Search

The integration of machine learning (ML) models enhances the efficiency, affordability, and reliability of feature detection in microscopy, yet their development and applicability are hindered by the dependency on scarce and often flawed manually labeled datasets and a lack of domain awareness. We addressed these challenges by creating a physics-based synthetic image and data generator, resulting in a machine learning model that achieves comparable precision (0.86), recall (0.63), F1 scores (0.71), and engineering property predictions (R2=0.82) to a model trained on human-labeled data. We enhanced both models by using feature prediction confidence scores to derive an image-wide confidence metric, enabling simple thresholding to eliminate ambiguous and out-of-domain images resulting in performance boosts of 5-30% with a filtering-out rate of 25%. Our study demonstrates that synthetic data can eliminate human reliance in ML and provides a means for domain awareness in cases where many feature detections per image are needed.

One compelling vision of the future of materials discovery and design involves the use of machine learning (ML) models to predict materials properties and then rapidly find materials tailored for specific applications. However, realizing this vision requires both providing detailed uncertainty quantification (model prediction errors and domain of applicability) and making models readily usable. At present, it is common practice in the community to assess ML model performance only in terms of prediction accuracy (e.g., mean absolute error), while neglecting detailed uncertainty quantification and robust model accessibility and usability. Here, we demonstrate a practical method for realizing both uncertainty and accessibility features with a large set of models. We develop random forest ML models for 33 materials properties spanning an array of data sources (computational and experimental) and property types (electrical, mechanical, thermodynamic, etc.). All models have calibrated ensemble error bars to quantify prediction uncertainty and domain of applicability guidance enabled by kernel-density-estimate-based feature distance measures. All data and models are publicly hosted on the Garden-AI infrastructure, which provides an easy-to-use, persistent interface for model dissemination that permits models to be invoked with only a few lines of Python code. We demonstrate the power of this approach by using our models to conduct a fully ML-based materials discovery exercise to search for new stable, highly active perovskite oxide catalyst materials.

Oxygen ion conductors are crucial for enhancing the efficiency of various clean energy technologies, including fuel cells, batteries, electrolyzers, membranes, sensors, and more. In this study, LaBi2O4Cl is identified as an ultra-fast oxygen conductor from the MBi2O4X (M=rare-earth element, X=halogen element) family, discovered by a structure-similarity analysis of >60k oxygen-containing compounds. Ab initio studies reveal that LaBi2O4Cl has an ultra-low migration barrier of 0.1 eV for oxygen vacancy, significantly lower than 0.6-0.8 eV for interstitial oxygen. Frenkel pairs are the dominant defects in intrinsic LaBi2O4Cl, facilitating notable oxygen diffusion primarily through vacancies at higher temperatures. LaBi2O4Cl with extrinsic oxygen vacancies (2.8%) exhibits a conductivity of 0.3 S/cm at 25{\deg}C, maintains a 0.1 eV diffusion barrier up to 1100{\deg}C, and transitions from extrinsic to mixed extrinsic and intrinsic behavior as the Frenkel pair concentration increases at higher temperatures. Experimental results on synthesized LaBi2O4Cl and Sr-doped LaBi2O4Cl demonstrate comparable or higher oxygen conductivity than YSZ and LSGM below 400 {\deg}C, with lower activation energies. Further experimental optimization of LaBi2O4Cl, including aliovalent doping and microstructure refinement, could significantly enhance its performance and efficiency, facilitating fast oxygen conduction approaching room temperature.

Knowledge of the domain of applicability of a machine learning model is essential to ensuring accurate and reliable model predictions. In this work, we develop a new approach of assessing model domain and demonstrate that our approach provides accurate and meaningful designation of in-domain versus out-of-domain when applied across multiple model types and material property data sets. Our approach assesses the distance between a test and training data point in feature space by using kernel density estimation and shows that this distance provides an effective tool for domain determination. We show that chemical groups considered unrelated based on established chemical knowledge exhibit significant dissimilarities by our measure. We also show that high measures of dissimilarity are associated with poor model performance (i.e., high residual magnitudes) and poor estimates of model uncertainty (i.e., unreliable uncertainty estimation). Automated tools are provided to enable researchers to establish acceptable dissimilarity thresholds to identify whether new predictions of their own machine learning models are in-domain versus out-of-domain., Comment: 43 pages, 34 figures, journal submission

Perovskite SrVO$_3$ has recently been proposed as a novel electron emission cathode material. Density functional theory (DFT) calculations suggest multiple low work function surfaces and recent experimental efforts have consistently demonstrated effective work functions of ~2.7 eV for polycrystalline samples, both results suggesting, but not directly confirming, some fraction of even lower work function surface is present. In this work, thermionic electron emission microscopy (ThEEM) and high-field ultraviolet photoemission spectroscopy are used to study the local work function distribution and measure the work function of a partially-oriented-(110)-SrVO$_3$ perovskite oxide cathode surface. Our results show direct evidence of low work function patches of about 2.1 eV on the cathode surface, with corresponding onset of observable thermionic emission at 750 $^o$C. We hypothesize that, in our ThEEM experiments, the high applied electric field suppresses the patch field effect, enabling the direct measurement of local work functions. This measured work function of 2.1 eV is comparable to the previous DFT-calculated work function value of the SrVO-terminated (110) SrVO$_3$ surface (2.3 eV) and SrO terminated (100) surface (1.9 eV). The measured 2.1 eV value is also much lower than the work function for the (001) LaB$_6$ single crystal cathode (~2.7 eV) and comparable to the effective work function of B-type dispenser cathodes (~2.1 eV). If SrVO$_3$ thermionic emitters can be engineered to access domains of this low 2.1 eV work function, they have potential to significantly improve thermionic emitter-based technologies.

