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Kyle P. Kelley

Publications and source records attributed to Kyle P. Kelley.

At least 19 recordsLinked to original sources
arXiv2026

Origin and Reduction of Coercive Fields in ZnO-based Wurtzite Ferroelectrics

Wurtzite ferroelectrics offer a route to semiconductor-compatible non-volatile devices, but their large coercive fields (E$_c$) constrain the operating window between polarization reversal, leakage and dielectric breakdown. Atomically localized and non-classical switching fronts have recently been identified in wurtzite nitrides, yet the microscopic feature that sets the coercive field remains unresolved. Here we use large-scale reactive molecular dynamics, parameterized against first-principles data, to follow field-driven reversal in pristine, Mg-modified and heterostructured ZnO. Reversal proceeds through rugged inversion-boundary filaments in agreement with recent observations in other wurtzite ferroelectrics. We find that the field required for switching is controlled by the advancing filament head, which is a under-coordinated reconstructed inversion-boundary region during the transient switching dynamics with a large field-aligned local polar-order amplitude that is only partially compensated by an oppositely oriented surrounding shell. Controlled strain-only and charge-doping-only perturbations show that charge redistribution lowers the coercive field more effectively than strain because it suppresses this field-setting unscreened local polar order at the filament head, with the combined effect lowering E$_c$ by $\sim$ 50 \%. Layered ZnO/ZnMgO architectures further create buried nucleation sites and shorten filament propagation lengths. These results connect atomistic switching topology to a materials-design principle for substantially reducing coercive fields in ZnO-based wurtzite ferroelectrics.

cond-mat.mtrl-sci↗
arXiv2026

Absence of lateral domain wall mobility in Zn1-xMgxO thin films

Polarization reversal in ferroelectrics arises from the coupled processes of domain nucleation and subsequent growth, yet the governing mechanisms differ fundamentally between classical perovskite oxides and emerging wurtzite ferroelectrics. While switching in perovskites is typically governed by mobile domain walls whose field-driven propagation dominates macroscopic kinetics, here we show that polarization reversal in wurtzite Zn1-xMgxO proceeds through a qualitatively different pathway. Using scanning oscillator microscopy, in combination with point pulse-imaging methods, we directly map local switching events and domain wall responses, revealing that domain walls in Zn1-xMgxO exhibit negligible lateral mobility (sub 10nm) and that polarization reversal proceeds predominantly through the nucleation of vertically extended columnar filaments with a lateral size on the order of the grains. This nucleation-controlled switching contrasts sharply with the growth-mediated dynamics characteristic of perovskite ferroelectrics and explains the abrupt, spatially localized switching behavior observed in wurtzite systems. These results establish nucleation-dominated filamentary reversal as a defining switching mechanism in Zn1-xMgxO and point towards the need for further studies to understand correlation lengths and nucleation processes across a range of grain sizes.

cond-mat.mtrl-sci↗
arXiv2026

Electromechanical Hysteresis in Phase Change Material Sb2S3

Antimony sulfide is an emerging phase change material for optical and electrical memory and computation elements. It has additionally been reported as a ferroelectric, with recent evidence from hysteresis in piezoresponse force microscopy. Here, we complete a rigorous set of piezoresponse force microscopy experiments on a congruently crystallized Sb2S3 glass-ceramic, where piezoelectric coupling should be forbidden in glassy Sb2S3. We replicate previous results and reveal that the behavior is absent in glassy Sb2S3 but show that the response originates primarily from non-piezoelectric contributions to the signal caused by an applied voltage. This hysteretic behavior in piezoresponse force microscopy is quite similar to some electrochemically active non-ferroelectric oxides, but uniquely, it appears here with a very clear spatial contrast that is decoupled from surface topography. This shows that the electromechanical signal reflects bulk-like properties and reveals differences in electrical behavior of crystalline and amorphous phases of Sb2S3.

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

Autonomous scanning probe microscopy with hypothesis learning: Exploring the physics of domain switching in ferroelectric materials

We report the development and implementation of a hypothesis learning based automated experiment, in which the microscope operating in the autonomous mode identifies the physical laws behind the material's response. Specifically, we explore the bias induced transformations that underpin the functionality of broad classes of devices and functional materials from batteries and memristors to ferroelectrics and antiferroelectrics. Optimization and design of these materials require probing the mechanisms of these transformations on the nanometer scale as a function of the broad range of control parameters such as applied potential and time, often leading to experimentally intractable scenarios. At the same time, often the behaviors of these systems are understood within potentially competing theoretical models, or hypotheses. Here, we develop a hypothesis list that covers the possible limiting scenarios for the domain growth, including thermodynamic, domain wall pinning, and screening limited. We further develop and experimentally implement the hypothesis driven automated experiment in Piezoresponse Force Microscopy, autonomously identifying the mechanisms of the bias induced domain switching. This approach can be applied for a broad range of physical and chemical experiments with relatively low dimensional control parameter space and for which the possible competing models of the system behavior that ideally cover the full range of physical eventualities are known or can be created. These include other scanning probe microscopy modalities such as force distance curve measurements and nanoindentation, as well as materials synthesis and optimization.

