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We report a microhardness indentation study for multicomponent refractory metal boride thin films that belong to the family of high‐entropy ceramics exhibiting superior hardness and high temperature properties. We focus on the nominally equimolar composition (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2, which we refer to as HEB3, on c‐plane sapphire substrates. Thin films are prepared using bipolar high power impulse magnetron sputtering (HiPIMS), where the positive kick pulse is optimized to produce films with high density, high crystallinity, and a microstructure that is isometric in nature as revealed by cross‐sectional fracture surface imaging, X‐ray diffraction, and X‐ray reflectometry. Low‐load Knoop indentation is used to measure microhardness. We find strong trends linking kick‐pulse magnitude, microstructure uniformity, high density, and Knoop hardness. Optimized conditions can produce films with low‐load Knoop hardness exceeding 30 GPa. To validate these trends, we present a rigorous indent characterization campaign and discussion considering possible artifacts from roughness, thickness, and indent loading. The key finding of our study is the ability of engineering bombardment by using a low duty‐cycle pulsed plasma to manipulate crystal structure without sacrificing crystallinity, and in turn boost material hardness. [ABSTRACT FROM AUTHOR]

Interest in high‐entropy inorganic compounds originates from their ability to stabilize cations and anions in local environments that rarely occur at standard temperature and pressure. This leads to new crystalline phases in many‐cation formulations with structures and properties that depart from conventional trends. The highest‐entropy homogeneous and random solid solution is a parent structure from which a continuum of lower‐entropy offspring can originate by adopting chemical and/or structural order. This report demonstrates how synthesis conditions, thermal history, and elastic and chemical boundary conditions conspire to regulate this process in Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O, during which coherent CuO nanotweeds and spinel nanocuboids evolve. We do so by combining structured synthesis routes, atomic‐resolution microscopy and spectroscopy, density functional theory, and a phase field modeling framework that accurately predicts the emergent structure and local chemistry. This establishes a framework to appreciate, understand, and predict the macrostate spectrum available to a high‐entropy system that is critical to rationalizing property engineering opportunities. [ABSTRACT FROM AUTHOR]

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)0.083O, a composition based on the parent HEO (MgNiCuCoZn)0.2O. 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 pO2 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)0.083O forms with varying initial conditions and advances fundamental knowledge of cation behavior in high entropy oxides. [ABSTRACT FROM AUTHOR]

This report demonstrates tunable carrier densities in CdO thin films through local ion irradiation, providing lateral control of mid‐IR optical properties. Ion‐solid interactions produce donor‐like defects that boost electron concentrations from the practical minimum of 2.5 × 1019 cm−3 to a maximum of 2.5 × 1020 cm−3 by metered ion exposure. This range is achieved using He, N, Ar, or Au ions at 1–2.8 MeV; when normalized by displacements per atom, all ion species produce comparable results. Since CdO is well‐described by the Drude model, irradiation‐tuned carrier densities directly alter the infrared dielectric function, and in turn, mid‐infrared optical properties. Further, it is demonstrated that by combining irradiation with traditional lithography, CdO films expose to ions in the presence of 3‐µm thick, patterned photoresist exhibit lateral carrier density profiles with ≈400‐nm resolution. Scanning near‐field optical microscopy reveals sharp optical interfaces with almost no companion contrast in surface morphology, microstructure, or crystallinity. Finally, CdO lateral homostructures supporting surface plasmon polaritons (SPPs) are demonstrated whose dispersion relation can be tuned through periodic patterning in a monolithic platform by simple nanofabrication. Numerical simulations show these polaritons result from strong coupling between excitations at CdO plasma frequencies and SPPs supported by the platinum substrate. [ABSTRACT FROM AUTHOR]

We report on the structure and dielectric properties of ternary A6B2O17 (A = Zr; B = Nb, Ta) thin films and ceramics. Thin films are produced via sputter deposition from dense, phase‐homogenous bulk ceramic targets, which are synthesized through a reactive sintering process at 1500°C. Crystal structure, microstructure, chemistry, and dielectric properties are characterized by X‐ray diffraction and reflectivity, atomic force microscopy, X‐ray photoelectron spectroscopy, and capacitance analysis, respectively. We observe relative permittivities approaching 60 and loss tangents <1 × 10−2 across the 103–105 Hz frequency range in the Zr6Nb2O17 and Zr6Ta2O17 phases. These observations create an opportunity space for this novel class of disordered oxide electroceramics. [ABSTRACT FROM AUTHOR]