Discovering new materials that efficiently catalyze the oxygen reduction and evolution reactions is critical for facilitating the widespread adoption of solid oxide fuel cell and electrolyzer (SOFC/SOEC) technologies. Here, we develop machine learning (ML) models to predict perovskite catalytic properties critical for SOFC/SOEC applications, including oxygen surface exchange, oxygen diffusivity, and area specific resistance (ASR). The models are based on trivial-to-calculate elemental features and are more accurate and dramatically faster than the best models based on ab initio-derived features, potentially eliminating the need for ab initio calculations in descriptor-based screening. Our model of ASR enables temperature-dependent predictions, has well calibrated uncertainty estimates and online accessibility. Use of temporal cross-validation reveals our model to be effective at discovering new promising materials prior to their initial discovery, demonstrating our model can make meaningful predictions. Using the SHapley Additive ExPlanations (SHAP) approach, we provide detailed discussion of different approaches of model featurization for ML property prediction. Finally, we use our model to screen more than 19 million perovskites to develop a list of promising cheap, earth-abundant, stable, and high performing materials, and find some top materials contain mixtures of less-explored elements (e.g., K, Bi, Y, Ni, Cu) worth exploring in more detail.

The discovery and design of new materials which can efficiently catalyze the oxygen reduction and evolution reactions at reduced temperatures is important for facilitating the widespread adoption of fuel cell and electrolyzer technologies. Numerous studies have produced correlations between catalytic properties, such as oxygen surface exchange or electrode area specific resistance (ASR), and properties of the catalyst material. However, correlations have historically been limited in scope (e.g., using only a few materials or at a single temperature) and it has been difficult to provide detailed assessments of their robustness. Here, we assess the ability of the O p-band center electronic structure descriptor, obtained from density functional theory (DFT) calculations, to correlate with oxygen surface exchange rates, diffusivities, and area specific resistances for a large database of perovskite oxide catalytic properties. By data mining the literature, we obtain 747 catalytic property value data points spanning 299 unique perovskite compositions from 313 studies. We assess linear correlations of each property with the O p-band center and find generally modest correlations that are qualitatively useful (prediction mean absolute errors of about 0.5 log units are typical), where the correlations are improved at higher temperatures (e.g., 800 {\deg}C vs. 500 {\deg}C) and significantly improve when considering fits to the subset of materials which have multiple independent measurements. These findings suggest that the spread of property data is significantly influenced by experimental uncertainty, and subsequent measurements of additional materials will likely improve the O p-band center correlations.

Thermionic electron emission cathodes are critical components of various high power and high frequency vacuum electronic devices, electron microscopes, e-beam lithographic devices, and thermionic energy converters, which all demand an efficient and long-lasting low work function cathode. Single phase, polycrystalline perovskite oxide SrVO$_3$, with its intrinsic low effective work function and facile synthesis process, is a promising cathode candidate, where previous works have shown evidence of an effective work function as low as 2.3 eV. However, assessment of the stability over time under conditions relevant for operation and the related interplay of evolving surface chemistry with emission performance are still missing, and necessary for understanding how to best prepare, process and operate SrVO$_3$ cathodes. In this work, we study the vacuum activation process of SrVO$_3$ and find it has promising emission stability over 15 days of continuous high temperature operation. We find that SrVO$_3$ shows surface Sr and O segregation during operation, which we hypothesize is needed to create a positive surface dipole, leading to low effective work function. Emission repeatability from cyclic heating and cooling suggests the promising stability of the low effective work function surface, and additional observations of drift-free emission during one hour of continuous emission testing at high temperature further demonstrates its excellent performance stability.

Materials discovery and design typically proceeds through iterative evaluation (both experimental and computational) to obtain data, generally targeting improvement of one or more properties under one or more constraints (e.g., time or budget). However, there can be great variation in the quality and cost of different data, and when they are mixed together in what we here call multifidelity data the optimal approaches to their utilization are not established. It is therefore important to develop strategies to acquire and use multifidelity data to realize the most efficient iterative materials exploration. In this work, we assess the impact of using multifidelity data through mock demonstration of designing solar cell materials, using the electronic bandgap as the target property. We propose a new approach of using multifidelity data through leveraging machine learning models of both low- and high-fidelity data, where using predicted low-fidelity data as an input feature in the high-fidelity model can improve the impact of a multifidelity data approach. We show how tradeoffs of low- versus high-fidelity measurement cost and acquisition can impact the materials discovery process, and find that the use of multifidelity data has maximal impact on the materials discovery campaign when approximately five low-fidelity measurements per high-fidelity measurement are performed, and when the cost of low-fidelity measurements is approximately 5% or less than that of high-fidelity measurements. This work provides practical guidance and useful qualitative measures for improving materials discovery campaigns that involve multifidelity data.

An essential aspect of extending safe operation of the active nuclear reactors is understanding and predicting the embrittlement that occurs in the steels that make up the Reactor pressure vessel (RPV). In this work we integrate state of the art machine learning methods using ensembles of neural networks with unprecedented data collection and integration to develop a new model for RPV steel embrittlement. The new model has multiple improvements over previous machine learning and hand-tuned efforts, including greater accuracy (e.g., at high-fluence relevant for extending the life of present reactors), wider domain of applicability (e.g., including a wide-range of compositions), uncertainty quantification, and online accessibility for easy use by the community. These improvements provide a model with significant new capabilities, including the ability to easily and accurately explore compositions, flux, and fluence effects on RPV steel embrittlement for the first time. Furthermore, our detailed comparisons show our approach improves on the leading American Society for Testing and Materials (ASTM) E900-15 standard model for RPV embrittlement on every metric we assessed, demonstrating the efficacy of machine learning approaches for this type of highly demanding materials property prediction.

New highly oxygen-active materials may enhance many energy-related technologies by enabling efficient oxygen-ion transport at lower temperatures, e.g., below 400 Celsius. Interstitial oxygen conductors have the potential to realize such performance but have received far less attention than vacancy-mediated conductors. Here, we combine physically-motivated structure and property descriptors, ab initio simulations, and experiments to demonstrate an approach to discover new fast interstitial oxygen conductors. Multiple new families were found which adopt completely different structures from known oxygen conductors. From these families, we synthesized and studied oxygen kinetics in La4Mn5Si4O22+d (LMS), a representative member of perrierite/chevkinite family. We found LMS has higher oxygen ionic conductivity than the widely used yttria-stabilized ZrO2, and among the highest surface oxygen exchange rates at intermediate temperature of known materials. The fast oxygen kinetics is the result of simultaneously active interstitial and interstitialcy diffusion pathways. This work developed and demonstrated a powerful approach for discovering new families of interstitial oxygen conductors and suggests many more such materials remain to be discovered.

