ) has the unique layered structure, providing a great flexibility regarding the optimization of its electronic structures and physicochemical properties. Here, it is demonstrated that the double perovskite oxide, i.e., NdBa_0.75Ca_0.25Co_1.5Fe_0.5O_5+δ, is a good ORR catalyst at both room and elevated temperatures. Under ambient condition, its half‐wave potential of ORR in alkaline media is as low as 0.74 V versus RHE; at 650 °C, the cathodic polarization resistance is merely 0.0276 Ω cm² according to a symmetric cell measurement, whereas the solid oxide fuel cells using this cathode exhibit a maximum power density of 1982 mW cm^?2. From various materials characterizations, it is hypothesized that its excellent ORR activity is strongly correlated with the crystallographic, electronic, and defect structures of the materials.     

Chemically Stable Pr and Y Co‐Doped Barium Zirconate Electrolytes with High Proton Conductivity for Intermediate‐Temperature Solid Oxide Fuel Cells

A chemically stable and highly proton‐conductive electrolyte is developed by partially substituting the Zr site of Y‐doped barium zirconate (BZY) with 10 mol% of Pr. Compared to BZY, BaZr_0.7Pr_0.1Y_0.2O_3‐δ (BZPY) shows improved sinterability as revealed by dilatometric measurements and scanning electron microscopy (SEM) analysis. Dense samples are obtained after sintering at 1500?C for 8 h. Moreover, BZPY shows good chemical stability in the wide range of fuel‐cell operating conditions. The larger density and the enhanced grain growth, compared to BZY, allow the volume content of grain boundaries, which generally show a high resistance for proton transport, to be reduced and, thus, a high proton conductivity can be achieved in the temperature range of interest for practical applications (above 10^?2 Scm^?1 at 600?C). The good sinterability, chemical stability, and high conductivity of the BZPY electrolyte enabled the fabrication of single‐cell prototypes based on a thin BZPY membrane by a simple and cost‐saving co‐pressing method. Electrochemical impedance spectroscopy (EIS) analysis performed during fuel‐cell tests under open‐circuit conditions confirms the good electrical performance of BZPY as electrolyte material. To improve the present fuel‐cell performance adapted cathode materials for this BZPY electrolyte need to be developed.     

A New Family of Proton‐Conducting Electrolytes for Reversible Solid Oxide Cells: BaHfxCe0.8−xY0.1Yb0.1O3−δ

Reversible solid oxide cells based on ceramic proton conductors have potential to be the most efficient system for large‐scale energy storage. The performance and long‐term durability of these systems, however, are often limited by the ionic conductivity or stability of the proton‐conducting electrolyte. Here new family of solid oxide electrolytes, BaHf_xCe_0.8?xY_0.1Yb_0.1O_3?δ (BHCYYb), which demonstrate a superior ionic conductivity to stability trade‐off than the state‐of‐the‐art proton conductors, BaZr_xCe_0.8?xY_0.1Yb_0.1O_3?δ (BZCYYb), at similar Zr/Hf concentrations, as confirmed by thermogravimetric analysis, Raman, and X‐ray diffraction analysis of samples over 500 h of testing are reported. The increase in performance is revealed through thermodynamic arguments and first‐principle calculations. In addition, lab scale full cells are fabricated, demonstrating high peak power densities of 1.1, 1.4, and 1.6 W cm^?2 at 600, 650, and 700 °C, respectively. Round‐trip efficiencies for steam electrolysis at 1 A cm^?2 are 78%, 72%, and 62% at 700, 650, and 600 °C, respectively. Finally, CO₂? H₂O electrolysis is carried out for over 700 h with no degradation.     

Pyrolyzed Cobalt Corrole as a Potential Non‐Precious Catalyst for Fuel Cells

Non‐precious metal catalysts of the oxygen reduction reaction are highly favored for use in polymer electrolyte fuel cells (PEFC) because of their relatively low cost. Here, a new carbon‐black‐supported pyrolyzed Co‐corrole (py‐Co‐corrole/C) catalyst of the oxygen reduction reaction (ORR) in a PEFC cathode is demonstrated to have high catalytic performance. The py‐Co‐corrole/C at 700 °C exhibits optimized ORR activity and participates in a direct four‐electron reduction pathway for the reduction of O₂ to H₂O. The H₂‐O₂ PEFC test of py‐Co‐corrole/C in the cathode reveals a maximum power density of 275 mW cm^?2, which yields a higher performance and a lower Co loading than previous studies of Co‐based catalysts for PEFCs. The enhancement of the ORR activity of py‐Co‐corrole/C is attributable to the four‐coordinated Co‐corrole structure and the oxidation state of the central cobalt.     