Zn0.64Mg0.36O (ZMO) is a newly discovered ferroelectric oxide with the wurtzite structure. Epitaxial Zn0.64Mg0.36O films from 0.036 to 0.5 μm in thickness are grown on Pt/sapphire with the crystallographic c-axis out of plane. At room temperature, the remanent polarization is ∼80 μC/cm2 and the coercive field is ∼3 MV/cm. The coercive field is strongly temperature dependent up to 240 °C with a pseudo-activation energy of 23 ± 0.3 meV, suggesting that polarization reversal occurs through an extrinsic process such as domain wall motion. ZMO films can be woken up in 20 electric field cycles on driving near the coercive field; they wake up in a single loop at fields in excess of 4 MV/cm. A thermally activated fluid imprint process, with a pseudo-activation energy of 67 ± 8 meV, enlarges the coercive field by several hundred kV cm−1 after switching the polarization. Additionally, ZMO films exhibit excellent retention characteristics; no reduction in the polarization is observed up to 1000 h from room temperature to 200 °C bakes. This current early generation of ZMO films can survive several thousand switching cycles before dielectric breakdown occurs. [ABSTRACT FROM AUTHOR]

The epsilon‐near‐zero (ENZ) frequency regime of transparent conducting oxide materials is known to yield large enhancements in their optical nonlinearity and electro‐optic response. Here, Faraday rotation is investigated in Gd and In‐doped CdO films and it is found that the Verdet constant peaks at values >3 105 deg T−1 m−1 near the ENZ frequency, which is tunable in the wavelength range 2 < λ< 10 µm by varying the doping concentration. These results are among the highest reported to date in the mid‐infrared spectral range and are in good agreement with the Drude model, which confirms that the magneto‐optic response of doped CdO derives from its free carriers. The combination of a tunable Verdet constant, low optical loss compared to other plasmonic materials, and the ability to deposit CdO on Si with no loss in performance make this material a promising platform for integrated magneto‐optic and magnetoplasmonic devices that operate across the mid‐infrared. [ABSTRACT FROM AUTHOR]

We report on temperature-dependent dielectric behavior of disordered ternary A6B2O17 (A = Zr, Hf; B = Nb, Ta)-form oxides in the GHz frequency range. The microwave dielectric properties including relative permittivity, dielectric loss, and temperature-dependent relative permittivity were characterized using cylindrical dielectric resonators using a resonant post measurement technique. Dielectric measurements through the resonant post method approach generally agree with dielectric measurements of A6B2O17 bulk ceramics measured through standard resonant post techniques. Coefficients describing the temperature-dependent relative permittivity for ternary A6B2O17 phases are strongly positive, suggesting contributions to polarizability arising from long-range mechanisms potentially associated with structural disorder. These observations support the working hypothesis that material functionality can be engineered by the chemical diversity and structural disorder possible in high configurational entropy A6B2O17 phases. [ABSTRACT FROM AUTHOR]

Super‐hard (Hf,Mo,Ti,V,W)B2 was synthesized by boro‐carbothermal reduction and densified by spark plasma sintering. This composition was produced for the first time as a single‐phase ceramic in the present research. The optimized ceramic had a single hexagonal AlB2‐type crystalline phase with a grain size of 3.8 µm and homogeneous distribution of the constituent metals. The Vickers hardness exhibited the indentation size effect, increasing from 27 GPa at a load of 9.8 N to as high as 66 GPa at a load of 0.49 N. This is the highest hardness reported to date for high entropy boride ceramics. [ABSTRACT FROM AUTHOR]