Accurately quantifying swelling of alloys that have undergone irradiation is essential for understanding alloy performance in a nuclear reactor and critical for the safe and reliable operation of reactor facilities. However, typical practice is for radiation-induced defects in electron microscopy images of alloys to be manually quantified by domain-expert researchers. Here, we employ an end-to-end deep learning approach using the Mask Regional Convolutional Neural Network (Mask R-CNN) model to detect and quantify nanoscale cavities in irradiated alloys. We have assembled the largest database of labeled cavity images to date, which includes 400 images, >34k discrete cavities, and numerous alloy compositions and irradiation conditions. We have evaluated both statistical (precision, recall, and F1 scores) and materials property-centric (cavity size, density, and swelling) metrics of model performance, and performed in-depth analysis of materials swelling assessments. We find our model gives assessments of material swelling with an average (standard deviation) swelling mean absolute error based on random leave-out cross-validation of 0.30 (0.03) percent swelling. This result demonstrates our approach can accurately provide swelling metrics on a per-image and per-condition basis, which can provide helpful insight into material design (e.g., alloy refinement) and impact of service conditions (e.g., temperature, irradiation dose) on swelling. Finally, we find there are cases of test images with poor statistical metrics, but small errors in swelling, pointing to the need for moving beyond traditional classification-based metrics to evaluate object detection models in the context of materials domain applications.

Quantifying charge-state transition energy levels of impurities in semiconductors is critical to understanding and engineering their optoelectronic properties for applications ranging from solar photovoltaics to infrared lasers. While these transition levels can be measured and calculated accurately, such efforts are time-consuming and more rapid prediction methods would be beneficial. Here, we significantly reduce the time typically required to predict impurity transition levels using multi-fidelity datasets and a machine learning approach employing features based on elemental properties and impurity positions. We use transition levels obtained from low-fidelity (i.e., local-density approximation or generalized gradient approximation) density functional theory (DFT) calculations, corrected using a recently proposed modified band alignment scheme, which well-approximates transition levels from high-fidelity DFT (i.e., hybrid HSE06). The model fit to the large multi-fidelity database shows improved accuracy compared to the models trained on the more limited high-fidelity values. Crucially, in our approach, when using the multi-fidelity data, high-fidelity values are not required for model training, significantly reducing the computational cost required for training the model. Our machine learning model of transition levels has a root mean squared (mean absolute) error of 0.36 (0.27) eV vs high-fidelity hybrid functional values when averaged over 14 semiconductor systems from the II-VI and III-V families. As a guide for use on other systems, we assessed the model on simulated data to show the expected accuracy level as a function of bandgap for new materials of interest. Finally, we use the model to predict a complete space of impurity charge-state transition levels in all zinc blende III-V and II-VI systems.

In a current density versus temperature (J-T) (Miram) curve in thermionic electron emission, experimental measurements demonstrate there is a smooth transition between the exponential region and the saturated emission regions, which is sometimes referred to as the "roll-off" or "Miram curve knee". The shape of the Miram curve knee is an important figure of merit for thermionic vacuum cathodes. Specifically, cathodes with a sharp Miram curve knee at low temperature with a flat saturated emission current are typically preferred. Our previous work on modeling nonuniform thermionic emission revealed that the space charge effect and patch field effect are key pieces of physics which impact the shape of the Miram curve knee. This work provides a more complete understanding of the physical factors connecting these physical effects and their relative impact on the shape of the knee, including the smoothness, the temperature, and the flatness of the saturated emission current density. For our analyses, we use a periodic, equal-width striped ("zebra crossing") work function distribution as a model system and illustrate how the space charge and patch field effects restrict the emission current density near the Miram curve knee. The results indicate there are three main physical parameters which significantly impact the shape of the Miram curve. Such physical knowledge directly connects the patch size, work function values, anode-cathode voltage, and anode-cathode gap distance to the shape of the Miram curve, providing new understanding and a guide to the design of thermionic cathodes used as electron sources in vacuum electronic devices (VEDs).

This paper provides an accurate theoretical defect energy database for pure and Bi-containing III-V (III-V:Bi) materials and investigates efficient methods for high-throughput defect calculations based on corrections of results obtained with local and semi-local functionals. Point defects as well as nearest-neighbor and second-nearest-neighbor pair defects were investigated in charge states ranging from -5 to 5. Ga-V:Bi systems (GaP:Bi, GaAs:Bi, and GaSb:Bi) were thoroughly investigated with significantly slower, higher fidelity hybrid Heyd-Scuseria-Ernzerhof (HSE) and significantly faster, lower fidelity local density approximation (LDA) calculations. In both approaches spurious electrostatic interactions were corrected with the Freysoldt correction. The results were verified against available experimental results and used to assess the accuracy of a previous band alignment correction. Here, a modified band alignment method is proposed in order to better predict the HSE values from the LDA ones. The proposed method allows prediction of defect energies with values that approximate those from the HSE functional at the computational cost of LDA (about 20x faster for the systems studied here). Tests of selected point defects in In-V:Bi materials resulted in corrected LDA values having a mean absolute error (MAE)=0.175 eV for defect levels vs. HSE. The method was further verified on an external database of defects and impurities in CdX (X=S, Se, Te) systems, yielding a MAE=0.194 eV. These tests demonstrate the correction to be sufficient for qualitative and semi-quantitative predictions, and may suggest transferability to many semiconductor systems without significant loss in accuracy. Properties of the remaining In-V:Bi defects and all Al-V:Bi defects were predicted with the use of the modified band alignment method.

Experimental observations of thermionic electron emission demonstrate a smooth transition between TL and FSCL regions of the emitted-current-density-versus-temperature (J-T) (Miram) curve and the emitted-current-density-versus-voltage (J-V) curve. Knowledge of the temperature and shape of the TL-FSCL transition is important in evaluating the thermionic electron emission performance of cathodes, including predicting the lifetime. However, there have been no first-principles physics-based models that can predict the smooth TL-FSCL transition region for real thermionic cathodes without applying physically difficult to justify a priori assumptions or empirical phenomenological equations. Previous work detailing the nonuniform thermionic emission found that the effects of 3-D space charge, patch fields, and Schottky barrier lowering can lead to a smooth TL-FSCL transition region from a model thermionic cathode surface with a checkerboard spatial distribution of work function values. In this work, we construct a physics-based nonuniform emission model for commercial dispenser cathodes for the first time. This emission model is obtained by incorporating the cathode surface grain orientation via electron backscatter diffraction (EBSD) and the facet-orientation-specific work function values from density functional theory (DFT) calculations. The model enables construction of two-dimensional emitted current density maps of the cathode surface and corresponding J-T and J-V curves. The predicted emission curves show excellent agreement with experiment, not only in TL and FSCL regions but, crucially, also in the TL-FSCL transition region. This model improves the understanding on the relationship between thermionic emission and cathode microstructure, which is beneficial to the design of vacuum electronic devices.