cond-mat.mtrl-sci↗
arXiv2024

Non-perturbative cathodoluminescence microscopy of beam-sensitive materials

Cathodoluminescence microscopy is now a well-established and powerful tool for probing the photonic properties of nanoscale materials, but in many cases, nanophotonic materials are easily damaged by the electron-beam doses necessary to achieve reasonable cathodoluminescence signal-to-noise ratios. Two-dimensional materials have proven particularly susceptible to beam-induced modifications, yielding both obstacles to high spatial-resolution measurement and opportunities for beam-induced patterning of quantum photonic systems. Here pan-sharpening techniques are applied to cathodoluminescence microscopy in order to address these challenges and experimentally demonstrate the promise of pan-sharpening for minimally-perturbative high-spatial-resolution spectrum imaging of beam-sensitive materials.

physics.optics↗
arXiv2024

Photoinduced Patterning of Oxygen Vacancies to Promote the Ferroelectric Phase of $\mathrm{Hf_{0.5}Zr_{0.5}O_2}$

Photoinduced reductions in the oxygen vacancy concentration were leveraged to increase the ferroelectric phase fraction of $\mathrm{Hf_{0.5}Zr_{0.5}O_2}$ (HZO) thin-films. Modest ($\sim 0.02-0.77~\mathrm{mJ/μm^2}$) laser doses of visible light (488 nm, 2.54 eV) spatially patterned the concentration of oxygen vacancies as monitored by photoluminescence imaging. Local, tip-based, near-field, nanoFTIR measurements showed that the photoinduced oxygen vacancy concentration reduction promoted formation of the ferroelectric phase (space group $Pca2_1$) resulting in an increase in the piezoelectric response measured by piezoresponse force microscopy. Photoinduced vacancy tailoring provides, therefore, a spatially prescriptive, post-synthesis, and low-entry method to modify phase in \hfo-based materials.

cond-mat.mtrl-sci↗
arXiv2023

Closed-Loop Electron-Beam-Induced Spectroscopy and Nanofabrication Around Individual Quantum Emitters

Color centers in diamond play a central role in the development of quantum photonic technologies, and their importance is only expected to grow in the near future. For many quantum applications, high collection efficiency from individual emitters is required, but the refractive index mismatch between diamond and air limits the optimal collection efficiency with conventional diamond device geometries. While different out-coupling methods with near-unity efficiency exist, many have yet to be realized due to current limitations in nanofabrication methods, especially for mechanically hard materials like diamond. Here, we leverage electron-beam-induced etching to modify Sn-implanted diamond quantum microchiplets containing integrated waveguides with width and thickness of 280 nm and 200 nm, respectively. This approach allows for simultaneous high-resolution imaging and modification of the host matrix with an open geometry and direct writing. When coupled with the cathodoluminescence signal generated from the electron-emitter interactions, we can monitor the enhancement of the quantum emitters in real-time with nanoscale spatial resolution. The operando measurement and manipulation of single photon emitters demonstrated here provides a new foundation for the control of emitter-cavity interactions in integrated quantum photonics.

physics.optics↗
arXiv2023

Ferroelectric domain nucleation and switching pathways in hafnium oxide

Nanoscale ferroelectrics that can be integrated into microelectronic fabrication processes are highly desirable for low-power computing and non-volatile memory devices. However, scalable novel ferroelectric materials, such as hafnium oxide (HfO2), remain in a state of development, and a clear understanding of the effects of relevant compositional and processing parameters to control their ferroelectric properties and the actual polarization switching mechanisms are still under investigation. One key fundamental knowledge gap is the polarization switching pathway in ferroelectric hafnia. To further our fundamental understanding of domain nucleation and switching, we have studied polarization switching pathways in HfO2-x thin films in real-time at the atomic scale using transmission electron microscopy. We employed differential phase contrast imaging that allows for the acquisition of both hafnium and oxygen atomic column signals and facilitates the observation of relative movement of atomic columns between both sublattices. Our results demonstrate that the switching pathway involves a transient tetragonal-like local structure, as oxygen ions shift in locations and remain within their parent hafnium polyhedra.

cond-mat.mtrl-sci↗
arXiv2023

An effective Landau-type model of Hf$_x$Zr$_{1-x}$O$_2$ thin film - graphene nanostructure

