arXiv subjects

Jon-Paul Maria

Publications and source records attributed to Jon-Paul Maria.

At least 37 records · Page 2Linked to original sources

arXiv2025

Rapid synthesis of dual-element isotope-enriched alpha-MoO3 crystals by reactive vapor transport

In this work, we develop a rapid reactive vapor transport technique to efficiently utilize limited isotopically pure precursors, particularly gaseous 18O2, and synthesize mm-scale, high-quality crystals within few-minute growth durations. We unlock this capability by using metallic molybdenum precursors with high source temperatures (900 C) and total pressures (1 atm) to maximize precursor efficiency and yield. Subsequently, we grow MoO3 single crystals with high and uniform enrichment levels of 98Mo and 18O isotopes in several different permutations. As probed by Raman spectroscopy, modest and significant phonon energy redshifts occur following 98Mo and 18O enrichment, respectively. By demonstrating control over both molybdenum and oxygen isotopic fractions, we establish a powerful tool to advance nanophotonics and thermal management goals using MoO3. This work is motivated by the possibility to enhance and engineer lattice vibrational mode phenomena including thermal conduction and hyperbolic phonon polariton (HPhP) dispersion, with particular interest in comparing the effects of light and heavy element enrichment.

cond-mat.mtrl-sci↗

arXiv2025

A Software Package for Generating Robust and Accurate Potentials using the Moment Tensor Potential Framework

We present the Plan for Robust and Accurate Potentials (PRAPs), a software package for training and using moment tensor potentials (MTPs) in concert with the Machine Learned Interatomic Potentials (MLIP) software package. PRAPs provides an automated workflow to train MTPs using active learning procedures, and a variety of utilities to ease and improve workflows when utilizing the MLIP software. PRAPs was originally developed in the context of crystal structure prediction, in which one calculates convex hulls and predicts low energy metastable and thermodynamically stable structures, but the potentials PRAPs develops are not limited to such applications. PRAPs produces two potentials, one capable of rough estimates of the energies, forces and stresses of almost any chemical structure in the specified compositional space -- the Robust Potential -- and a second potential intended to provide more accurate descriptions of ground state and metastable structures -- the Accurate Potential. We also present a Python library, mliputils, designed to assist users in working with the chemical structural files used by the MLIP package.

physics.chem-ph↗

arXiv2025

Resolving Structural Transitions in Lanthanide High-Entropy Oxides

We report a temperature-composition phase diagram for the chemically disordered and CeO2-LA2O3 high entropy oxides (HEOs), where LA denotes equimolar Y, La, Sm, and Pr, delineating stability regions for bixbyite, disordered fluorite, and intermediate vacancy-ordered fluorite phases. The diagram is constructed from a characterization package applied to bulk ceramics including X-ray diffraction (XRD), transmission electron microscopy (TEM) electron diffraction, Raman spectroscopy, energy-dispersive spectroscopy, X-ray absorption near-edge structure spectroscopy, and ultraviolet-visible spectroscopy, to quantify crystal structure at multiple length-scales, local coordination environments, and electronic structures across the formulation space. This comprehensive measurement suite is critical to identify boundaries between the closely related phases. For example, Raman scattering reveals local structural and defect environments unique to bixbyite local order that persist to ~50% Ce under equilibrium synthesis conditions but are invisible to XRD and TEM. We also report a companion thin film study to demonstrate that quenched kinetic energy from a physical deposition process can metastabilize the high symmetry, and thus high entropy, fluorite phase with only 20% Ce. This is noteworthy because electroneutrality constraints demand an exceptionally vacated oxygen sublattice; we estimate 16.7%, approaching that of delta-Bi2O3. Together, our equilibrium ceramics and far-from-equilibrium thin films show that when synthesis is coupled with rigorously chosen, multi-length-scale characterization, now one can identify the phase stability thermodynamic drivers and simultaneously derive practical guidelines for experimentally realizing targeted phases and structures - and thereby deliberately engineer properties in CeO2-LA2O3 HEOs, whose broad defect chemistries demand such an approach.