In this work, we perform semantic segmentation of multiple defect types in electron microscopy images of irradiated FeCrAl alloys using a deep learning Mask Regional Convolutional Neural Network (Mask R-CNN) model. We conduct an in-depth analysis of key model performance statistics, with a focus on quantities such as predicted distributions of defect shapes, defect sizes, and defect areal densities relevant to informing modeling and understanding of irradiated Fe-based materials properties. To better understand the performance and present limitations of the model, we provide examples of useful evaluation tests which include a suite of random splits, and dataset size-dependent and domain-targeted cross validation tests. Overall, we find that the current model is a fast, effective tool for automatically characterizing and quantifying multiple defect types in microscopy images, with a level of accuracy on par with human domain expert labelers. More specifically, the model can achieve average defect identification F1 scores as high as 0.8, and, based on random cross validation, have low overall average (+/- standard deviation) defect size and density percentage errors of 7.3 (+/- 3.8)% and 12.7 (+/- 5.3)%, respectively. Further, our model predicts the expected material hardening to within 10-20 MPa (about 10% of total hardening), which is about the same error level as experiments. Our targeted evaluation tests also suggest the best path toward improving future models is not expanding existing databases with more labeled images but instead data additions that target weak points of the model domain, such as images from different microscopes, imaging conditions, irradiation environments, and alloy types. Finally, we discuss the first phase of an effort to provide an easy-to-use, open-source object detection tool to the broader community for identifying defects in new images.

Materials with low work functions are critical for an array of applications requiring the facile removal or efficient transport of electrons through a device. Perovskite oxides are a promising class of materials for finding low work functions, and here we target applications in thermionic and field electron emission. Perovskites have highly malleable compositions which enable tunable work function values over a wide range, robust stability at high temperatures, and high electronic conductivities. In this work, we screened over 2900 perovskite oxides in search of stable, conductive, low-work-function materials using Density Functional Theory (DFT) methods. Our work provides insight into the materials chemistry governing the work function value of a perovskite, where materials with barely filled d bands possess the lowest work functions. Our screening has resulted in a total of seven promising compounds, such as BaMoO3 and SrNb0.75Co0.25O3 with work functions of 1.1 eV and 1.5 eV, respectively. These promising materials and others presented in this study may find use as low work function electron emitters in high power vacuum electronic and thermionic energy conversion devices. Moreover, the database of calculated work functions and materials chemistry trends governing the value of the work function may aid in the engineering of perovskite heterojunction devices.

LaB6 has been used as a commercial electron emitter for decades. Despite the large number of studies on the work function of LaB6, there is no comprehensive understanding of work function trends in the hexaboride materials family. In this study, we use Density Functional Theory (DFT) calculations to calculated trends of rare earth hexaboride work function and rationalize these trends based on the electronegativity of the metal element. We predict that alloying LaB6 with Ba can further lower the work function by ~0.2 eV. Interestingly, we find that alloyed (La, Ba)B6 can have lower work functions than either LaB6 or BaB6, benefitting from an enhanced surface dipole due to metal element size mismatch. In addition to hexaborides we also investigate work function trends of similar materials families, namely tetraborides and transition metal nitrides, which, like hexaborides, are electrically conductive and refractory and thus may also be promising materials for electron emission applications. We find that tetraborides consistently have higher work functions than their hexaboride analogues as the tetraborides having less ionic bonding and smaller positive surface dipoles. Finally, we find that HfN has a low work function of about 2.2 eV, making HfN a potentially promising new electron emitter material.

Obtaining accurate estimates of machine learning model uncertainties on newly predicted data is essential for understanding the accuracy of the model and whether its predictions can be trusted. A common approach to such uncertainty quantification is to estimate the variance from an ensemble of models, which are often generated by the generally applicable bootstrap method. In this work, we demonstrate that the direct bootstrap ensemble standard deviation is not an accurate estimate of uncertainty and propose a calibration method to dramatically improve its accuracy. We demonstrate the effectiveness of this calibration method for both synthetic data and physical datasets from the field of Materials Science and Engineering. The approach is motivated by applications in physical and biological science but is quite general and should be applicable for uncertainty quantification in a wide range of machine learning regression models.

SrVO3 thin films with a high figure of merit for applications as transparent conductors were crystallized from amorphous layers using solid phase epitaxy (SPE). Epitaxial SrVO3 films crystallized on SrTiO3 using SPE exhibit a room temperature resistivity of 2.5 x 10-5 Ohms cm, a residual resistivity ratio of 3.8, and visible light transmission above 0.5 for a 60 nm-thick film. SrVO3 layers were deposited at room temperature using radio-frequency sputtering in an amorphous form and subsequently crystallized by heating in controlled gas environment. The lattice parameters and mosaic angular width of x-ray reflections from the crystallized films are consistent with partial relaxation of the strain resulting from the epitaxial mismatch between SrVO3 and SrTiO3. A reflection high-energy electron diffraction study of the kinetics of SPE indicates that crystallization occurs via the thermally activated propagation of the crystalline/amorphous interface, similar to SPE phenomena in other perovskite oxides. Thermodynamic calculations based on density functional theory predict the temperature and oxygen partial pressure conditions required to produce the SrVO3 phase and are consistent with the experiments. The separate control of deposition and crystallization conditions in SPE presents new possibilities for the crystallization of transparent conductors in complex geometries and over large areas., Comment: Keywords: epitaxial transparent conducting oxides, solid-phase epitaxy, strontium vanadate, phase selection in oxide synthesis