Phosphorus‐Doped Perovskite Oxide as Highly Efficient Water Oxidation Electrocatalyst in Alkaline Solution

Developing cost‐effective and efficient electrocatalysts for oxygen evolution reaction (OER) is of paramount importance for the storage of renewable energies. Perovskite oxides serve as attractive candidates given their structural and compositional flexibility in addition to high intrinsic catalytic activity. In a departure from the conventional doping approach utilizing metal elements only, here it is shown that non‐metal element doping provides an another attractive avenue to optimize the structure stability and OER performance of perovskite oxides. This is exemplified by a novel tetragonal perovskite developed in this work, i.e., SrCo_0.95P_0.05O_{3– δ} (SCP) which features higher electrical conductivity and larger amount of O₂ ^2?/O^? species relative to the non‐doped parent SrCoO_{3– δ} (SC), and thus shows improved OER activity. Also, the performance of SCP compares favorably to that of well‐developed perovskite oxides reported. More importantly, an unusual activation process with enhanced activity during accelerated durability test (ADT) is observed for SCP, whereas SC delivers deactivation for the OER. Such an activation phenomenon for SCP may be primarily attributed to the in situ formation of active A‐site‐deficient structure on the surface and the increased electrochemical surface area during ADT. The concept presented here bolsters the prospect to develop a viable alternative to precious metal‐based catalysts.     

Integration of Self‐Assembled Epitaxial BiFeO3–CoFe2O4 Multiferroic Nanocomposites on Silicon Substrates

Perovskite‐spinel epitaxial nanocomposite thin films are commonly grown on single crystal perovskite substrates, but integration onto a Si substrate can greatly increase their usefulness in devices. Epitaxial BiFeO₃–CoFe₂O₄ nanocomposites consisting of CoFe₂O₄ pillars in a BiFeO₃ matrix are grown on (001) Si with two types of buffer layers: molecular beam epitaxy (MBE)‐grown SrTiO₃‐coated Si and pulsed‐laser‐deposited (PLD) Sr(Ti_0.65Fe_0.35)O₃/CeO₂/yttria‐stabilized ZrO₂/Si. The nanocomposite grows with the same crystallographic orientation and morphology as that observed on single crystal SrTiO₃ when the buffered Si substrates are smooth, but roughness of the Sr(Ti_0.65Fe_0.35)O₃ promoted additional CoFe₂O₄ pillar orientations with 45° rotation. The nanocomposites on MBE‐buffered Si show very high magnetic anisotropy resulting from magnetoelastic effects, whereas the hysteresis of nanocomposites on PLD‐buffered Si can be understood as a combination of the hysteresis of the Sr(Ti_0.65Fe_0.35)O₃ film and the CoFe₂O₄ pillars.     

Unusual Strain Accommodation and Conductivity Enhancement by Structure Modulation Variations in Sr4Fe6O12+δ Epitaxial Films

Mixed ionic and electronic conducting (MIEC) films can be applied in solid state electrochemical devices such as oxygen separation membranes for producing pure oxygen, gas sensors or as cathode in solid oxide fuel cells. The current interest in layered perovskite‐related phases, like Sr₄Fe₆O₁₃ (SFO), arises from their significant oxygen permeability as predicted from theoretical studies. Nevertheless, before any practical application further fundamental study on this fairly unknown oxide is required mainly to assess the mechanisms affecting the transport properties. Epitaxial Sr₄Fe₆O_12+δ (SFO) films of b‐axis orientation with different thicknesses have been prepared by the pulsed laser deposition technique onto different perovskite substrates: SrTiO₃, NdGaO₃ and LaAlO₃. The strain accommodation has been found to vary as a function of film thickness as well as the substrate material causing different type of defects in the film microstructure, as well as variations in the oxygen anion content and ordering. Correspondingly, the total electrical conductivity of the films has been also found to vary significantly as a function of thickness and substrate type showing an unexpected enhancement for strained thin films. The variations in the transport properties are discussed in terms of the different strain accommodation mechanisms and the variation of the modulated structure observed for this compound.     

Carbon Nanotube Based Inverted Flexible Perovskite Solar Cells with All‐Inorganic Charge Contacts

Organolead halide perovskite solar cells (PSC) are arising as promising candidates for next‐generation renewable energy conversion devices. Currently, inverted PSCs typically employ expensive organic semiconductor as electron transport material and thermally deposited metal as cathode (such as Ag, Au, or Al), which are incompatible with their large‐scale production. Moreover, the use of metal cathode also limits the long‐term device stability under normal operation conditions. Herein, a novel inverted PSC employs a SnO₂‐coated carbon nanotube (SnO₂@CSCNT) film as cathode in both rigid and flexible substrates (substrate/NiO‐perovskite/Al₂O₃‐perovskite/SnO₂@CSCNT‐perovskite). Inverted PSCs with SnO₂@CSCNT cathode exhibit considerable enhancement in photovoltaic performance in comparison with the devices without SnO₂ coating owing to the significantly reduced charge recombination. As a result, a power conversion efficiency of 14.3% can be obtained on rigid substrates while the flexible ones achieve 10.5% efficiency. More importantly, SnO₂@CSCNT‐based inverted PSCs exhibit significantly improved stability compared to the standard inverted devices made with silver cathode, retaining over 88% of their original efficiencies after 550 h of full light soaking or thermal stress. The results indicate that SnO₂@CSCNT is a promising cathode material for long‐term device operation and pave the way toward realistic commercialization of flexible PSCs.     