cond-mat.mtrl-sci↗

arXiv2025

Automated Materials Discovery Platform Realized: Scanning Probe Microscopy of Combinatorial Libraries

Combinatorial materials libraries provide a powerful platform for mapping how physical properties evolve across binary and ternary cross-sections of multicomponent phase diagrams. While synthesis of such libraries has advanced since the 1960s and been accelerated by laboratory automation, their broader utility depends on rapid, quantitative measurements of composition-dependent structures and functionalities. Scanning probe microscopies (SPM), including piezoresponse force microscopy (PFM), offer unique potential for providing these functionally relevant, spatially resolved readouts. Here, we demonstrate a fully automated SPM framework for exploring ferroelectric properties across combinatorial libraries, focusing on binary Sm-doped BiFeO3 (SmBFO) and ternary Al$_{1-x-y}$Sc$_x$B$_y$N (Al,Sc,B)N systems. In SmBFO, automated exploration identifies the known morphotropic phase boundary with enhanced ferroelectric response and reveals a previously unreported double-peak fine structure. In the (Al,Sc,B)N library, ferroelectric behavior emerges at the phase-stability boundary, correlating with variations in morphology and defect concentration. By integrating automated SPM with wavelength-dispersive spectroscopy (WDS) and photoluminescence mapping, we resolve the composition-morphology-defect-property relationships underlying ferroelectric response and demonstrate a pathway toward a multi-tool, high-throughput characterization platform. Finally, we implement Gaussian-process-based single- and multi-objective Bayesian optimization to enable autonomous exploration, highlighting the Pareto front as a powerful framework for balancing competing physical rewards and accelerating data-driven physics discovery.

cond-mat.mtrl-sci↗

arXiv2025

Exploring Cation Selection and Disorder within Entropy-Driven $A_{6}B_{2}$O$_{17}$ ($A$=Zr/Hf, $B$=Nb/Ta) Oxides

We investigate the local atomic and electronic structure, thermodynamic stability, and defect chemistry of $A_{6}B_{2}$O$_{17}$ ($A$ = Zr/Hf, $B$ = Nb/Ta) oxides using first-principles density functional theory (DFT) calculations. We examine both ordered unit cells as well as fully disordered special quasirandom structures to clearly discern the effects of cation disorder. Structural predictions align closely with previous experimental results and follow established ionic radii trends. The electronic structure is strongly dependent on $B$-cation species: $A_{6}$Ta$_{2}$O$_{17}$ compositions have ~30% larger band gaps than their $A_{6}$Nb$_{2}$O$_{17}$ counterparts. Defect chemistry is similar for all compositions, with anion vacancies being more energetically favorable than corresponding cation defects. All explored $A_{6}B_{2}$O$_{17}$ compositions are enthalpically unstable with respect to their $A$O$_{2}$ and $B_{2}$O$_{5}$ competing oxides and are therefore classified as entropy-stabilized materials, supporting prior experimental results. The pronounced agreement between our disordered supercell predictions with experimental measurements indicates all explored $A_{6}B_{2}$O$_{17}$ compositions contain substantial cation disorder across all 6-, 7-, and 8-coordinated sites. Our findings collectively provide a fundamental understanding of the $A_{6}B_{2}$O$_{17}$ material family through DFT calculations, establishing a framework for future compositional tuning to engineer targeted material properties.