Experimental observations have long-established that there exists a smooth roll-off or knee transition between the temperature-limited (TL) and full-space-charge-limited (FSCL) emission regions of the emission current density-temperature J-T (Miram) curve, or the emission current density-voltage J-V curve for a thermionic emission cathode. In this paper, we demonstrate that this experimentally observed smooth transition does not require frequently used a priori assumptions of a continuous distribution of work functions on the cathode surface. Instead, we find the smooth transition arises as a natural consequence of the physics of nonuniform thermionic emission from a spatially heterogeneous cathode surface. We obtain this smooth transition for both J-T and J-V curves using a predictive nonuniform thermionic emission model that includes 3-D space charge, patch fields (electrostatic potential nonuniformity on the cathode surface based on local work function values), and Schottky barrier lowering physics and illustrate that a smooth knee can arise from a thermionic cathode surface with as few as two discrete work function values. Importantly, we find that the inclusion of patch field effects is crucial for obtaining accurate J-T and J-V curves, and the further inclusion of Schottky barrier lowering is needed for accurate J-V curves. This finding, and the emission model provided in this paper have important implications for modeling electron emission from realistic, heterogeneous surfaces. Such modeling is important for improved understanding of the interplay of emission physics, cathode materials engineering, and design of numerous devices employing electron emission cathodes., Comment: IEEE Transactions on Electron Devices (2021)

Advances in machine learning have impacted myriad areas of materials science, ranging from the discovery of novel materials to the improvement of molecular simulations, with likely many more important developments to come. Given the rapid changes in this field, it is challenging to understand both the breadth of opportunities as well as best practices for their use. In this review, we address aspects of both problems by providing an overview of the areas where machine learning has recently had significant impact in materials science, and then provide a more detailed discussion on determining the accuracy and domain of applicability of some common types of machine learning models. Finally, we discuss some opportunities and challenges for the materials community to fully utilize the capabilities of machine learning.

The electronic, magnetic, thermoelectric, and topological properties of Heusler compounds (composition $XYZ$ or $X_2 YZ$) are highly sensitive to stoichiometry and defects. Here we establish the existence and experimentally map the bounds of a \textit{semi} adsorption-controlled growth window for semiconducting half Heusler FeVSb films, grown by molecular beam epitaxy (MBE). We show that due to the high volatility of Sb, the Sb stoichiometry is self-limiting for a finite range of growth temperatures and Sb fluxes, similar to the growth of III-V semiconductors such as GaSb and GaAs. Films grown within this window are nearly structurally indistinguishable by X-ray diffraction (XRD) and reflection high energy electron diffraction (RHEED). The highest electron mobility and lowest background carrier density are obtained towards the Sb-rich bound of the window, suggesting that Sb-vacancies may be a common defect. Similar \textit{semi} adsorption-controlled bounds are expected for other ternary intermetallics that contain a volatile species $Z=$\{Sb, As, Bi\}, e.g., CoTiSb, LuPtSb, GdPtBi, and NiMnSb. However, outstanding challenges remain in controlling the remaining Fe/V ($X/Y$) transition metal stoichiometry.

As data science and machine learning methods are taking on an increasingly important role in the materials research community, there is a need for the development of machine learning software tools that are easy to use (even for nonexperts with no programming ability), provide flexible access to the most important algorithms, and codify best practices of machine learning model development and evaluation. Here, we introduce the Materials Simulation Toolkit for Machine Learning (MAST-ML), an open source Python-based software package designed to broaden and accelerate the use of machine learning in materials science research. MAST-ML provides predefined routines for many input setup, model fitting, and post-analysis tasks, as well as a simple structure for executing a multi-step machine learning model workflow. In this paper, we describe how MAST-ML is used to streamline and accelerate the execution of machine learning problems. We walk through how to acquire and run MAST-ML, demonstrate how to execute different components of a supervised machine learning workflow via a customized input file, and showcase a number of features and analyses conducted automatically during a MAST-ML run. Further, we demonstrate the utility of MAST-ML by showcasing examples of recent materials informatics studies which used MAST-ML to formulate and evaluate various machine learning models for an array of materials applications. Finally, we lay out a vision of how MAST-ML, together with complementary software packages and emerging cyberinfrastructure, can advance the rapidly growing field of materials informatics, with a focus on producing machine learning models easily, reproducibly, and in a manner that facilitates model evolution and improvement in the future.

The effective charge of an element is a parameter characterizing the electromgration effect, which can determine the reliability of interconnection in electronic technologies. In this work, machine learning approaches were employed to model the effective charge (z*) as a linear function of physically meaningful elemental properties. Average 5-fold (leave-out-alloy-group) cross-validation yielded root-mean-square-error divided by whole data set standard deviation (RMSE/$\sigma$) values of 0.37 $\pm$ 0.01 (0.22 $\pm$ 0.18), respectively, and $R^2$ values of 0.86. Extrapolation to z* of totally new alloys showed limited but potentially useful predictive ability. The model was used in predicting z* for technologically relevant host-impurity pairs., Comment: 9 pages, 5 figures

Two critical limitations of organic-inorganic lead halide perovskite materials for solar cells are their poor stability in humid environments and inclusion of toxic lead. In this study, high-throughput density functional theory (DFT) methods are used to computationally model and screen 1845 halide perovskites in search of new materials without these limitations that are promising for solar cell applications. This study focuses on finding materials that are comprised of nontoxic elements, stable in a humid operating environment, and have an optimal bandgap for one of single junction, tandem Si-perovskite, or quantum dot-based solar cells. Single junction materials are also screened on predicted single junction photovoltaic (PV) efficiencies exceeding 22.7%, which is the current highest reported PV efficiency for halide perovskites. Generally, these methods qualitatively reproduce the properties of known promising nontoxic halide perovskites that have either been experimentally evaluated or predicted from theory. From a set of 1845 materials, 15 materials pass all screening criteria for single junction cell applications, 13 of which have not been previously investigated, such as (CH3NH3)0.75Cs0.25SnI3, ((NH2)2CH)Ag0.5Sb0.5Br3, CsMn0.875Fe0.125I3, ((CH3)2NH2)Ag0.5Bi0.5I3, and ((NH2)2CH)0.5Rb0.5SnI3. These materials, together with others predicted in this study, may be promising candidate materials for stable, highly efficient, and non-toxic perovskite-based solar cells.