Versatile and Highly Efficient Controls of Reversible Topotactic Metal–Insulator Transitions through Proton Intercalation

The ability to tailor a new crystalline structure and associated functionalities with a variety of stimuli is one of the key issues in material design. Developing synthetic routes to functional materials with partially absorbed nonmetallic elements (i.e., hydrogen and nitrogen) can open up more possibilities for preparing novel families of electronically active oxide compounds. Fast and reversible uptake and release of hydrogen in epitaxial ABO₃ manganite films through an adapted low‐frequency inductively coupled plasma technology is introduced. Compared with traditional dopants of metallic cations, the plasma‐assisted hydrogen implantations not only produce reversibly structural transformations from pristine perovskite (PV) phase to a newly found protonation‐driven brownmillerite one but also regulate remarkably different electronic properties driving the material from a ferromagnetic metal to a weakly ferromagnetic insulator for a range of manganite (La_1?xSr_xMnO₃) thin films. Moreover, a reversible perovskite‐brownmillerite‐perovskite transition is achieved at a relatively low temperature (T ≤ 350 °C), enabling multifunctional modulations for integrated electronic systems. The fast, low‐temperature control of structural and electronic properties by the facile hydrogenation/dehydrogenation treatment substantially widens the space for exploring new possibilities of novel properties in proton‐based multifunctional materials.     

Large Nonclassical Electrostriction in (Y,Nb)‐Stabilized δ‐Bi2O3

Classical electrostriction, describing a second‐order electromechanical response of insulating solids, scales with elastic compliance, S, and inversely with dielectric susceptibility, ε. This behavior, first noted 20 years ago by Robert Newnham, is shown to apply to a wide range of electrostrictors including polymers, glasses, crystalline linear dielectrics, and relaxor ferroelectrics. Electrostriction in fluorite ceramics of (Y, Nb)‐stabilized δ‐Bi₂O₃ is examined with 16%–23% vacant oxygen sites. Given the values of compliance and dielectric susceptibility, the electrostriction coefficients are orders of magnitude larger than those expected from Newnham's scaling law. In ambient temperature nanoindentation measurements, (Y, Nb)‐stabilized δ‐Bi₂O₃ displays primary creep. These findings, which are strikingly similar to those reported for Gd‐doped ceria, support the suggestion that ion conducting ceramics with the fluorite structure, a large concentration of anion vacancies and anelastic behavior, may constitute a previously unknown class of electrostrictors.     

Epitaxial Magnetic Oxide Nanocrystals Via Phase Decomposition of Bismuth Perovskite Precursors

The phase instability of bismuth perovskite (BiMO₃), where M is a ferromagnetic cation, is exploited to create self‐assembled magnetic oxide nanocrystal arrays on oxide supports. Conditions during pulsed laser deposition are tuned so as to induce complete breakdown of the perovskite precursor into bismuth oxide (Bi₂O₃) and metal oxide (M‐O_x) pockets. Subsequent cooling in vacuum volatizes the Bi₂O₃ leaving behind an array of monodisperse nanocrystals. In situ reflective high energy electron diffraction beam is exploited to monitor the synthesis in real‐time. Analysis of the patterns confirms the phase separation and volatization process. Successful synthesis of M‐O_x, where M = Mn, Fe, Co, and Cr, is shown using this template‐free facile approach. Detailed magnetic characterization of nanocrystals is carried out to reveal the functionalities such as magnetic anisotropy as well as larger than bulk moments, as expected in these oxide nanostructures.     

Non‐stoichiometry in Oxide Thin Films: A Chemical Capacitance Study of the Praseodymium‐Cerium Oxide System

While the properties of functional oxide thin films often depend strongly on their oxygen stoichiometry, there have been few ways to extract this information reliably and in situ. In this work, the derivation of the oxygen non‐stoichiometry of dense Pr_0.1Ce_0.9O_2?δ thin films from an analysis of chemical capacitance obtained by impedance spectroscopy is described. Measurements are performed on electrochemical cells of the form Pr_0.1Ce_0.9O_2?δ/Y_0.16Zr_0.84O_1.92/Pr_0.1Ce_0.9O_2?δ over the temperature range of 450 to 800 °C and oxygen partial pressure range of 10^?5 to 1 atm O₂. With the aid of a defect equilibria model, approximations relate chemical capacitance directly to non‐stoichiometry, without need for fitting parameters. The calculated non‐stoichiometry allows extraction of the thermodynamic constants defining defect generation. General agreement of these constants with bulk values derived by thermogravimetric analysis is found, thereby confirming the suitability of this technique for measuring oxygen non‐stoichiometry of thin oxide films. Potential sources of error observed in earlier chemical capacitance studies on perovskite structured oxide films are also discussed.