arXiv subjects

James M. LeBeau

Publications and source records attributed to James M. LeBeau.

At least 19 recordsLinked to original sources

arXiv2026

Quasicrystalline oxide interfaces by twisting SrTiO3 membranes

Quasicrystals reveal that long-range order can exist without translational periodicity, but deterministic routes for designing strongly bonded quasicrystalline interfaces remain unexplored. Here, we show that such interfaces can be engineered by growing epitaxial SrTiO3 membranes on a sacrificial layer, releasing them, twisting them by prescribed angles, and bonding them onto a chosen substrate. SrTiO3 bilayers twisted by 45° form an octagonal quasicrystalline interface with eight-fold rotational symmetry, whereas trilayers assembled with successive 30° rotations form a dodecagonal interface with twelve-fold symmetry. Selected-area and nano-beam electron diffraction, multislice electron ptychography, atomic-resolution dark field imaging, Fourier analysis, and real-space tiling establish long-range quasicrystalline order with electronic reconstruction evident from electron energy-loss spectroscopy after annealing. Atomistic simulations based on machine-learned interatomic potentials show that octagonal order emerges as the bilayer twist angle approaches 45°. Polarization-dependent X-ray absorption spectroscopy in 1.5 nm twisted bilayers reveals a twist-dependent electronic response, and terahertz-field-induced second-harmonic generation circular dichroism identifies a symmetry-dependent nonlinear optical response at the 45° quasicrystalline condition. Twisted oxide membranes therefore provide an extendable route to engineer quasiperiodic order and couple it to interfacial bonding, orbital reconstruction, and nonlinear optical response in complex oxides.

cond-mat.mtrl-sci↗

arXiv2026

On Transmission Function Amplitude and Phase Recovery in Multislice Electron Ptychography

{Multislice electron ptychography commonly accounts for inelastic scattering by including an absorptive object potential in the reconstruction forward model that attenuates the elastic signal. However, it remains unclear how the reconstruction is quantitatively impacted by thermal scattering. Here, we use the quantum excitation of phonons (QEP) formalism, which explicitly separates elastic and inelastic (thermal diffuse) scattering within a single multislice propagation, to simulate four-dimensional scanning transmission electron microscopy (4D STEM) datasets of PbTiO$_3$ and SrTiO$_3$ and reconstruct their phase and amplitude. We find that reconstructions of the QEP total and elastic-only datasets are nearly indistinguishable across sample thicknesses from 11 to 40 nm and across atomic species, demonstrating that the reconstruction is largely insensitive to incoherent thermal diffuse scattering within the collected angular range. Reconstructions from multislice phase-only simulations further confirm that appreciable amplitude does not arise from multiple elastic scattering, but instead reflects attenuation of the coherent elastic signal due to thermal scattering. Further comparison of the QEP elastic-only reconstruction with absorptive multislice simulations reveals substantial amplitude contrast deviations for heavy Pb columns (up to 17\%), arising from the approximations used to evaluate the absorptive potential for the 4D STEM simulation. These results thus indicate that reconstruction phase and amplitude accuracy are not significantly limited by the absorptive potential forward model, even in the presence of thermal diffuse scattering.

cond-mat.mtrl-sci↗

arXiv2026

Anion Ordering and Phase Stability Govern Optical Band Gaps in BaZr(S,Se)3

Chalcogenide perovskites have emerged as promising lead free materials for photovoltaic and thermoelectric applications. Among them, BaZrS3 has attracted particular attention due to its thermal and chemical stability, favorable optoelectronic properties, and low thermal conductivity. Here, we combine molecular dynamics and Monte Carlo simulations based on machine learned interatomic potentials with scanning transmission electron microscopy to investigate mixing thermodynamics and phase stability in the BaZr(S,Se)3 system. We identify an unusual ordered structure that persists at room temperature, most prominently at 33% S, where S and Se atoms form alternating layers within the crystal. Free energy calculations yield the temperature composition phase diagram, including a nonperovskite delta phase in the Se rich limit and a perovskite phase in the S rich limit, separated by a broad two phase region. Analysis of the dielectric function and the absorption coefficient demonstrates that composition, crystal structure, and anion ordering jointly control the optical band gap. Selenium alloying enables tuning between approximately 1.6 and 1.9eV, while anion ordering within a given composition reduces the gap by about 0.12eV. Lastly, variations between structural polymorphs give rise to band gap differences of up to 0.4eV.