Electronic structure descriptors are computationally efficient quantities used to construct qualitative correlations for a variety of properties. In particular, the oxygen p-band center has been used to guide material discovery and fundamental understanding of an array of perovskite compounds for use in catalyzing the oxygen reduction and evolution reactions. However, an assessment of the effectiveness of the oxygen p-band center at predicting key measures of perovskite catalytic activity has not been made, and would be highly beneficial to guide future predictions and codify best practices. Here, we have used Density Functional Theory at the PBE, PBEsol, PBE+U, SCAN and HSE06 levels to assess the correlations of numerous measures of catalytic performance for a series of technologically relevant perovskite oxides, using the bulk oxygen p-band center as an electronic structure descriptor. We have analyzed correlations of the calculated oxygen p-band center for all considered functionals with the experimentally measured X-ray emission spectroscopy oxygen p-band center and multiple measures of catalytic activity, including high temperature oxygen reduction surface exchange rates, aqueous oxygen evolution current densities, and binding energies of oxygen evolution intermediate species. Our results show that the best correlations for all measures of catalytic activity considered here are made with PBE-level calculations, with strong observed linear correlations with the bulk oxygen p-band center (R2 = 0.81-0.87). This study shows that strong linear correlations between numerous important measures of catalytic activity and the oxygen p-band bulk descriptor can be obtained under a consistent computational framework, and these correlations can serve as a guide for future experiments and simulations for development of perovskite and related oxide catalysts.

The development of Ruddlesden-Popper (RP) oxides as oxygen exchange and transport materials will benefit from mechanistic understanding of how oxygen transports through these materials. Using Density Functional Theory, we found there are two distinct oxygen interstitial diffusion mechanisms involving two different oxygen interstitial species that can be active in La2-xSrxNiO4+delta, and, we believe, in hyperstoichiometric RP oxides in general. The first mechanism is the previously proposed interstitialcy-mediated mechanism, which consists of diffusing oxide interstitials. The second mechanism is newly discovered in this work, and consists of both oxide and peroxide interstitial species. This mechanism exhibits a similar or possibly lower migration barrier than the interstitialcy mechanism for high oxidation states. Which mechanism contributes to the oxygen interstitial diffusion is the result of the change in relative stability between the oxide interstitial and peroxide interstitial. The stability of the oxide and peroxide, and the competition between the two oxygen diffusion mechanisms, is sensitive to the overall oxidation state of the system. Therefore, the oxygen diffusion mechanism is a function of the material composition, oxygen off-stoichiometry, operating temperature and oxygen partial pressure. We also examined the effect of epitaxial strain on both oxygen diffusion mechanisms, and found that tensile and compressive epitaxial strain of up to 2% had less than 100 meV/(% strain) effects on oxygen interstitial formation, migration, and activation energies, and that total achievable activation energy reductions are likely less than 100 meV for -2% to +2% epitaxial strain. The presented understanding of factors governing interstitial oxygen diffusion has significant implications for the engineering of RP oxides in numerous alternative energy technologies.

In this work we developed a practical and general modeling approach for thermal conductivity of metals and metal alloys that integrates ab initio and semiempirical physics-based models to maximize the strengths of both techniques. The approach supports creation of highly accurate, mechanistic, and extensible thermal conductivity modeling of alloys. The model was demonstrated on {\alpha}-U and U-rich U-Zr and U-Mo alloys, which are potential fuels for advanced nuclear reactors. The safe use of U-based fuels requires quantitative understanding of thermal transport characteristics of the fuel. The model incorporated both phonon and electron contributions, displayed good agreement with experimental data over a wide temperature range, and provided insight into the different physical factors that govern the thermal conductivity under different temperatures. This model is general enough to incorporate more complex effects like additional alloying species, defects, transmutation products, and noble gas bubbles to predict the behavior of complex metallic alloys like U-alloy fuel systems under burnup.

Perovskite materials have become ubiquitous in many technologically relevant applications, ranging from catalysts in solid oxide fuel cells to light absorbing layers in solar photovoltaics. The thermodynamic phase stability is a key parameter that broadly governs whether the material is expected to be synthesizable, and whether it may degrade under certain operating conditions. Phase stability can be calculated using Density Functional Theory (DFT), but the significant computational cost makes such calculation potentially prohibitive when screening large numbers of possible compounds. In this work, we developed machine learning models to predict the thermodynamic phase stability of perovskite oxides using a dataset of more than 1900 DFT-calculated perovskite oxide energies. The phase stability was determined using convex hull analysis, with the energy above the convex hull (Ehull) providing a direct measure of the stability. We generated a set of 791 features based on elemental property data to correlate with the Ehull value of each perovskite compound. For classification, the extra trees algorithm achieved the best prediction accuracy of 0.93 (+/- 0.02), with an F1 score of 0.88 (+/- 0.03). For regression, leave-out 20% cross-validation tests with kernel ridge regression achieved the minimal root mean square error (RMSE) of 28.5 (+/- 7.5) meV/atom between cross-validation predicted Ehull values and DFT calculations, with the mean absolute error (MAE) in cross-validation energies of 16.7 (+/- 2.3) meV/atom. We further validated our model by predicting the stability of compounds not present in the training set and demonstrated our machine learning models are a fast and effective means of obtaining qualitatively useful guidance for a wide-range of perovskite oxide stability, potentially impacting materials design choices in a variety of technological applications., Comment: 32 pages, 6 figures, 5 tables

Critical to the development of improved solid oxide fuel cell (SOFC) technology are novel compounds with high oxygen reduction reaction (ORR) catalytic activity and robust stability under cathode operating conditions. Approximately 2145 distinct perovskite compositions are screened for potential use as high activity, stable SOFC cathodes, and it is verified that the screening methodology qualitatively reproduces the experimental activity, stability, and conduction properties of well-studied cathode materials. The calculated oxygen p-band center is used as a first principle-based descriptor of the surface exchange coefficient (k*), which in turn correlates with cathode ORR activity. Convex hull analysis is used under operating conditions in the presence of oxygen, hydrogen, and water vapor to determine thermodynamic stability. This search has yielded 52 potential cathode materials with good predicted stability in typical SOFC operating conditions and predicted k* on par with leading ORR perovskite catalysts. The established trends in predicted k* and stability are used to suggest methods of improving the performance of known promising compounds. The material design strategies and new materials discovered in the computational search help enable the development of high activity, stable compounds for use in future solid oxide fuel cells and related applications.