AlN thin films are enabling significant progress in modern optoelectronics, power electronics, and microelectromechanical systems. The various AlN growth methods and conditions lead to different film microstructures. In this report, phonon scattering mechanisms that impact the cross-plane (κz; along the c-axis) and in-plane (κr; parallel to the c-plane) thermal conductivities of AlN thin films prepared by various synthesis techniques are investigated. In contrast to bulk single crystal AlN with an isotropic thermal conductivity of ∼330 W/m K, a strong anisotropy in the thermal conductivity is observed in the thin films. The κz shows a strong film thickness dependence due to phonon-boundary scattering. Electron microscopy reveals the presence of grain boundaries and dislocations that limit the κr. For instance, oriented films prepared by reactive sputtering possess lateral crystalline grain sizes ranging from 20 to 40 nm that significantly lower the κr to ∼30 W/m K. Simulation results suggest that the self-heating in AlN film bulk acoustic resonators can significantly impact the power handling capability of RF filters. A device employing an oriented film as the active piezoelectric layer shows an ∼2.5× higher device peak temperature as compared to a device based on an epitaxial film. [ABSTRACT FROM AUTHOR]

The prototype high-entropy oxide (HEO) Y0.2La0.2Ce0.2Pr0.2Sm0.2O2−δ represents a particularly complex class of HEOs with significant anion sublattice entropy. The system takes either a fluorite or bixbyite-type crystal structure, depending on synthesis kinetics and thermal history. Here, we synthesize bulk ceramics and epitaxial thin films of Y0.2La0.2Ce0.2Pr0.2Sm0.2O2−δ and use diffraction to explore crystal symmetry and phase. Thin films exhibit the high symmetry fluorite phase, while bulk ceramics adopt the lower symmetry bixbyite phase. The difference in chemical ordering and observed symmetry between vapor-deposited and reactively sintered specimens suggests that synthesis kinetics can influence accessible local atomic configurations, i.e., the high kinetic energy adatoms quench in a higher-effective temperature, and thus higher symmetry structure with more configurational entropy. More generally, this demonstration shows that recovered HEO specimens can exhibit appreciably different local configurations depending on synthesis kinetics, with potential ramifications on macroscopic physical properties. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

This report demonstrates Al0.93B0.7N thin films grown epitaxially on n-type GaN (0002)/c-plane sapphire substrates by reactive magnetron sputtering at 300 °C. At 200 nm film thickness, the Al0.93B0.07N layers exhibit partially relaxed substrate-induced epitaxial strain, a 0.16° wide (0002) rocking curve, in-plane crystallographic registry, and sub-nanometer surface roughness. Electrically, the stack shows robust hysteresis over three frequency decades, a remanent polarization of ∼125 μC/cm2, a strongly frequency dependent coercive field, highly uniform dc leakage currents, and endurance >106 field cycles. This report validates possibilities for ferroelectric nitride integration into conventional III-nitride heterostructures with high crystalline fidelity, high electrical resistivity, and persistent hysteresis. Such materials are synthesizable at thermal budgets and temperatures compatible with back-end-of-the-line boundary conditions. [ABSTRACT FROM AUTHOR]

The interplay of stress, disorder, and Coulomb screening dictating the mobility of doped cadmium oxide (CdO) is examined using Raman spectroscopy to identify the mechanisms driving dopant incorporation and scattering within this emerging infrared optical material. Specifically, multi-wavelength Raman and UV-vis spectroscopies are combined with electrical Hall measurements on a series of yttrium (X = Y) and indium (X = In) doped X:CdO thin-films. Hall measurements confirm n-type doping and establish carrier concentrations and mobilities. Spectral fitting along the low-frequency Raman combination bands, especially the TA+TO(X) mode, reveals that the evolution of strain and disorder within the lattice as a function of dopant concentration is strongly correlated with mobility. Coupling between the electronic and lattice environments was examined through analysis of first- and second-order longitudinal–optical phonon–plasmon coupled modes that monotonically decrease in energy and asymmetrically broaden with increasing dopant concentration. By fitting these trends to an impurity-induced Fröhlich model for the Raman scattering intensity, exciton–phonon and exciton–impurity coupling factors are quantified. These coupling factors indicate a continual decrease in the amount of ionized impurity scattering with increasing dopant concentration and are not as well correlated with mobility. This shows that lattice strain and disorder are the primary determining factors for mobility in donor-doped CdO. In aggregate, the study confirms previously postulated defect equilibrium arguments for dopant incorporation in CdO while at the same time identifying paths for its further refinement. [ABSTRACT FROM AUTHOR]