cond-mat.mtrl-sci↗

arXiv2026

Emergence of unconventional magnetic order in strain-engineered RuO2/TiO2 superlattices

The spin ordering in RuO2 remains a highly debated topic, owing to its elusive nature, with reports ranging from a nonmagnetic ground state to signatures of unconventional magnetic order. Here we provide the first unambiguous, and direct evidence of unconventional magnetism in epitaxial, fully strained RuO2/TiO2 superlattices on TiO2 (110) substrate grown by hybrid molecular beam epitaxy. Polarized neutron reflectometry reveals a finite magnetic moment localized within the compressively strained RuO2 layers, consistent with predictions obtained from first-principles calculations. Complementary density functional theory and X-ray photoemission spectroscopy show that epitaxial strain drives the Ru 4d states toward the Fermi level, triggering a Stoner-type instability that stabilizes non-compensated magnetic order. These unique results reveal that RuO2 exhibits unconventional magnetic states under epitaxial strain, which are not accessible in bulk and establish strain engineering as a powerful route to uncover and control magnetic phases in RuO2 and related oxides.

cond-mat.mtrl-sci↗

arXiv2025

Direct determination of antiferroelectric-to-ferroelectric phase transition pathways in PbZrO$_3$ with Operando Electron Microscopy

Under a sufficiently high applied electric field, a non-polar antiferroelectric material, such as \ce{PbZrO3}, can undergo a rapid transformation to a polar ferroelectric phase. While this behavior is promising for energy storage and electromechanical applications, a complete understanding of the atomic-scale mechanisms governing the phase transition remain elusive. Here, we employ \textit{operando} scanning transmission electron microscopy electric field biasing to directly resolve the antiferroelectric-to-ferroelectric transition pathway in \ce{PbZrO3} thin films under device-relevant conditions. Atomic-resolution imaging reveals a multi-step transition that includes several metastable phases. Complementary nano-beam electron diffraction and atomic scale analysis further show that this pathway and its end states can be modulated, leading to the formation of a \quotes{dead layer} near the substrate with suppressed switching behavior. Taking advantage of this depth-dependent heterogeneity, dynamic phase transformations are observed between coexisting antiferroelectric and metastable ferroelectric phases. At this dynamic transition front, repeated phase interconversion is shown to be driven by competing internal (due to substrate clamping and extended defects) and external fields, allowing the relative energies of intermediate phases to be compared as a function of electric field. This work highlights the critical role of local energetics in phase stability and provides key experimental insights into field-induced phase transitions, guiding the design of antiferroelectric-based devices.

cond-mat.mtrl-sci↗

arXiv2025

Microstructural and preliminary optical and microwave characterization of erbium doped CaMoO$_4$ thin films

This work explores erbium-doped calcium molybdate (CaMoO$_4$) thin films grown on silicon and yttria stabilized zirconia (YSZ) substrates, as a potential solid state system for C-band (utilizing the $\sim$1.5 $μ$m Er$^{3+}$ 4f-4f transition) quantum emitters for quantum network applications. Through molecular beam epitaxial growth experiments and electron microscopy, X-ray diffraction and reflection electron diffraction studies, we identify an incorporation limited deposition regime that enables a 1:1 Ca:Mo ratio in the growing film leading to single phase CaMoO$_4$ formation that can be in-situ doped with Er (typically 2-100 ppm). We further show that growth on silicon substrates is single phase but polycrystalline in morphology; while growth on YSZ substrates leads to high-quality epitaxial single crystalline CaMoO$_4$ films. We perform preliminary optical and microwave characterization on the suspected $Y_1 - Z_1$ transition of 2 ppm, 200 nm epitaxial CaMoO$_4$ annealed thin films and extract an optical inhomogeneous linewidth of 9.1(1) GHz, an optical excited state lifetime of 6.7(2) ms, a spectral diffusion-limited homogeneous linewidth of 6.7(4) MHz, and an EPR linewidth of 1.10(2) GHz.

cond-mat.mtrl-sci↗

arXiv2025

Operando Electron Microscopy of Nanoscale Electronic Devices on Non-Conductive Substrates