To describe the charge-polarization coupling in the nanostructure formed by a thin Hf$_x$Zr$_{1-x}$O$_2$ film with a single-layer graphene as a top electrode, we develop the "effective" Landau-Ginzburg-Devonshire model. This approach is based on the parametrization of the Landau expansion coefficients for the polar (FE) and antipolar (AFE) orderings in thin Hf$_x$Zr$_{1-x}$O$_2$ films from a limited number of polarization-field curves and hysteresis loops. The Landau expansion coefficients are nonlinearly dependent on the film thickness h and Zr/[Hf+Zr] ratio x, in contrast to h-independent and linearly x-dependent expansion coefficients of a classical Landau energy. We explain the dependence of the Landau expansion coefficients by the strong nonmonotonic dependence of the polar properties on the Hf$_x$Zr$_{1-x}$O$_2$ film thickness, grain size and surface energy. The proposed Landau free energy with five "effective" expansion coefficients, which are interpolation functions of x and h, describes the continuous transformation of polarization dependences on applied electric field and hysteresis loop shapes induced by the changes of x and h in the range 0 < x < 1 and 5 nm < h < 35 nm. Using the effective free energy, we demonstrated that the polarization of Hf$_x$Zr$_{1-x}$O$_2$ films influences strongly on the graphene conductivity, and the full correlation between the distribution of polarization and charge carriers in graphene is revealed. In accordance with our modeling, the polarization of the (5 - 25) nm thick Hf$_x$Zr$_{1-x}$O$_2$ films, which are in the ferroelectric-like or antiferroelectric-like states for the chemical compositions 0.35 < x < 0.95, determine the concentration of carriers in graphene and can control its field dependence. The result can be promising for creation of next generation Si-compatible nonvolatile memories and graphene-ferroelectric FETs.

cond-mat.mtrl-sci↗
arXiv2023

The interplay between ferroelectricity and electrochemical reactivity on the surface of binary ferroelectric Al$_x$B$_{1-x}$N

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.

cond-mat.mtrl-sci↗
arXiv2023

Bending-induced isostructural transitions in ultrathin layers of van der Waals ferrielectrics

Using Landau-Ginzburg-Devonshire (LGD) phenomenological approach we analyze the bending-induced re-distribution of electric polarization and field, elastic stresses and strains inside ultrathin layers of van der Waals ferrielectrics. We consider a CuInP2S6 (CIPS) thin layer with fixed edges and suspended central part, the bending of which is induced by external forces. The unique aspect of CIPS is the existence of two ferrielectric states, FI1 and FI2, corresponding to big and small polarization values, which arise due to the specific four-well potential of the eighth-order LGD functional. When the CIPS layer is flat, the single-domain FI1 state is stable in the central part of the layer, and the FI2 states are stable near the fixed edges. With an increase of the layer bending below the critical value, the sizes of the FI2 states near the fixed edges decreases, and the size of the FI1 region increases. When the bending exceeds the critical value, the edge FI2 states disappear being substituted by the FI1 state, but they appear abruptly near the inflection regions and expand as the bending increases. The bending-induced isostructural FI1-FI2 transition is specific for the bended van der Waals ferrielectrics described by the eighth (or higher) order LGD functional with consideration of linear and nonlinear electrostriction couplings. The isostructural transition, which is revealed in the vicinity of room temperature, can significantly reduce the coercive voltage of ferroelectric polarization reversal in CIPS nanoflakes, allowing for the curvature-engineering control of various flexible nanodevices.

cond-mat.mtrl-sci↗
arXiv2023

Disentangling stress and curvature effects in layered 2D ferroelectric CuInP2S6

Nanoscale ferroelectric 2D materials offer unique opportunity to investigate curvature and strain effects on materials functionalities. Among these, CuInP2S6 (CIPS) has attracted tremendous research interest in recent years due to combination of room temperature ferroelectricity, scalability to a few layers thickness, and unique ferrielectric properties due to coexistence of 2 polar sublattices. Here, we explore the local curvature and strain effect on the polarization in CIPS via piezoresponse force microscopy and spectroscopy. To explain the observed behaviors and decouple the curvature and strain effects in 2D CIPS, we introduce finite element Landau-Ginzburg-Devonshire model. The results show that bending induces ferrielectric domains in CIPS, and the polarization-voltage hysteresis loops differ in bending and non-bending regions. Our simulation indicates that the flexoelectric effect can affect local polarization hysteresis. These studies open a novel pathway for the fabrication of curvature-engineered nanoelectronic devices.

cond-mat.mtrl-sci↗
arXiv2023

Large Enhancements in Optical and Piezoelectric Properties in Ferroelectric Zn1-xMgxO Thin Films through Engineering Electronic and Ionic Anharmonicities

