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Polarization dynamics and domain structure evolution in ferroelectric Al$_{0.93}$B$_{0.07}$N 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 Al$_{0.93}$B$_{0.07}$N surface and 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 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., 16 pages; 5 figures

Multifunctionality as a paradigm requires materials exhibiting multiple superior properties. Integrating second-order optical nonlinearity and large bandgap with piezoelectricity could, for example, enable broadband, strain-tunable photonics. Though very different phenomena at distinct frequencies, both second-order optical nonlinearity and piezoelectricity are third-rank polar tensors present only in acentric crystal structures. However, simultaneously enhancing both phenomena is highly challenging since it involves competing effects with tradeoffs. Recently, a large switchable ferroelectric polarization of ~ 80 uC cm-2 was reported in Zn1-xMgxO films. Here, ferroelectric Zn1-xMgxO is demonstrated to be a platform that hosts simultaneously a 30% increase in the electronic bandgap, a 50% enhancement in the second harmonic generation coefficients, and a near 200% improvement in the piezoelectric coefficients over pure ZnO. These enhancements are shown to be due to a 400% increase in the electronic anharmonicity and a ~200% decrease in the ionic anharmonicity with Mg substitution. Precisely controllable periodic ferroelectric domain gratings are demonstrated down to 800 nm domain width, enabling ultraviolet quasi-phase-matched optical harmonic generation as well as domain-engineered piezoelectric devices.

Supplemental Material document referred to as "Supplement 1" in the body of the manuscript. This carries an additional figure and details on modelling parameters used by not expanded upon in the main body of the manuscript.

Ferroelectric polarization switching is one common example of a process that occurs via nucleation and growth, and understanding switching kinetics is crucial for applications such as ferroelectric memory. Here we describe and interpret anomalous switching dynamics in the wurtzite nitride thin film ferroelectrics Al0.7Sc0.3N and Al0.94B0.06N using a general model that can be directly applied to other abrupt transitions that proceed via nucleation and growth. When substantial growth and impingement occur while nucleation rate is increasing, such as in these wurtzite ferroelectrics under high electric fields, abrupt polarization reversal leads to very large Avrami coefficients (e.g., n = 11), inspiring an extension of the KAI (Kolmogorov-Avrami-Ishibashi) model. We apply this extended model to two related but distinct scenarios that crossover between (typical) behavior described by sequential nucleation and growth and a more abrupt transition arising from significant growth prior to peak nucleation rate. This work therefore provides more complete description of general nucleation and growth kinetics applicable to any system while specifically addressing both the anomalously abrupt polarization reversal behavior in new wurtzite ferroelectrics., Comment: 4 figures

Supplemental document referred to as Supplement 1. Contains additional figures and tables referenced in the manuscript.

This paper reports the fatigue and retention behavior for Al1-xBxN thin films, a member of the novel family of wurtzite ferroelectrics, with an emphasis on the role of capacitor architecture. By modifying the capacitor architecture, and thus thermal and electrical boundary conditions, we create insight regarding the relative importance of intrinsic and extrinsic contributors to the degradation tendencies. Our experiments suggest that bipolar cycling of metal (Pt/W)/Al0.93B0.07N/W/Al2O3 film stacks first induced wake-up, then a region of constant switchable polarization. On additional cycling, the film leakage current increased, and then films underwent dielectric breakdown. For unpatterned first generation Al0.93B0.07N films with 100 nm thick Pt top electrodes survive ~104 bipolar cycles, whereas films with 1000 nm W top electrodes survive ~10^5 cycles before thermal dielectric breakdown. Sentaurus modeling was used to design an SU8 field plate which improved the performance to ~10^6 fatigue cycles. It was found that the thermal failures during fatigue were not due to surface flashover events but were associated with hard breakdown events in the dielectric. The films showed excellent retention of the stored polarization state. As expected, data retention was slightly inferior in the opposite state (OS) measurements. However, it is noted that even after 3.6x10^6 sec (1000 hr). at 200{\deg}C, the OS signal margin still exceeded 200 uC/cm2. The predicted OS retention is 82% after 10 years baking at 200oC.

We develop and implement an automated experiment in multimodal imaging to probe structural, chemical, and functional behaviors in complex materials and elucidate the dominant physical mechanisms that control device function. Here the emergence of non-linear electromechanical responses in piezoresponse force microscopy (PFM) is explored. Non-linear responses in PFM can originate from multiple mechanisms, including intrinsic material responses often controlled by domain structure, surface topography that affects the mechanical phenomena at the tip-surface junction, and, potentially, the presence of surface contaminants. Using an automated experiment to probe the origins of non-linear behavior in model ferroelectric lead titanate (PTO) and ferroelectric Al0.93B0.07N films, it was found that PTO showed asymmetric nonlinear behavior across a/c domain walls and a broadened high nonlinear response region around c/c domain walls. In contrast, for Al0.93B0.07N, well-poled regions showed high linear piezoelectric responses paired with low non-linear responses and regions that were multidomain indicated low linear responses and high nonlinear responses. We show that formulating dissimilar exploration strategies in deep kernel learning as alternative hypotheses allows for establishing the preponderant physical mechanisms behind the non-linear behaviors, suggesting that this approach automated experiments can potentially discern between competing physical mechanisms. This technique can also be extended to electron, probe, and chemical imaging., 18 pages, 5 figures

