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Peter A. Crozier

Publications and source records attributed to Peter A. Crozier.

At least 19 recordsLinked to original sources

Atomic Depth Estimation From Noisy Electron Microscopy Data Via Deep Learning

We present a novel approach for extracting 3D atomic-level information from transmission electron microscopy (TEM) images affected by significant noise. The approach is based on formulating depth estimation as a semantic segmentation problem. We address the resulting segmentation problem by training a deep convolutional neural network to generate pixel-wise depth segmentation maps using simulated data corrupted by synthetic noise. The proposed method was applied to estimate the depth of atomic columns in CeO2 nanoparticles from simulated images and real-world TEM data. Our experiments show that the resulting depth estimates are accurate, calibrated and robust to noise.

cs.CV↗

Revealing Information from Weak Signal in Electron Energy-Loss Spectroscopy with a Deep Denoiser

Electron energy-loss spectroscopy (EELS) coupled with scanning transmission electron microscopy (STEM) is a powerful technique to determine materials composition and bonding with high spatial resolution. Noise is often a limitation especially with the increasing sophistication of EELS experiments. The signal characteristics from direct electron detectors provide a new opportunity to design superior denoisers. We have developed a CNN based denoiser, the unsupervised deep video denoiser (UDVD), which can be applied to EELS datasets acquired with direct electron detectors. We described UDVD and explained how to adapt the denoiser to energy-loss spectral series. To benchmark the performance of the denoiser on EELS datasets, we generated and denoised a set of simulated spectra. We demonstrate the charge spreading effect associated with pixel interfaces on direct electron detectors, which leads to artifacts after denoising. To suppress such artifacts, we propose some adjustments. We demonstrate the effectiveness of the denoiser using two challenging real data examples: mapping Gd dopants in $CeO_2$ nanoparticles and characterizing vibrational modes in hexagonal boron nitride (h-BN) with atomic resolution.

physics.ins-det↗

Atomic Resolution Observations of Nanoparticle Surface Dynamics and Instabilities Enabled by Artificial Intelligence

Nanoparticle surface structural dynamics is believed to play a significant role in regulating functionalities such as diffusion, reactivity, and catalysis but the atomic-level processes are not well understood. Atomic resolution characterization of nanoparticle surface dynamics is challenging since it requires both high spatial and temporal resolution. Though ultrafast transmission electron microscopy (TEM) can achieve picosecond temporal resolution, it is limited to nanometer spatial resolution. On the other hand, with the high readout rate of new electron detectors, conventional TEM has the potential to visualize atomic structure with millisecond time resolutions. However, the need to limit electron dose rates to reduce beam damage yields millisecond images that are dominated by noise, obscuring structural details. Here we show that a newly developed unsupervised denoising framework based on artificial intelligence enables observations of metal nanoparticle surfaces with time resolutions down to 10 ms at moderate electron dose. On this timescale, we find that many nanoparticle surfaces continuously transition between ordered and disordered configurations. The associated stress fields can penetrate below the surface leading to defect formation and destabilization making the entire nanoparticle fluxional. Combining this unsupervised denoiser with electron microscopy greatly improves spatio-temporal characterization capabilities, opening a new window for future exploration of atomic-level structural dynamics in materials.

cond-mat.mtrl-sci↗

An Open-Cell Environmental Transmission Electron Microscopy Technique for In Situ Characterization of Samples in Aqueous Liquid Solutions

The desire to image specimens in liquids has led to the development of open-cell and closed-cell techniques in transmission electron microscopy (TEM). The closed-cell approach is currently more common in TEM and has yielded new insights into a number of biological and materials processes in liquid environments. The open-cell approach, which requires an environmental TEM (ETEM), is technically challenging but may be advantageous in certain circumstances due to fewer restrictions on specimen and detector geometry. Here, we demonstrate a novel approach to open-cell liquid TEM, in which we use salt particles to facilitate the in situ formation of droplets of aqueous solution that envelope specimen particles coloaded with the salt. This is achieved by controlling sample temperature between 1 and 10°C and introducing water vapor to the ETEM chamber above the critical pressure for the formation of liquid water on the salt particles. Our use of in situ hydration enables specimens to be loaded into a microscope in a dry state using standard 3 mm TEM grids, allowing specimens to be prepared using trivial sample preparation techniques. Our future aim will be to combine this technique with an in situ light source to study photocorrosion in aqueous environments.