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.

cond-mat.mtrl-sci↗
arXiv2023

Learning the right channel in multimodal imaging: automated experiment in Piezoresponse Force Microscopy

We report the development and experimental implementation of the automated experiment workflows for the identification of the best predictive channel for a phenomenon of interest in spectroscopic measurements. The approach is based on the combination of ensembled deep kernel learning for probabilistic predictions and a basic reinforcement learning policy for channel selection. It allows the identification of which of the available observational channels, sampled sequentially, are most predictive of selected behaviors, and hence have the strongest correlations. We implement this approach for multimodal imaging in Piezoresponse Force Microscopy (PFM), with the behaviors of interest manifesting in piezoresponse spectroscopy. We illustrate the best predictive channel for polarization-voltage hysteresis loop and frequency-voltage hysteresis loop areas is amplitude in the model samples. The same workflow and code are universal and applicable for any multimodal imaging and local characterization methods.

cond-mat.mtrl-sci↗
arXiv2022

Exploring the microstructural origins of conductivity and hysteresis in metal halide perovskites via active learning driven automated scanning probe microscopy

Electronic transport and hysteresis in metal halide perovskites (MHPs) are key to the applications in photovoltaics, light emitting devices, and light and chemical sensors. These phenomena are strongly affected by the materials microstructure including grain boundaries, ferroic domain walls, and secondary phase inclusions. Here, we demonstrate an active machine learning framework for 'driving' an automated scanning probe microscope (SPM) to discover the microstructures responsible for specific aspects of transport behavior in MHPs. In our setup, the microscope can discover the microstructural elements that maximize the onset of conduction, hysteresis, or any other characteristic that can be derived from a set of current-voltage spectra. This approach opens new opportunities for exploring the origins of materials functionality in complex materials by SPM and can be integrated with other characterization techniques either before (prior knowledge) or after (identification of locations of interest for detail studies) functional probing.

cond-mat.mtrl-sci↗
arXiv2022

Disentangling electronic transport and hysteresis at individual grain boundaries in hybrid perovskites via automated scanning probe microscopy

Underlying the rapidly increasing photovoltaic efficiency and stability of metal halide perovskites (MHPs) is the advance in the understanding of the microstructure of polycrystalline MHP thin film. Over the past decade, intense efforts have aimed to understand the effect of microstructure on MHP properties, including chemical heterogeneity, strain disorder, phase impurity, etc. It has been found that grain and grain boundary (GB) are tightly related to lots of microscale and nanoscale behavior in MHP thin film. Atomic force microscopy (AFM) is widely used to observe grain and boundary structures in topography and subsequently to study the correlative surface potential and conductivity of these structures. For now, most AFM measurements have been performed in imaging mode to study the static behavior, in contrast, AFM spectroscopy mode allows us to investigate the dynamic behavior of materials, e.g. conductivity under sweeping voltage. However, a major limitation of AFM spectroscopy measurements is that it requests manual operation by human operators, as such only limited data can be obtained, hindering systematic investigations of these microstructures. In this work, we designed a workflow combining the conductive AFM measurement with a machine learning (ML) algorithm to systematically investigate grain boundaries in MHPs. The trained ML model can extract GBs locations from the topography image, and the workflow drives the AFM probe to each GB location to perform a current-voltage (IV) curve automatically. Then, we are able to IV curves at all GB locations, allowing us to systematically understand the property of GBs. Using this method, we discover that the GB junction points are more photoactive, while most previous works only focused on the difference between GB and grains.

cond-mat.mtrl-sci↗
arXiv2022

Ferroelectricity in Hafnia Controlled via Surface Electrochemical State

Ferroelectricity in binary oxides including hafnia and zirconia have riveted the attention of the scientific community due to highly unconventional physical mechanisms and the potential for integration of these materials into semiconductor workflows. Over the last decade, it has been argued that behaviors such as wake-up phenomena and an extreme sensitivity to electrode and processing conditions suggests that ferroelectricity in these materials is strongly coupled with additional mechanisms, with possible candidates including the ionic subsystem or strain. Here we argue that the properties of these materials emerge due to the interplay between the bulk competition between ferroelectric and structural instabilities, similar to that in classical antiferroelectrics, coupled with non-local screening mediated by the finite density of states at surfaces and internal interfaces. Via decoupling of electrochemical and electrostatic controls realized via environmental and ultra-high vacuum PFM, we show that these materials demonstrate a rich spectrum of ferroic behaviors including partial pressure- and temperature-induced transitions between FE and AFE behaviors. These behaviors are consistent with an antiferroionic model and suggest novel strategies for hafnia-based device optimization.

cond-mat.mtrl-sci↗