cond-mat.mtrl-sci↗

arXiv2025

Material-Limited Switching in Nanoscale Ferroelectrics

The ferroelectric switching speed has been experimentally obfuscated by the interaction between the measurement circuit and the ferroelectric switching itself. This has prohibited the observation of real material responses at nanosecond timescales and lower. Here, fundamental polarization switching speeds in ferroelectric materials with the perovskite, fluorite, and wurtzite structures are reported. Upon lateral scaling of island capacitors from micron to nanoscales, a clear transition from circuit-limited switching to a material-limited switching regime is observed. In La$_{0.15}$Bi$_{0.85}$FeO$_{3}$ capacitors, switching is as fast as ~150 ps, the fastest switching time reported. For polycrystalline Hf$_{0.5}$Zr$_{0.5}$O$_{2}$ capacitors, a fundamental switching limit of ~210 ps is observed. Switching times for Al$_{0.92}$B$_{0.08}$N are near 20 ns, limited by the coercive and breakdown electric fields. The activation field, instantaneous pseudo-resistivity, and energy-delay are reported in this material-limited regime. Lastly, a criterion for reaching the material-limited regime is provided. This regime enables observation of intrinsic material properties and favorable scaling trends for high-performance computing.

cond-mat.mtrl-sci↗

arXiv2025

Exploring the Complex Landscape of Entropy Stabilized Oxides

Entropy-stabilized oxides (ESOs), driven by high configurational entropy, have gained phenomenological research interest due to their potential for tailoring structure property relationships. However, the chemical short range ordering (SRO) and its interplay with local lattice distortion (LD) remain to be explored, although they could diminish the configurational entropy and potentially impact structure property relationships. A combination of experimental and theoretical approaches are employed to investigate the SRO and LD in the prototype ESO, Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O, generally referred to as J14. We demonstrate that the efficiency and accuracy of density functional theory (DFT) relaxed special quasirandom structures (SQS) enhances the analysis of the local structure of J14, unveiling the unique local cationic environments. Importantly, this joint experimental and computational approach sheds light on the understanding of local structure and structure property relationships in J14, demonstrating the necessity for further research into other high entropy and compositionally complex materials.

cond-mat.mtrl-sci↗

arXiv2025

Quantitative Nonlinear Optical Polarimetry with High Spatial Resolution

Nonlinear optical microscopy such as in the optical second-harmonic generation (SHG) modality has become a popular tool today for probing materials in the physical and biological sciences. While imaging and spectroscopy are widely used in the microscopy mode, nonlinear polarimetry, which can shed light on materials' symmetry and microstructure, is relatively underdeveloped. This is partly because quantitative analytical modeling of the optical SHG response for anisotropic crystals and films largely assumes low-numerical aperture (NA) focusing of light, where the plane-wave approximation is sufficient. Tight focusing provides unique benefits in revealing out-of-plane polarization responses, which cannot be detected by near-plane-wave illumination at normal incidence. Here, we outline a method for quantitatively analyzing SHG polarimetry measurements obtained under high-NA focusing within a microscope geometry. Experiments and simulations of a variety of standard samples, from single crystals to thin films, are in good agreement, including measured and simulated spatial SHG maps of ferroelectric domains. A solution to the inverse problem is demonstrated, where the spatial distribution of an SHG tensor with unknown tensor coefficient magnitudes is determined by experimentally measured polarimetry. The ability to extract the out-of-plane component of the nonlinear polarization in normal incidence is demonstrated, which can be valuable for high-resolution polarimetry of 2D materials, thin films, heterostructures, and uniaxial crystals with a strong out-of-plane response. Copyright 2025 Optica Publishing Group. Users may use, reuse, and build upon the article, or use the article for text or data mining, so long as such uses are for non-commercial purposes and appropriate attribution is maintained. All other rights are reserved. https://doi.org/10.1364/OPTICA.559060

cond-mat.mtrl-sci↗

arXiv2025

Chemically-Disordered Transparent Conductive Perovskites with High Crystalline Fidelity