Achieving operating conditions comparable to ``bulk'' electronic devices, such as thin film capacitors, during \textit{operando} electron microscopy remains challenging, particularly when devices are grown on non-conductive substrates. Limited precision of focused ion beam milling for sample preparation often necessitates the use of conductive substrates or artificially thick layers that differ from actual device architectures. These modifications can alter native strain, electrostatic boundary conditions, and ultimately device response. Here, we present a generic and versatile workflow for \textit{operando} biasing of thin-film capacitors in the (scanning) transmission electron microscope, including sample fabrication and device operation. By introducing a patterned insulating barrier adjacent to the bulk-characterized capacitors, our approach enables sample preparation without altering the original film structure. As a case study, we apply the method to a piezoelectric thin-film capacitor grown on an insulating substrate, and demonstrate that it preserves the boundary-condition-sensitive domain switching at the atomic scale under applied electric fields. Overall, the process can help to establish a foundation for systematic \textit{operando} studies of complex thin-film systems under representative bulk testing geometries.

cond-mat.mtrl-sci↗

arXiv2025

phaser: A unified and extensible framework for fast electron ptychography

We present \code{phaser}, an open-source Python package that provides a unified interface to both conventional and gradient descent-based ptychographic algorithms. Features such as mixed-state probe, probe position correction, and multislice ptychography make experimental reconstructions practical and robust. Reconstructions are specified in a declarative format and can be run from a command line, Jupyter notebook, or web interface. Multiple computational backends are supported to provide maximum flexibility. With the JAX computational backend, a six-fold improvement in iteration speed is achieved over a widely used package implemented in MATLAB, fold\_slice/PtychoShelves. We report reconstruction success for a variety of experimental datasets, and detail the effects of regularization on convergence and reconstruction quality. The software promises to speed the application and development of ptychographic methods for materials science.

physics.comp-ph↗

arXiv2025

Strain-Stabilized Interfacial Polarization Tunes Work Function Over 1 eV in RuO2/TiO2 Heterostructures

Interfacial polarization-charge accumulation at the heterointerface-is a well-established tool in semiconductors, but its influence in metals remains unexplored. Here, we demonstrate that interfacial polarization can robustly modulate surface work function in metallic rutile RuO2 layers in epitaxial RuO2/TiO2 heterostructures grown by hybrid molecular beam epitaxy. Using multislice electron ptychography, we directly visualize polar displacements of transition metal ions relative to oxygen octahedra near the interface, despite the conductive nature of RuO2. This interfacial polarization enables over 1 eV modulation of the RuO2 work function, controlled by small thickness variation (2-4 nm) as measured by Kelvin probe probe microscopy, with a critical thickness of 4 nm - corresponding to the transition from fully strained to relaxed film. These results establish interfacial polarization as a powerful route to control electronic properties in metals and have implications for designing tunable electronic, catalytic, and quantum devices through interfacial control in polar metallic systems.

cond-mat.mtrl-sci↗

arXiv2025

Optimizing Atomic Number Contrast in Multislice Electron Ptychography

Here we explore the atomic number ($Z$) dependence of multislice electron ptychography and approaches to optimize Z sensitivity. Specifically, we show that ptychography's $Z$-dependence is highly dependent on the integrated area of an atom column considered. A monotonic $Z$-dependence is found when the reconstructed projected atomic potentials are integrated over a small region. When increasing the integration area, $Z$-contrast changes significantly, becoming highly non-monotonic and following trends in the orbital shell-structure. Moreover, the reconstructed projected potential aligns with the transmission function with an overall deviation of only 2.4\%. The non-monotonic $Z$-dependence is further shown to be useful to accentuate contrast between certain elements, allowing for distinguishability of elements that are only a single atomic number apart, and even in $>$ 20 nm thick samples. This is demonstrated for $β$-CuZn ($Z$ = 29 and 30), with the differentiability between the elements explored for different signal quantification methods. The impact of electron dose and finite effective source size are also considered. These results demonstrate that the atom column integration area can optimize ptychographic $Z$-contrast for specific applications and experimental conditions.

cond-mat.mtrl-sci↗

arXiv2025

Sensitivity of Multislice Electron Ptychography to Point Defects: A Case Study in SiC

Here, we evaluate multislice electron ptychography as a tool to carry out depth-resolved atomic resolution characterization of point defects, using silicon carbide as a case study. Through multislice electron scattering simulations and multislice ptychographic reconstructions, we investigate the phase contrast arising from individual silicon vacancies, antisite defects, and a wide range of substitutional transition metal dopants (V\textsubscript{Si} to W\textsubscript{Si}) and potential detectability. Simulating defect types, positions, and microscope conditions, we show that isolated point defects can be located within a unit cell along the sample's depth. The influence of electron energy, dose, defocus, and convergence semi-angle is also explored to determine their role in governing defect contrast. These results guide experiments aiming to analyze point defects with multislice electron ptychography.