The slow kinetics of the oxygen reduction reaction (ORR) is one of the key challenges in developing high performance energy devices, such as solid oxide fuel cells. Straining a film by growing on a lattice-mismatched substrate has been a conventional approach to enhance the ORR activity. However, due to the limited choice of electrolyte substrates to alter the degree of strain, a systematic study in various materials has been a challenge. Here, we explore the strain modulation of the ORR kinetics by growing epitaxial La0.6Sr0.4CoO3-{\delta} (LSCO) films on yttria-stabilized zirconia substrates with the film thickness below and above the critical thickness for strain relaxation. Two orders of magnitude higher ORR kinetics is achieved in an ultra-thin film with ~0.8% tensile strain as compared to unstrained films. Time-of-flight secondary ion mass spectrometry depth profiling confirms that the Sr surface segregation is not responsible for the enhanced ORR in strained films. We attribute this enhancement of ORR kinetics to the increase in oxygen vacancy concentration in the tensile-strained LSCO film owing to the reduced activation barrier for oxygen surface exchange kinetics. Density functional theory calculations reveal an upshift of the oxygen 2p-band center relative to the Fermi level by tensile strain, indicating the origin of the enhanced ORR kinetics.

Materials that exhibit a low work function and therefore easily emit electrons into vacuum form the basis of electronic devices used in applications ranging from satellite communications to thermionic energy conversion. W-Ba-O is the canonical materials system that functions as the thermionic electron emitter used commercially in a range of high power electron devices. However, the work functions, surface stability, and kinetic characteristics of a polycrystalline W emitter surface are still not well understood or characterized. In this study, we examined the work function and surface stability of the eight lowest index surfaces of the W-Ba-O system using Density Functional Theory methods. We found that under the typical thermionic cathode operating conditions of high temperature and low oxygen partial pressure, the most stable surface adsorbates are Ba-O species with compositions in the range of Ba0.125O to Ba0.25O per surface W atom, with O passivating all dangling W bonds and Ba creating work function-lowering surface dipoles. Wulff construction analysis reveals that the presence of O and Ba significantly alters the surface energetics and changes the proportions of surface facets present under equilibrium conditions. Analysis of previously published data on W sintering kinetics suggests that fine W particles in the size range of 100-500 nm may be at or near equilibrium during cathode synthesis, and thus may exhibit surface orientation fractions well-described by the calculated Wulff construction.

Electrolyte decomposition reactions on Li-ion battery electrodes contribute to the formation of solid electrolyte interphase (SEI) layers. These SEI layers are one of the known causes for the loss in battery voltage and capacity over repeated charge/discharge cycles. In this work, density functional theory (DFT)-based ab-initio calculations are applied to study the initial steps of the decomposition of the organic electrolyte component ethylene carbonate (EC) on the (10-14) surface of a layered Li(Nix,Mny,Co1-x-y)O2 (NMC) cathode crystal, which is commonly used in commercial Li-ion batteries. The effects on the EC reaction pathway due to dissolved Li+ ions in the electrolyte solution and different NMC cathode surface terminations containing absorbed hydroxyl -OH or fluorine -F species are explicitly considered. We predict a very fast chemical reaction consisting of an EC ring-opening process on the bare cathode surface, the rate of which is independent of the battery operation voltage. This EC ring-opening reaction is unavoidable once the cathode material contacts with the electrolyte because this process is purely chemical rather than electrochemical in nature. The -OH and -F adsorbed species display a passivation effect on the surface against the reaction with EC, but the extent is limited except for the case of -OH bonded to a surface transition metal atom. Our work implies that the possible rate-limiting steps of the electrolyte molecule decomposition are the reactions on the decomposed organic products on the cathode surface rather than on the bare cathode surface., Comment: ACS Applied Materials and Interfaces, 2017

Interfaces are ubiquitous in Li-ion battery electrodes, occurring across compositional gradients, regions of multiphase intergrowths, and between electrodes and solid electrolyte interphases or protective coatings. However, the impact of these interfaces on Li energetics remains largely unknown. In this work, we calculated Li intercalation-site energetics across cathode interfaces and demonstrated the physics governing these energetics on both sides of the interface. We studied the olivine/olivine-structured LixFePO4/LixMPO4 (x=0 and 1, M=Co, Ti, Mn) and layered/layered-structured LiNiO2/TiO2 interfaces to explore different material structures and transition metal elements. We found that across an interface from a high- to low-voltage material the Li voltage remains constant in the high-voltage material and decays approximately linearly in the low-voltage region, approaching the Li voltage of the low-voltage material. This effect ranges from 0.5-9nm depending on the interfacial dipole screening. This effect provides a mechanism for a high-voltage material at an interface to significantly enhance the Li intercalation voltage in a low-voltage material over nanometer scale. We showed that this voltage enhancement is governed by a combination of electron transfer (from low- to high-voltage regions), strain and interfacial dipole screening. We explored the implications of this voltage enhancement for a novel heterostructured-cathode design and redox pseudocapacitors.

Understanding the structure of ZnO surface reconstructions and their resultant properties is crucial to the rational design of ZnO-containing devices ranging from optoelectronics to catalysts. Here, we are motivated by recent experimental work which showed a new surface reconstruction containing Zn vacancies ordered in a Zn(3x3) pattern in the subsurface of (0001)-O terminated ZnO. A reconstruction with Zn vacancies on (0001)-O is surprising and counterintuitive because Zn vacancies enhance the surface dipole rather than reduce it. In this work, we show using Density Functional Theory (DFT) that subsurface Zn vacancies can form on (0001)-O when coupled with adsorption of surface H and are in fact stable under a wide range of common conditions. We also show these vacancies have a significant ordering tendency and that Sb-doping created subsurface inversion domain boundaries (IDBs) enhances the driving force of Zn vacancy alignment into large domains of the Zn(3x3) reconstruction.