This manuscript presents a working model linking chemical disorder and transport properties in correlated-electron perovskites with high-entropy formulations and a framework to actively design them. We demonstrate this new learning in epitaxial Sr$x$(Ti,Cr,Nb,Mo,W)O$3$ thin films that exhibit exceptional crystalline fidelity despite a diverse chemical formulation where most B-site species are highly misfit with respect to valence and radius. X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy confirm a unique combination of chemical disorder and structural perfection in thick epitaxial layers. This combination produces significant electron correlation, low electrical resistivity, and an optical transparency window that surpasses that of constituent end-members, with a flattened frequency- and temperature-dependent response. We address the computational challenges of modeling such systems and investigate short-range ordering using cluster expansion. These results showcase that unusual d-metal combinations access an expanded property design space that is predictable using end-member characteristics -- though unavailable to them -- thus offering performance advances in optical, spintronic, and quantum devices.

cond-mat.mtrl-sci↗

arXiv2025

Nitrogen Vacancies Induce Fatigue in Ferroelectric $\mathrm{Al_{0.93}B_{0.07}N}$

Wurtzite ferroelectrics (e.g., $\mathrm{Al_{0.93}B_{0.07}N}$) are being explored for high-temperature and emerging near-, or in-compute, memory architectures due to the material advantages offered by their large remanent polarization and robust chemical stability. Despite these advantages, current $\mathrm{Al_{0.93}B_{0.07}N}$ devices do not have sufficient endurance lifetime to meet roadmap targets. To identify the defects responsible for this limited endurance, a combination of electronic measurements and optical spectroscopies characterized the evolution of defect states within $\mathrm{Al_{0.93}B_{0.07}N}$ with cycling. Ultrathin ($\sim$10 nm) metal contacts were used to optically probe regions subject to ferroelectric switching; photoluminescence spectroscopy identified the emergence of a transition near 2.1 eV whose intensity scaled with the non-switching polarization quantified via positive-up negative-down (PUND) measurements. Accompanying thermally stimulated depolarization current (TSDC) and modulus spectroscopy measurements also observed the strengthening of a state near 2.1 eV. The origin of this feature is ascribed to transitions between a nitrogen vacancy and another defect deeper in the bandgap. Recognizing that the impurity concentration is largely fixed, strengthening of this transition indicates an increase in the number of nitrogen vacancies. Switching, therefore, creates vacancies in $\mathrm{Al_{0.93}B_{0.07}N}$ likely due to hot-atom damage induced by the aggressive fields necessary to switch wurtzite materials that ultimately limits endurance.

cond-mat.mtrl-sci↗

arXiv2025

Maximizing solubility in rock salt high-entropy oxides

To explore and quantitatively map the cation-size mismatch solubility limits in high-entropy oxides (HEOs), we report on Ca$^{2+}$ substitution in prototypical MgCoNiCuZnO, because, while isovalent, Ca$^{2+}$ is 38% larger than its partners' average ionic radii. Using the thermodynamics-grounded bond-length distribution descriptor, we identify Ca$^{2+}$-Cu$^{2+}$ interactions as the primary prospective lattice destabilizer. Bulk synthesis confirms only 4% Ca solubility with Cu at 950$^o$C, modestly rising to 5% after Cu removal at 1150$^o$C. We then employ far-from-equilibrium pulsed-laser deposition to investigate metastable solubility: epitaxial films incorporate 10% Ca with Cu and a full 20% Ca without, doubling and quadrupling the respective bulk limits. This Ca uptake additionally enables deterministic lattice-parameter control via Ca concentration. Overall, our results demonstrate both the extended solubility possible in HEO systems, particularly when accessing metastable states through quenching from high-energy plasma, and that the specific constellation of solid-solvent cations can be rationally engineered to minimize bond-length distributions when largely misfit cations are added, thus expanding the accessible compositional space.

cond-mat.mtrl-sci↗

arXiv2025

Lanthanide L-Edge Spectroscopy of High-Entropy Oxides: Insights into Valence and Phase Stability