Wurtzite ferroelectric materials are promising candidates for energy‐efficient memory technologies, particularly for applications requiring high operating temperatures. Asymmetric wake‐up behaviors, in which the polarization reversal depends both on polarity and cycle number for the first few dozen cycles, must be better understood for reliable device operation. Here, the detailed analysis of the asymmetric wake‐up behavior of thin film Al0.94B0.06N was performed combining time‐resolved switching measurements with Rayleigh analysis, piezoelectric measurements, and etching experiments of progressively switched samples. The analysis shows that the gradual opening of the polarization hysteresis loops associated with wake‐up is driven by a gradual increase in the domain‐wall density and/or domain‐wall mobility with electric field cycle to the polarity opposite to the growth polarity. The insights of this discovery will help to guide interface and polarity design in the eventual deployment of reliable devices based on these materials. [ABSTRACT FROM AUTHOR]

Polarization dynamics and domain structure evolution in ferroelectric Al0.93B0.07N are studied using piezoresponse force microscopy and spectroscopies in ambient and controlled atmosphere environments. The application of negative unipolar and bipolar first‐order reverse curve (FORC) waveforms leads to a protrusion‐like feature on the Al0.93B0.07N surface and a reduction of electromechanical response due to electrochemical reactivity. A surface change is also observed on the application of fast alternating current bias. At the same time, the application of positive biases does not lead to surface changes. Comparatively in a controlled glove box atmosphere, stable polarization patterns can be observed, with minuscule changes in surface morphology. This surface morphology change is not isolated to applying biases to free surface, a similar topographical change is also observed at the electrode edges when cycling a capacitor in an ambient environment. The study suggests that surface electrochemical reactivity may have a significant impact on the functionality of this material in the ambient environment. However, even in the controlled atmosphere, the participation of the surface ions in polarization switching phenomena and ionic compensation is possible. [ABSTRACT FROM AUTHOR]

The discovery of ferroelectricity in polar wurtzite-based ternary materials, such as Al1−xBxN, has attracted attention due to their compatibility with complementary metal–oxide–semiconductor processes and potential use in integrated non-volatile memory devices. However, the origin of ferroelectricity and the fundamental control of the polarization switching in these materials are still under intensive investigation but appear to be related to local disorder induced from the alloying. In this work, we report the effect of boron alloying on the local structure of Al1−xBxN films deposited by magnetron sputtering. Our results reveal a diminished crystalline order as a function of boron concentration, accompanied by a reduction in the spontaneous polarization. The film disorder is primarily associated with the dissimilar bond lengths between Al–N and B–N and the formation of threading dislocations induced by B incorporation in the structure. [ABSTRACT FROM AUTHOR]

We demonstrate ferroelectricity in Mg-substituted ZnO thin films with the wurtzite structure. Zn1−xMgxO films are grown by dual-cathode reactive magnetron sputtering on (111)-Pt // (0001)-Al2O3 substrates at temperatures ranging from 26 to 200 °C for compositions spanning from x = 0 to x = 0.37. X-ray diffraction indicates a decrease in the c-lattice parameter and an increase in the a-lattice parameter with increasing Mg content, resulting in a nearly constant c/a axial ratio of 1.595 over this composition range. Transmission electron microscopy studies show abrupt interfaces between Zn1−xMgxO films and the Pt electrode. When prepared at pO2 = 0.025, film surfaces are populated by abnormally oriented grains as measured by atomic force microscopy for Mg concentrations >29%. Raising pO2 to 0.25 eliminates the misoriented grains. Optical measurements show increasing bandgap values with increasing Mg content. When prepared on a 200 °C substrate, films display ferroelectric switching with remanent polarizations exceeding 100 μC cm−2 and coercive fields below 3 MV cm−1 when the Mg content is between ∼30% and ∼37%. Substrate temperature can be lowered to ambient conditions, and when doing so, capacitor stacks show only minor sacrifices to crystal orientation and nearly identical remanent polarization values; however, coercive fields drop below 2 MV/cm. Using ambient temperature deposition, we demonstrate ferroelectric capacitor stacks integrated directly with polymer substrate surfaces. [ABSTRACT FROM AUTHOR]