cond-mat.mtrl-sci↗

arXiv2025

Grain Boundary Space Charge Engineering of Solid Oxide Electrolytes: Model Thin Film Study

Grain boundaries (GB) profoundly influence the electrical properties of polycrystalline ionic solids. Yet, precise control of their transport characteristics has remained elusive, thereby limiting the performance of solid-state electrochemical devices. Here, we demonstrate unprecedented manipulation of space charge controlled ionic grain boundary resistance (up to 12 orders of magnitude) in metal oxide thin films. We exploit the orders of magnitude higher grain boundary diffusivities of substrate cation elements (i.e. Al from $Al_2O_3$ and Mg from MgO) relative to the bulk to modify the grain boundary chemistry, and thereby GB core charge, in a model oxygen ion conducting polycrystalline thin film solid electrolyte, Gd-doped $CeO_2$. This approach, confirmed jointly by TEM imaging and by extracting the respective GB and bulk diffusivities from measured SIMS profiles, enabled us to selectively control the chemistry of the GBs, while minimally modifying grain (bulk) chemistry or film microstructure, thereby ruling out potential effects of microstructure, strain or secondary phases. Broad tuning of GB space charge potentials is achieved by manipulating GB core charge density by over an order of magnitude, thereby providing a powerful tool for systematic studies of grain boundary phenomena across various functional materials. The implications of such control are far-reaching in achieving new functionality, improving efficiency and longevity of solid-state electrochemical devices.

cond-mat.mtrl-sci↗

arXiv2025

Metallicity and Anomalous Hall Effect in Epitaxially-Strained, Atomically-thin RuO2 Films

The anomalous Hall effect (AHE), a hallmark of time-reversal symmetry breaking, has been reported in rutile RuO2, a debated metallic altermagnetic candidate. Previously, AHE in RuO2 was observed only in strain-relaxed thick films under extremely high magnetic fields (~50 T). Yet, in ultrathin strained films with distinctive anisotropic electronic structures, there are no reports, likely due to disorder and defects suppressing metallicity thus hindering its detection. Here, we demonstrate that ultrathin, fully-strained 2 nm TiO2/t nm RuO2/TiO2 (110) heterostructures, grown by hybrid molecular beam epitaxy, retain metallicity and exhibit a sizeable AHE at a significantly lower magnetic field (< 9 T). Density functional theory calculations reveal that epitaxial strain stabilizes a non-compensated magnetic ground state and reconfigures magnetic ordering in RuO2 (110) thin films. These findings establish ultrathin RuO2 as a platform for strain-engineered magnetism and underscore the transformative potential of epitaxial design in advancing spintronic technologies.

cond-mat.mtrl-sci↗

arXiv2025

Additively manufacturable high-strength aluminum alloys with thermally stable microstructures enabled by hybrid machine learning-based design

Additively manufactured (AM) aluminum alloys with high strength and thermal stability have broad applications in turbine engines, vacuum pumps, heat exchangers, and many other industrial systems. Employing precipitates with an L1$_2$ structure to block dislocation motions is a widespread strategy to strengthen aluminum. However, to achieve high strength, a high volume fraction of small precipitates is required, and these characteristics are generally mutually exclusive. Here, we show that for certain compositions of Al alloys, L1$_2$ phases initially precipitate as sub-micron metastable ternary phases under the rapid solidification conditions of powder bed AM, yet the subsequent L1$_2$ phases that precipitate during heat treatment of the sample remain at the nanoscale, imparting high strength. For strength to be retained at elevated temperature, these nanoprecipitates must have low coarsening rates. To inversely design the composition of an alloy to have these target microstructural features, we used hybrid calculation of phase diagram (CALPHAD)-based integrated computational materials engineering (ICME) and Bayesian optimization techniques. We tested our approach by designing an Al-Er-Zr-Y-Yb-Ni model alloy, and the selected composition was manufactured in powder form as AM feedstock. The strength of specimens manufactured via laser powder bed fusion (LPBF) from the designed composition is comparable to that of wrought Al 7075, yet without cracking that occurs upon LPBF of Al 7075. After high-temperature (400$^\circ$C) aging the designed alloy is 50% stronger than the strongest known benchmark printable Al alloy.

cond-mat.mtrl-sci↗

arXiv2024

Insights into Chemical and Structural Order at Planar Defects in a Functional Oxide Using Multislice Electron Ptychography