High-entropy oxides (HEOs) are a promising class of multicomponent ceramics with tunable structural and electronic properties. In this study, we investigate the local electronic structure of rare-earth HEOs in the (Ce, Sm, Pr, La, Y)O2 system using X-ray absorption spectroscopy (XAS). By systematically increasing the Ce concentration, we observe a phase transition from bixbyite to fluorite, tracked by X-ray diffraction (XRD) and corroborated by L-edge XANES analysis of La, Sm, Ce, and Pr. The oxidation states of La and Sm remain trivalent, while Ce exhibits a minor Ce 3+ fraction and Pr shows a consistent mixed-valence state. Density functional theory (DFT) calculations with Bader charge analysis support these findings and reveal that the phase transition is driven by compositional effects rather than cation redox. Our combined experimental and computational approach provides new insights into structure-valence correlations in RE-HEOs and their implications for ionic transport and phase stability.

cond-mat.mtrl-sci↗

arXiv2025

A Thermodynamic Theory of Proximity Ferroelectricity

Proximity ferroelectricity has recently been reported as a new design paradigm for inducing ferroelectricity, where a non-ferroelectric polar material becomes a ferroelectric by interfacing with a thin ferroelectric layer. Strongly polar materials, such as AlN and ZnO, which were previously unswitchable with an external field below their dielectric breakdown fields, can now be switched with practical coercive fields when they are in intimate proximity to a switchable ferroelectric. Here, we develop a general Landau-Ginzburg theory of proximity ferroelectricity in multilayers of non-ferroelectrics and ferroelectrics to analyze their switchability and coercive fields. The theory predicts regimes of both "proximity switching" where the multilayers collectively switch, as well as "proximity suppression" where they collectively do not switch. The mechanism of the proximity ferroelectricity is an internal electric field determined by the polarization of the layers and their relative thickness in a self-consistent manner that renormalizes the double-well ferroelectric potential to lower the steepness of the switching barrier. Further reduction in the coercive field emerges from charged defects in the bulk that act as nucleation centers. The application of the theory to proximity ferroelectricity in Alx-1ScxN/AlN and Zn1-xMgxO/ZnO bilayers is demonstrated. The theory further predicts that multilayers of dielectric/ferroelectric and paraelectric/ferroelectric layers can potentially result in induced ferroelectricity in the dielectric or paraelectric layers, resulting in the entire stack being switched, an exciting avenue for new discoveries. This thawing of "frozen ferroelectrics", paraelectrics and potentially dielectrics, promises a large class of new ferroelectrics with exciting prospects for previously unrealizable domain-patterned optoelectronic and memory technologies.

cond-mat.mtrl-sci↗

arXiv2025

Ferroelectric Al$_{1-x}$B$_x$N sputtered thin films on n-type Si bottom electrodes

Ferroelectric Al$_{1-x}$B$_x$N thin films are grown on highly doped and plasma treated (100) n-type Si. We demonstrate ferroelectricity for x = <0.01, 0.02, 0.06, 0.08, 0.13, and 0.17 where the n-type Si is both the substrate and bottom electrode. Polarization hysteresis reveals remanent polarization values between 130-140 $μ$C/cm$^2$ and coercive field values as low as 4 MV/cm at 1 Hz with low leakage. The highest re-sistivity and most saturating hysteresis occurs with B contents between x = 0.06 and 0.13. We also demonstrate the impact of substrate plasma treatment time on Al$_{1-x}$B$_x$N crystallinity and switching. Cross-sectional transmission electron microscopy and electron energy loss spectra reveal an amorphous 3.5 nm SiNx layer at the Al$_{1-x}$B$_x$N interface post-plasma treatment and deposition. The first $\sim 5$ nm of Al$_{1-x}$B$_x$N is crystallographically defective. Using the n-type Si substrate we demonstrate Al$_{1-x}$B$_x$N thick-ness scaling to 25 nm via low frequency hysteresis and CV. Serving as the bottom electrode and sub-strate, the n-type Si enables a streamlined growth process for Al$_{1-x}$B$_x$N for a wide range of Al$_{1-x}$B$_x$N compositions and layer thicknesses.

