Ferroelectric Modulation of Surface Electronic States in BaTiO3 for Enhanced Hydrogen Evolution Activity.

Ferroelectric nanomaterials offer the promise of switchable electronic properties at the surface, with implications for photo- and electrocatalysis. Studies to date on the effect of ferroelectric surfaces in electrocatalysis have been primarily limited to nanoparticle systems where complex interfaces arise. Here, we use MBE-grown epitaxial BaTiO3 thin films with atomically sharp interfaces as model surfaces to demonstrate the effect of ferroelectric polarization on the electronic structure, intermediate binding energy, and electrochemical activity toward the hydrogen evolution reaction (HER). Surface spectroscopy and ab initio DFT+U calculations of the well-defined (001) surfaces indicate that an upward polarized surface reduces the work function relative to downward polarization and leads to a smaller HER barrier, in agreement with the higher activity observed experimentally. Employing ferroelectric polarization to create multiple adsorbate interactions over a single electrocatalytic surface, as demonstrated in this work, may offer new opportunities for nanoscale catalysis design beyond traditional descriptors.

Single Atomic Layer Ferroelectric on Silicon.

A single atomic layer of ZrO2 exhibits ferroelectric switching behavior when grown with an atomically abrupt interface on silicon. Hysteresis in capacitance-voltage measurements of a ZrO2 gate stack demonstrate that a reversible polarization of the ZrO2 interface structure couples to the carriers in the silicon. First-principles computations confirm the existence of multiple stable polarization states and the energy shift in the semiconductor electron states that result from switching between these states. This monolayer ferroelectric represents a new class of materials for achieving devices that transcend conventional complementary metal oxide semiconductor (CMOS) technology. Significantly, a single atomic layer ferroelectric allows for more aggressively scaled devices than bulk ferroelectrics, which currently need to be thicker than 5-10 nm to exhibit significant hysteretic behavior (Park, et al. Adv. Mater. 2015, 27, 1811).

Drift of Schottky Barrier Height in Phase Change Materials.

Phase-change memory (PCM) devices have great potential as multilevel memory cells and artificial synapses for neuromorphic computing hardware. However, their practical use is hampered by resistance drift, a phenomenon commonly attributed to structural relaxation or electronic mechanisms primarily in the context of bulk effects. In this study, we reevaluate the electrical manifestation of resistance drift in sub-100 nm Ge2Sb2Te5 (GST) PCM devices, focusing on the contributions of bulk vs interface effects. We employ a combination of measurement techniques to elucidate the current transport mechanism and the electrical manifestation of resistance drift. Our steady-state temperature-dependent measurements reveal that resistance in these devices is predominantly influenced by their electrical contacts, with conduction occurring through thermionic emission (Schottky) at the contacts. Additionally, temporal current-voltage characterization allows us to link the resistance drift to a time-dependent increase in the Schottky barrier height. These findings provide valuable insights, pinpointing the primary contributor to resistance drift in PCM devices: the Schottky barrier height for hole injection at the interface. This underscores the significance of contacts (interface) in the electrical manifestation of drift in PCM devices.

Elastic and inelastic mean free paths for scattering of fast electrons in thin-film oxides.

Quantitative transmission electron microscopy (TEM) often requires accurate knowledge of sample thickness for determining defect density, structure factors, sample dimensions, electron beam and X-ray photons signal broadening. The most common thickness measurement is by Electron Energy Loss Spectroscopy which can be applied effectively to crystalline and amorphous materials. The drawback is that sample thickness is measured in units of Inelastic Mean Free Path (MFP) which depends on the material, the electron energy and the collection angle of the spectrometer. Furthermore, the Elastic MFP is an essential parameter for selecting optimal sample thickness to reduce dynamical scatterings, such as for short-range-order characterization of amorphous materials. Finally, the Inelastic to Elastic MFP ratio can predict the dominant mechanism for radiation damage due to the electron beam. We implement a fast and precise method for the extraction of inelastic and elastic MFP values in technologically important oxide thin films. The method relies on the crystalline Si substrate for calibration. The Inelastic MFP of Si was measured as a function of collection semi-angle (ß) by combining Energy-Filtered TEM thickness maps followed by perpendicular cross-sectioning of the sample by Focused-Ion-Beam. For example, we measured a total Inelastic MFP (ß∼157 mrad) in Si of 145 ± 10 nm for 200 keV electrons. The MFP of the thin oxide films is determined by their ratio at their interface with Si or SiO2. The validity of this method was verified by direct TEM observation of cross-to-cross sectioning of TEM samples. The high precision of this method was enabled mainly by implementing a wedge preparation technique, which provides large sampling areas with uniform thickness. We measured the Elastic and Inelastic Mean Free Paths for 200 keV and 80 keV electrons as a function of collection angle for: SiO2 (Thermal, CVD), low-κ SiOCH, Al2O3, TiO2, ZnO, Ta2O5 and HfO2. The measured MFP values were compared to calculations based on models of Wenzel, Malis and Iakoubovskii. These models deviate from measurements by up to 30%, especially for 80 keV electrons. Hence, we propose functional relations for the Elastic MFP and Inelastic MFP in oxides with respect to the mass density and effective atomic number, which reduce deviations by a factor of 2-3. In addition, the effects of sample cooling on the measurements and sample stability are examined.

Electronic Inhomogeneity Influence on the Anomalous Hall Resistivity Loops of SrRuO3 Epitaxially Interfaced with 5d Perovskites.

SrRuO3, a 4d ferromagnet with multiple Weyl nodes at the Fermi level, offers a rich playground to design epitaxial heterostructures and superlattices with fascinating magnetic and magnetotransport properties. Interfacing ultrathin SrRuO3 layers with large spin-orbit coupling 5d transition-metal oxides, such as SrIrO3, results in pronounced peaklike anomalies in the magnetic field dependence of the Hall resistivity. Such anomalies have been attributed either to the formation of Néel-type skyrmions or to modifications of the Berry curvature of the topologically nontrivial conduction bands near the Fermi level of SrRuO3. Here, epitaxial multilayers based on SrRuO3 interfaced with 5d perovskite oxides, such as SrIrO3 and SrHfO3, were studied. This work focuses on the magnetotransport properties of the multilayers, aiming to unravel the role played by the interfaces with 5d perovskites in the peaklike anomalies of the Hall resistance loops of SrRuO3 layers. Interfacing with large band gap insulating SrHfO3 layers did not influence the anomalous Hall resistance loops, while interfacing with the nominally paramagnetic semimetal SrIrO3 resulted in pronounced peaklike anomalies, which have been lately attributed to a topological Hall effect contribution as a result of skyrmions. This interpretation is, however, under strong debate and lately alternative causes, such as inhomogeneity of the thickness and the electronic properties of the SrRuO3 layers, have been considered. Aligned with these latter proposals, our findings reveal the central role played in the anomalies of the Hall resistivity loops by electronic inhomogeneity of SrRuO3 layers due to the interfacing with semimetallic 5d5 SrIrO3.