High entropy carbides (HECs) are a promising new class of ultra-high temperature ceramics that could provide novel material solutions for leading edges of hypersonic vehicles, which can reach temperatures above 3500C and experience extreme thermal gradients. Although the mechanical and thermal properties of HECs have been studied extensively at room temperature, few works have examined HEC properties at high temperatures or considered these materials' responses to thermal shock. In this work, we measure the thermal conductivity of a five-cation HEC up to 1200C. We find that thermal conductivity increases with temperature, consistent with trends demonstrated in single-metal carbides. We also measure thermal conductivity of an HEC deposited with varying CH4 flow rate, and find that although thermal conductivity is reduced when carbon content surpasses stoichiometric concentrations, the films all exhibited the same temperature dependent trends regardless of carbon content. To compare the thermal shock resistance of HECs with a refractory carbide, we conduct pulsed laser ablation measurements to determine the fluence threshold the HECs can withstand before damaging. We find that this metric for the average bond strength trends with the theoretical hardness of the HECs as expected., Comment: 22 pages, 6 figures

As various property studies continue to emerge on high entropy and entropy-stabilized ceramics, we seek further understanding of property changes across the phase boundary between \enquote{high-entropy} and \enquote{entropy-stabilized}. The thermal and mechanical properties of bulk ceramic entropy stabilized oxide composition Mg$_{0.2}$Co$_{0.2}$Ni$_{0.2}$Cu$_{0.2}$Zn$_{0.2}$O are investigated across this critical transition temperature via the transient plane-source method, temperature-dependent X-ray diffraction, and nano-indentation. Thermal conductivity remains constant within uncertainty across the multi-to-single phase transition at a value of ~2.5 W/mK, while the linear coefficient of thermal expansion increases nearly 24 % from 10.8 to 14.1 x 10$^{-6}$ K$^{-1}$. Mechanical softening is also observed across the transition., Comment: 14 pages, 4 figures, to be published in APL Materials

Fermi level engineering and mechanical properties evolution in high entropy carbides are investigated by theoretical and experimental means. Massive elemental diversity in high entropy ceramics broadens the compositional space but imposes great challenges in composition selection and property investigation. We have utilized the valence electron concentration (VEC) descriptor to design and predict properties of high entropy carbides. The VEC regulates the Fermi energy and systematically alters the bonding characteristics of materials. As a result, mechanical properties evolve as function of the VEC. At VEC 8.4, the strong {\sigma} bonding states stem from filled overlapping metal d and carbon p orbitals, which results in maximum resistance to shear deformation and highest hardness. Beyond or below the optimum VEC point of 8.4, mechanical response degrades due to filling or emptying of energy orbitals that facilitates shear deformation. Furthermore, the optimum VEC point can shift based on the constituent metals that formulate the high entropy carbide. Our analyses demonstrate strong correlation between calculated hardness and shear modulus. As an experimental complement, a set of high entropy carbides are synthesized, and mechanical properties investigated. The measured hardness follows theoretical predictions and the highest hardness of ~30 GPa is achieved at VEC 8.4. In contrast, hardness decreases by 50% when VEC is 9.4. Designing high entropy carbides based on VEC and understanding mechanical properties at an electronic level enables one to manipulate the composition spectrum to procure a desired mechanical response from a chemically disordered crystal., Comment: 15 pages, 4 figures, Full Length Paper

Polaritonic materials that support epsilon-near-zero (ENZ) modes offer the opportunity to design light-matter interactions at the nanoscale through phenomena like resonant perfect absorption and extreme sub-wavelength light concentration. To date, the utility of ENZ modes is limited in propagating polaritonic systems by a relatively flat spectral dispersion, which gives ENZ modes small group velocities and short propagation lengths. Here we overcome this constraint by coupling ENZ modes to surface plasmon polariton (SPP) modes in doped cadmium oxide ENZ-on-SPP bilayers. What results is a strongly coupled hybrid mode, characterized by strong anti-crossing and a large spectral splitting on the order of 1/3 of the mode frequency. The resonant frequencies, dispersion, and coupling of these polaritonic-hybrid-epsilon-near-zero (PH-ENZ) modes are controlled by tailoring the modal oscillator strength and the ENZ-SPP spectral overlap, which can potentially be utilized for actively tunable strong coupling at the nanoscale. PH-ENZ modes ultimately leverage the most desirable characteristics of both ENZ and SPP modes through simultaneous strong interior field confinement and mode propagation.

We present experimental measurements of the thermal boundary conductance (TBC) from $77 - 500$ K across isolated heteroepitaxially grown ZnO films on GaN substrates. These data provide an assessment of the assumptions that drive the phonon gas model-based diffuse mismatch models (DMM) and atomistic Green's function (AGF) formalisms for predicting TBC. Our measurements, when compared to previous experimental data, suggest that the TBC can be influenced by long wavelength, zone center modes in a material on one side of the interface as opposed to the "vibrational mismatch" concept assumed in the DMM; this disagreement is pronounced at high temperatures. At room temperature, we measure the ZnO/GaN TBC as $490\lbrack +150, -110\rbrack$ MW m$^{-2}$ K$^{-1}$. The disagreement among the DMM and AGF and the experimental data these elevated temperatures suggests a non-negligible contribution from additional modes contributing to TBC that not accounted for in the fundamental assumptions of these harmonic formalisms, such as inelastic scattering. Given the high quality of these ZnO/GaN interface, these results provide an invaluable critical and quantitive assessment of the accuracy of assumptions in the current state of the art of computational approaches for predicting the phonon TBC across interfaces., 7 pages, 3 figures