cond-mat.mtrl-sci↗

arXiv2025

Thermodynamics-Inspired High-Entropy Oxide Synthesis

High-entropy oxide (HEO) thermodynamics transcend temperature-centric approaches, spanning a multidimensional landscape where oxygen chemical potential plays a decisive role. Here, we experimentally demonstrate how controlling the oxygen chemical potential coerces multivalent cations into divalent states in rock salt HEOs. We construct a preferred valence phase diagram based on thermodynamic stability and equilibrium analysis, alongside a high throughput enthalpic stability map derived from atomistic calculations leveraging machine learning interatomic potentials. We identify and synthesize seven equimolar single-phase rock salt compositions that accommodate multivalent Mn, Fe, or both, as confirmed by X-ray diffraction and fluorescence. X-ray absorption fine structure spectra reveal predominantly divalent cations. Ultimately, we introduce oxygen chemical potential overlap as a key complementary descriptor predicting HEO stability and synthesizability. Although we focus on rock salt HEOs, our methods are chemically and structurally agnostic, providing a broadly adaptable framework for navigating HEOs thermodynamics and enabling a broader compositional range with contemporary property interest.

cond-mat.mtrl-sci↗

arXiv2025

Processing-dependent Chemical Ordering in a Metallic Alloy Characterized via Non-destructive Bragg Coherent Diffraction Imaging

Of current importance for alloy design is controlling chemical ordering through processing routes to optimize an alloy's mechanical properties for a desired application. However, characterization of chemical ordering remains an ongoing challenge, particularly when nondestructive characterization is needed. In this study, Bragg coherent diffraction imaging is used to reconstruct morphology and lattice displacement in model Cu$_3$Au nanocrystals that have undergone different heat treatments to produce variation in chemical ordering. The magnitudes and distributions of the scattering amplitudes (proportional to electron density) and lattice strains within these crystals are then analyzed to correlate them to the expected amount of chemical ordering present. Nanocrystals with increased amounts of ordering are found to generally have less extreme strains present and reduced strain distribution widths. In addition, statistical correlations are found between the spatial arrangement of scattering amplitude and lattice strains.

cond-mat.mtrl-sci↗

arXiv2025

Discovering High-Entropy Oxides with a Machine-Learning Interatomic Potential

High-entropy materials shift the traditional materials discovery paradigm to one that leverages disorder, enabling access to unique chemistries unreachable through enthalpy alone. We present a self-consistent approach integrating computation and experiment to understand and explore single-phase rock salt high-entropy oxides. By leveraging a machine-learning interatomic potential, we rapidly and accurately map high-entropy composition space using our two descriptors: bond length distribution and mixing enthalpy. The single-phase stabilities for all experimentally stabilized rock salt compositions are correctly resolved, with dozens more compositions awaiting discovery.

cond-mat.mtrl-sci↗

arXiv2024

Interfacial defect properties of high-entropy carbides: Stacking faults, Shockley partial dislocations, and a new Evans-Polanyi-Semenov relation

Using first principles calculations, {111} intrinsic stacking fault (ISF) energies in Group IVB, VB, and VIB high-entropy transition metal carbides are shown to be predictable from an optimized rule of mixtures based on the properties of the single metal carbide constituents present near the stacking fault. A composition-independent linear relationship is demonstrated between the ISF energies and the unstable stacking fault (USF) energies along the <112>{111} gamma surface slip path. Treating the ISF and USF energies as analogous to the heat of reaction and transition state barrier in chemical reactions, this linear relationship represents a new application of the Evans-Polanyi-Semenov principle. Further, a full defect energy distribution can be obtained from the predicted ISF energies with only the composition as an input for the mixed early-transition metal carbides. Applying a model that balances the elastic repulsion between partial dislocations with the distribution of ISF energies, we show that Shockley partial edge dislocations should remain bound for all valence electron concentration values up to about 9.6, even when the average stacking fault energy is negative.

cond-mat.mtrl-sci↗