The surface coating of cathodes using insulator films has proven to be a promising method for high-voltage cathode stabilization in Li-ion batteries. However, there is still substantial uncertainty about how these films function, specifically with regard to important coating design principles such as lithium solubility and transport through the films. This study uses Density Functional Theory to examine the diffusivity of interstitial lithium in crystalline {\alpha}-$AlF_3$, {\alpha}-$Al_2O_3$, m-$ZrO_2$, c-MgO, and {\alpha}-quartz $SiO_2$, which provide benchmark cases for further understanding of insulator coatings in general. In addition, we propose an Ohmic electrolyte model to predict resistivities and overpotential contributions under battery operating conditions. For the crystalline materials considered we predict that Li+ diffuses quite slowly, with a migration barrier larger than 0.9 eV in all crystalline materials except {\alpha}-quartz $SiO_2$, which is predicted to have a migration barrier of 0.276 eV along <001>. These results suggest that the stable crystalline forms of these insulator materials, except for oriented {\alpha}-quartz $SiO_2$, are not practical for conformal cathode coatings. Amorphous $Al_2O_3$ and $AlF_3$ have higher Li+ diffusivities than their crystalline counterparts. Our predicted amorphous $Al_2O_3$ resistivity (1789 M{\Omega}m) is near the top of the range of fitted resistivities extracted from previous experiments on nominal $Al_2O_3$ coatings (7.8 to 913 M{\Omega}m) while our predicted amorphous $AlF_3$ resistivity (114 M{\Omega}m) is close to the middle of the range. These comparisons support our framework for modeling and understanding the impact on overpotential of conformal coatings in terms of their fundamental thermodynamic and kinetic properties, and support that these materials can provide practical conformal coatings in their amorphous form.

Perovskite oxides containing transition metals are promising materials in a wide range of electronic and electrochemical applications. However, neither their work function values nor an understanding of their work function physics have been established. Here, we predict the work function trends of a series of perovskite ($ABO_3$ formula) materials using Density Functional Theory, and show that the work functions of (001)-terminated AO- and $BO_2$-oriented surfaces can be described using concepts of electronic band filling, bond hybridization, and surface dipoles. The calculated range of AO ($BO_2$) work functions are 1.60-3.57 eV (2.99-6.87 eV). We find an approximately linear correlation ($R^2$ between 0.77-0.86, depending on surface termination) between work function and position of the oxygen 2p band center, which correlation enables both understanding and rapid prediction of work function trends. Furthermore, we identify $SrVO_3$ as a stable, low work function, highly conductive material. Undoped (Ba-doped) $SrVO_3$ has an intrinsically low AO-terminated work function of 1.86 eV (1.07 eV). These properties make $SrVO_3$ a promising candidate material for a new electron emission cathode for application in high power microwave devices, and as a potential electron emissive material for thermionic energy conversion technologies.

Metal fluoride and oxides can store multiple lithium-ions through conversion chemistry to enable high energy-density lithium-ion batteries. However, their practical applications have been hindered by an unusually large voltage hysteresis between charge and discharge voltage-profiles and the consequent low energy efficiency (< 80%). The physical origins of such hysteresis are rarely studied and poorly understood. Here we employ in situ X-ray absorption spectroscopy (XAS), transmission electron microscopy (TEM), density-functional-theory (DFT) calculations, and galvanostatic intermittent titration technique (GITT) to first correlate the voltage profile of iron fluoride ($FeF_3$), a representative conversion electrode material, with evolution and spatial distribution of intermediate phases in the electrode. The results reveal that, contrary to conventional belief, the phase evolution in the electrode is symmetrical during discharge and charge. However, the spatial evolution of the electrochemically active phases, which is controlled by reaction kinetics, is different. We further propose that the voltage hysteresis in the $FeF_3$ electrode is kinetic in nature. It is the result of Ohmic voltage drop, reaction overpotential, and different spatial distributions of electrochemically-active phases (i.e. compositional inhomogeneity). Therefore, the large hysteresis can be expected to be mitigated by rational design and optimization of material microstructure and electrode architecture to improve the energy efficiency of lithium-ion batteries based on conversion chemistry.

In this study we employ Density Functional Theory (DFT) methods to investigate the surface energy barrier for electron emission (surface barrier) and thermodynamic stability of Ba and Ba-O species adsorption under conditions of high temperature (approximately 1200 K) and low pressure (approximately $10^{-10}$ Torr) on the low index surfaces of bixbyite $Sc_2O_3$. The role of Ba in lowering the cathode surface barrier is investigated via adsorption of atomic Ba and Ba-O dimers, where the highest simulated dimer coverage corresponds to a single monolayer film of rocksalt BaO. The change of the surface barrier of a semiconductor due to adsorption of surface species is decomposed into two parts: a surface dipole component and doping component. The lowest surface barrier with atomic Ba on $Sc_2O_3$ was found to be 2.12 eV and 2.04 eV for the (011) and (111) surfaces at 3 and 1 Ba atoms per surface unit cell (0.250 and 0.083 Ba per surface O), respectively. The lowest surface barrier for Ba-O on $Sc_2O_3$ was found to be 1.21 eV on (011) for a 7 Ba-O dimer-per-unit-cell coverage (0.583 dimers per surface O). Generally, we found that Ba in its atomic form on $Sc_2O_3$ surfaces is not stable relative to bulk BaO, while Ba-O dimer coverages between 3 to 7 Ba-O dimers per (011) surface unit cell (0.250 to 0.583 dimers per surface O) produce stable structures relative to bulk BaO. Ba-O dimer adsorption on $Sc_2O_3$ (111) surfaces was found to be unstable versus BaO over the full range of coverages studied. Investigation of combined n-type doping and surface dipole modification showed that their effects interact to yield a reduction less than the two contributions would yield separately.

Recent experimental observations indicate that bulk $Sc_2O_3$ (~200 nm thick), an insulator at room temperature and pressure, must act as a good electronic conductor during thermionic cathode operation, leading to the observed high emitted current densities and overall superior emission properties over conventional thermionic emitters which do not contain $Sc_2O_3$. Here, we employ ab initio methods using both semilocal and hybrid functionals to calculate the intrinsic defect energetics of Sc and O vacancies and interstitials and their effects on the electronic properties of $Sc_2O_3$ in an effort to explain the good conduction of $Sc_2O_3$ observed in experiment. The defect energetics were used in an equilibrium defect model to calculate the concentrations of defects and their compensating electron and hole concentrations at equilibrium. Overall, our results indicate that the conductivity of $Sc_2O_3$ solely due to the presence of intrinsic defects in the cathode operating environment is unlikely to be high enough to maintain the magnitude of emitted current densities obtained from experiment, and that presence of impurities are necessary to raise the conductivity of $Sc_2O_3$ to a high enough value to explain the current densities observed in experiment. The necessary minimum impurity concentration to impart sufficient electronic conduction is very small (approximately $7.5x10^{-3}$ ppm) and is probably present in all experiments.