Switchable order parameters in ferroic materials are essential for functional electronic devices, yet disruptions of the ordering can take the form of planar boundaries or defects that exhibit distinct properties. Characterizing the structure of these boundaries is challenging due to their confined size and three-dimensional nature. Here, a chemical anti-phase boundary in the highly ordered double perovskite \ce{Pb2MgWO6} is investigated using multislice electron ptychography. The boundary is revealed to be inclined along the electron beam direction with a finite width of chemical intermixing. Additionally, regions at and near the boundary exhibit antiferroelectric-like displacements, contrasting with the predominantly paraelectric matrix. Spatial statistics and density functional theory calculations further indicate that despite their higher energy, chemical anti-phase boundaries form due to kinetic constraints during growth, with extended antiferroelectric-like distortions induced by the chemically frustrated environment in the proximity of the boundary. The three-dimensional imaging provides critical insights into the interplay between local chemistry and the polar environment, elucidating the role of anti-phase boundaries and their associated confined structural distortions and offering new opportunities for engineering ferroic thin films.

cond-mat.mtrl-sci↗

arXiv2024

Bridging experiment and theory of relaxor ferroelectrics at the atomic scale with multislice electron ptychography

Introducing structural and/or chemical heterogeneity into otherwise ordered crystals can dramatically alter material properties. Lead-based relaxor ferroelectrics are a prototypical example, with decades of investigation having connected chemical and structural heterogeneity to their unique properties. While theory has pointed to the formation of an ensemble of ``slush''-like polar domains, the lack of direct, spatially resolved volumetric data comparable to simulations presents a significant challenge in measuring the spatial distribution and correlation of local chemistry and structure with the physics underlying relaxor behavior. Here, we address this challenge through three-dimensional volumetric characterization of the prototypical relaxor ferroelectric \ce{0.68Pb(Mg$_{1/3}$Nb$_{2/3}$)O3-0.32PbTiO$_3$} using multislice electron ptychography. Direct comparison with molecular dynamics simulations reveals the intimate relationship between the polar structure and unit-cell level charge imbalance induced by chemical disorder. Further, polar nanodomains are maintained through local correlations arising from residual short-range chemical order. Acting in concert with the chemical heterogeneities, it is also shown that compressive strain enhances out-of-plane correlations and ferroelectric-like order without affecting the in-plane relaxor-like structure. Broadly, these findings provide a pathway to enable detailed atomic scale understanding for hierarchical control of polar domains in relaxor ferroelectric materials and devices, and also present significant opportunities to tackle other heterogeneous systems using complementary theoretical and experimental studies.

cond-mat.mtrl-sci↗

arXiv2024

Atomic Structure of Self-Buffered BaZr(S,Se)$_3$ Epitaxial Thin Film Interfaces

Understanding and controlling the growth of chalcogenide perovskite thin films through interface design is important for tailoring film properties. Here, the film and interface structure of BaZr(S,Se)$_3$ thin films grown on LaAlO$_3$ by molecular beam epitaxy and post-growth anion exchange is resolved using aberration-corrected scanning transmission electron microscopy. Epitaxial films are achieved from self-assembly of an interface ``buffer'' layer, which accommodates the large film/substrate lattice mismatch of nearly 40\% for the alloy film studied here. The self-assembled buffer layer, occurring for both the as-grown sulfide and post-selenization alloy films, is shown to have rock-salt-like atomic stacking akin to a Ruddlesden-Popper phase. Above this buffer, the film quickly transitions to the perovskite structure. Overall, these results provide insights into oxide-chalcogenide heteroepitaxial film growth, illustrating a process that yields relaxed, crystalline, epitaxial chalcogenide perovskite films that support ongoing studies of optoelectronic and device properties.

cond-mat.mtrl-sci↗

arXiv2024

A Processing Route to Chalcogenide Perovskites Alloys with Tunable Band Gap via Anion Exchange

We demonstrate synthesis of BaZr(S,Se)3 chalcogenide perovskite alloys by selenization of BaZrS3 thin films. The anion-exchange process produces films with tunable composition and band gap without changing the orthorhombic perovskite crystal structure or the film microstructure. The direct band gap is tunable between 1.5 and 1.9 eV. The alloy films made in this way feature 100x stronger photoconductive response and a lower density of extended defects, compared to alloy films made by direct growth. The perovskite structure is stable in high-selenium-content thin films with and without epitaxy. The manufacturing-compatible process of selenization in H2Se gas may spur the development of chalcogenide perovskite solar cell technology.

cond-mat.mtrl-sci↗