Alloying is an age-old strategy for synthesizing materials with enhanced properties. Recently, multicomponent systems such as high-entropy oxides have garnered widespread attention due to their tunable and often superior properties compared to their constituent oxides. Here, we study the local structural and chemical nuances of six-component (Mg0.167Co0.167Ni0.167Cu0.167Zn0.167Mn0.167)O and (Mg0.167Co0.167Ni0.167Cu0.167Zn0.167Cr0.167)O thin films. The Mn-alloyed thin film exhibits a higher exchange bias and greater magnetic frustration compared with the Cr-containing thin film. Scanning/transmission electron microscopy investigations reveal that the Mn-alloyed thin film exhibits the coexistence of rock salt and spinel-like regions, unlike the single-phase rock salt structure observed in the Cr-alloyed thin film. Electron energy loss spectroscopy indicates changes in Co and Mn valences within the Mn-containing thin film, suggesting the presence of mixed-valence states, which are further confirmed by X-ray absorption spectroscopy measurements. These observations are further validated by cation-site-preference energy calculations using density functional theory. Our results demonstrate how the chemistry, site occupations, and cation valences result in pronounced changes in the overall properties of high-entropy oxides.

Ferroelectric materials provide pathways to higher performance logic and memory technologies, with Hf0.5Zr0.5O2 being the most popular among them. However, critical challenges exist in understanding the material’s failure mechanisms to design long endurance lifetimes. In this work, dielectric failure due to repeated switching cycles, occurring through oxygen vacancy motion and leading to the formation of a conductive filament, is demonstrated. A field modified hopping barrier of ∼150–400 meV is observed, indicating a vacancy charge of 0.4–0.6e markedly different from the charge states predicted in the literature. After failure, the capacitor leakage current is high (∼25 mA) and constant with capacitor area, consistent with filament formation. Conductive atomic force microscopy measurements and field distribution simulations suggest a local failure mechanism consistent with filament formation along the boundary of the island capacitor due to an enhanced electric field.

High entropy oxides (HEOs) have garnered much interest due to their available high degree of tunability. Here, we study the local structure of (MgNiCuCoZn)(0.167)(MnCr)(0.083)O, a composition based on the parent HEO (MgNiCuCoZn)(0.2)O. We synthesized a series of thin films via pulsed laser deposition at incremental oxygen partial pressures. X-ray diffraction shows lattice parameters to decrease with increased pO(2) pressures until the onset of phase separation. X-ray absorption fine structure shows that specific atomic species in the composition dictate the global structure of the material as Cr, Co, and Mn shift to energetically favorable coordination with increasing pressure. Transmission electron microscopy analysis on a lower-pressure sample exhibits a rock salt structure, but the higher-pressure sample reveals reflections reminiscent of the spinel structure. In all, these findings give a more complete picture of how (MgNiCuCoZn)(0.167)(MnCr)(0.083)O forms with varying initial conditions and advances fundamental knowledge of cation behavior in high entropy oxides.

Memristive devices are of potential use in a range of computing applications. However, many of these devices are based on amorphous materials, where systematic control of the switching dynamics is challenging. Here we report tunable and stable memristors based on an entropy-stabilized oxide. We use single-crystalline (Mg,Co,Ni,Cu,Zn)O films grown on an epitaxial bottom electrode. By adjusting the magnesium composition (XMg = 0.11-0.27) of the entropy-stabilized oxide films, a range of internal time constants (159-278 ns) for the switching process can be obtained. We use the memristors to create a reservoir computing network that classifies time-series input data and show that the reservoir computing system, which has tunable reservoirs, offers better classification accuracy and energy efficiency than previous reservoir system implementations. Tunable and stable memristors based on single-crystalline entropy-stabilized oxide films grown on epitaxial bottom electrodes can be used to create energy-efficient reservoir computing networks.

Entropy-stabilized oxides are single-phase, multicomponent oxides that are stabilized by a large entropy of mixing, ΔS, overcoming a positive enthalpy. Due to the −TΔS term in the Gibbs' free energy, G, it can be hypothesized that entropy-stabilized oxides demonstrate a robust thermal stability. Here, we investigate the high temperature stability (1300–1700 °C) of the prototypical entropy-stabilized rocksalt oxide (MgCoNiCuZn)0.2O in air. We find that at temperatures >1300 °C, the material gradually loses Cu and Zn with increasing temperature. Cu is lost through a selective melting as a Cu-rich liquid phase is formed. Zn is sublimed from the rocksalt phase at approximately similar temperatures to those corresponding to the Cu loss, significantly below both the melting temperature of ZnO and its solubility limit in a rocksalt phase. The elemental loss progressively reduces the entropy of mixing and results in a multiphase solid upon quenching to room temperature. We posit that the high-temperature solubility of Cu and Zn is correlated providing further evidence for entropic stabilization over general solubility arguments.

Functional thin film superlattices with stability in extreme environments can lead to transformative performance in optical and thermal applications such as thermophotovoltaics. In this work, key issues associated with defects that prevent layer-by-layer growth in epitaxial, low-miscibility oxide superlattices are investigated. Layer protrusions, approximately 8 nm wide and 3 nm thick, arise from a strain relaxation mechanism in 8 nm bilayer superlattices of Ba(Zr0.5Hf0.5)O3/MgO and propagate through the subsequent superlattice layers forming an inverted pyramid structure that is spatially phase offset from the matrix. The density and size of these defects scales with the number of interfaces in the sample, indicating that surface roughness during growth is a significant factor in the formation of these defects. In situ high temperature transmission electron microscopy (1000 °C, in vacuo) measurement reveals that phase decomposition of Ba(Zr0.5Hf0.5)O3 and decoherence of the superlattice is nucleated by these defects. This work highlights that achieving optimum growth conditions is imperative to the synthesis of single-crystalline superlattices with sharp interfaces for optimized performance in extreme environments.

Nanophotonic materials offer spectral and directional control over thermal emission, but in high-temperature oxidizing environments, their stability remains low. This limits their applications in technologies such as solid-state energy conversion and thermal barrier coatings. Here we show an epitaxial heterostructure of perovskite BaZr 0.5 Hf 0.5 O 3 (BZHO) and rocksalt MgO that is stable up to 1,100 °C in air. The heterostructure exhibits coherent atomic registry and clearly separated refractive-index-mismatched layers after prolonged exposure to this extreme environment. The immiscibility of the two materials is corroborated by the high formation energy of substitutional defects from density functional theory calculations. The epitaxy of immiscible refractory oxides is, therefore, an effective method to avoid prevalent thermal instabilities in nanophotonic materials, such as grain-growth degradation, interlayer mixing and oxidation. As a functional example, a BZHO/MgO photonic crystal is implemented as a filter to suppress long-wavelength thermal emission from the leading bulk selective emitter and effectively raise its cutoff energy by 20%, which can produce a corresponding gain in the efficiency of mobile thermophotovoltaic systems. Beyond BZHO/MgO, computational screening shows that hundreds of potential cubic oxide pairs fit the design principles of immiscible refractory photonics. Extending the concept to other material systems could enable further breakthroughs in a wide range of photonic and energy conversion applications.

Interfacial resistive switching and composition-tunable RLRS are realized in ionically conducting Na0.5Bi0.5TiO3 thin films, allowing optimised ON/OFF ratio (>104) to be achieved with low growth temperature (600 °C) and low thickness (<20 nm).