Ferroelectric hafnium zirconium oxide holds great promise for a broad spectrum of complementary metal–oxide–semiconductor (CMOS) compatible and scaled microelectronic applications, including memory, low-voltage transistors, and infrared sensors, among others. An outstanding challenge hindering the implementation of this material is polarization instability during field cycling. In this study, the nanoscale phenomena contributing to both polarization fatigue and wake-up are reported. Using synchrotron X-ray diffraction, the conversion of non-polar tetragonal and polar orthorhombic phases to a non-polar monoclinic phase while field cycling devices comprising noble metal contacts is observed. This phase exchange accompanies a diminishing ferroelectric remanent polarization and provides device-scale crystallographic evidence of phase exchange leading to ferroelectric fatigue in these structures. A reduction in the full width at half-maximum of the superimposed tetragonal (101) and orthorhombic (111) diffraction reflections is observed to accompany wake-up in structures comprising tantalum nitride and tungsten electrodes. Combined with polarization and relative permittivity measurements, the observed peak narrowing and a shift in position to lower angles is attributed, in part, to a phase exchange of the non-polar tetragonal to the polar orthorhombic phase during wake-up. These results provide insight into the role of electrodes in the performance of hafnium oxide-based ferroelectrics and mechanisms driving wake-up and fatigue, and demonstrate a non-destructive means to characterize the phase changes accompanying polarization instabilities.

Magnetic van der Waals (vdW) materials are the centerpiece of atomically thin devices with spintronic and optoelectronic functions. Exploring new chemistry paths to tune their magnetic and optical properties enables significant progress in fabricating heterostructures and ultracompact devices by mechanical exfoliation. The key parameter to sustain ferromagnetism in 2D is magnetic anisotropy-a tendency of spins to align in a certain crystallographic direction known as easy-axis. In layered materials, two limits of easy-axis are in-plane (XY) and out-of-plane (Ising). Light polarization and the helicity of topological states can couple to magnetic anisotropy with promising photoluminescence or spin-orbitronic functions. Here, a unique experiment is designed to control the easy-axis, the magnetic transition temperature, and the optical gap simultaneously in a series of CrCl Br crystals between CrCl with XY and CrBr with Ising anisotropy. The easy-axis is controlled between the two limits by varying spin-orbit coupling with the Br content in CrCl Br . The optical gap, magnetic transition temperature, and interlayer spacing are all tuned linearly with x. This is the first report of controlling exchange anisotropy in a layered crystal and the first unveiling of mixed halide chemistry as a powerful technique to produce functional materials for spintronic devices.

The family of binary Lanthanum monopnictides, LaBi and LaSb, have attracted a great deal of attention as they display an unusual extreme magnetoresistance (XMR) that is not well understood. Two classes of explanations have been raised for this: the presence of non-trivial topology, and the compensation between electron and hole densities. Here, by synthesizing a new member of the family, LaAs, and performing transport measurements, Angle Resolved Photoemission Spectroscopy (ARPES), and Density Functional Theory (DFT) calculations, we show that (a) LaAs retains all qualitative features characteristic of the XMR effect but with a siginificant reduction in magnitude compared to LaSb and LaBi, (b) the absence of a band inversion or a Dirac cone in LaAs indicates that topology is insignificant to XMR, (c) the equal number of electron and hole carriers indicates that compensation is necessary for XMR but does not explain its magnitude, and (d) the ratio of electron and hole mobilities is much different in LaAs compared to LaSb and LaBi. We argue that the compensation is responsible for the XMR profile and the mobility mismatch constrains the magnitude of XMR.

The presence of the top electrode on hafnium oxide‐based thin films during processing has been shown to drive an increase in the amount of metastable ferroelectric orthorhombic phase and polarization performance. This “Clamping Effect,” also referred to as the Capping or Confinement Effect, is attributed to the mechanical stress and confinement from the top electrode layer. However, other contributions to orthorhombic phase stabilization have been experimentally reported, which may also be affected by the presence of a top electrode. In this study, it is shown that the presence of the top electrode during thermal processing results in larger tensile biaxial stress magnitudes and concomitant increases in ferroelectric phase fraction and polarization response, whereas film chemistry, microstructure, and crystallization temperature are not affected. Through etching experiments and measurement of stress evolution for each processing step, it is shown that the top electrode locally inhibits out‐of‐plane expansion in the HZO during crystallization, which prevents equilibrium monoclinic phase formation and stabilizes the orthorhombic phase. This study provides a mechanistic understanding of the clamping effect and orthorhombic phase formation in ferroelectric hafnium oxide‐based thin films, which informs the future design of these materials to maximize ferroelectric phase purity and corresponding polarization behavior.

Electrochemical CO 2 reduction can convert CO 2 into fuels and valuable chemicals using renewable electricity, which provides a prospective path toward large-scale energy storage. Au nanostructured electrodes have demonstrated the best catalytic performance for CO 2 conversion: high catalytic selectivity for CO formation at low overpotentials, high current density, and long-term durability. Here, we report selective electrocatalytic CO 2 reduction to CO on nanostructured Au with various morphologies, prepared via electrocrystallization with a megahertz potential oscillation. X-ray diffraction showed that the proportion of {100} and {110} to {111} surfaces increased at more negative deposition potentials. Cyclic voltammetry showed the potential of zero charge on an Au film was approximately 0.35 V vs standard hydrogen electrode (SHE) and that the surface energy decreased by ∼1 eV/nm 2 at −0.5 V vs SHE, tending to 0 within several volts in either direction. Scanning electron micrograms showed that the Au crystals grow primarily in the ⟨110⟩ directions. From these data, a model for crystallization from melts was adapted to calculate the roughening temperature of the {111}, {100}, and {110} Miller indices as 7000, 4000, and 1000 K, decreasing for more negative deposition potentials. This offers a framework for exposed facet control in electrocrystallization. In CO 2 electrocatalysis, −0.35 V vs reversible hydrogen electrode was observed to be a turn-on potential for improved CO 2 reduction activity; dendrites showed 50% Faradaic efficiency for CO production at more cathodic potentials. The Tafel slope was measured to be 40 mV/decade for {100} and {110}-rich Au dendrites and 110 mV/decade for {111}-dominated Au plates, suggesting the higher surface energy crystal facets may stabilize all of the CO 2 reduction reaction intermediates.