physics.app-ph↗

Atomic Level Strain Induced by Static and Dynamic Oxygen Vacancies on Reducible Oxide Surfaces

Surface strain often controls properties of the material including charge transport and chemical reactivity. Localized surface strain is measured with atomic resolution on (111) ceria nanoparticle surfaces using environmental transmission electron microscopy under different redox conditions. Density Functional Theory (DFT) coupled with TEM image simulations have been used for aid in interpreting the experimental data. Oxygen vacancy creation/annihilation introduces strain at surface and near surface regions on cation sublattice. Static and fluxional strainmaps are generated from images at these different conditions and compared. While fluxional strain is highest at locations associated with unstable vacancies at active sites, highly inhomogeneous static strain fields comprising of alternating tensile/compressing strain is seen at surface and subsurfaces linked to the presence of stable oxygen vacancies. Interestingly, both stable and unstable oxygen vacancies are found within a few atomic spacing of each other on the same surface. The static strain pattern depends on the ambient inside TEM. Oxidizing environments tend to lower vacancy concentrations at the surface whereas a highly reducing environment created using high electron dose creates oxygen vacancies everywhere (bulk and surfaces) in the nanoparticle.

cond-mat.mtrl-sci↗

Dynamic Atomic Column Detection in Transmission Electron Microscopy Videos via Ridge Estimation

Ridge detection is a classical tool to extract curvilinear features in image processing. As such, it has great promise in applications to material science problems; specifically, for trend filtering relatively stable atom-shaped objects in image sequences, such as Transmission Electron Microscopy (TEM) videos. Standard analysis of TEM videos is limited to frame-by-frame object recognition. We instead harness temporal correlation across frames through simultaneous analysis of long image sequences, specified as a spatio-temporal image tensor. We define new ridge detection algorithms to non-parametrically estimate explicit trajectories of atomic-level object locations as a continuous function of time. Our approach is specially tailored to handle temporal analysis of objects that seemingly stochastically disappear and subsequently reappear throughout a sequence. We demonstrate that the proposed method is highly effective and efficient in simulation scenarios, and delivers notable performance improvements in TEM experiments compared to other material science benchmarks.

stat.AP↗

Feature detection and hypothesis testing for extremely noisy nanoparticle images using topological data analysis

We propose a flexible algorithm for feature detection and hypothesis testing in images with ultra low signal-to-noise ratio using cubical persistent homology. Our main application is in the identification of atomic columns and other features in transmission electron microscopy (TEM). Cubical persistent homology is used to identify local minima and their size in subregions in the frames of nanoparticle videos, which are hypothesized to correspond to relevant atomic features. We compare the performance of our algorithm to other employed methods for the detection of columns and their intensity. Additionally, Monte Carlo goodness-of-fit testing using real valued summaries of persistence diagrams derived from smoothed images (generated from pixels residing in the vacuum region of an image) is developed and employed to identify whether or not the proposed atomic features generated by our algorithm are due to noise. Using these summaries derived from the generated persistence diagrams, one can produce univariate time series for the nanoparticle videos, thus providing a means for assessing fluxional behavior. A guarantee on the false discovery rate for multiple Monte Carlo testing of identical hypotheses is also established.

stat.AP↗

Spectroscopic Observation and Modeling of Photonic Modes in CeO2 Nanocubes

Photonic modes in dielectric nanostructures, e.g., wide gap semiconductor like CeO2 (ceria), has potential for various applications such as light harvesting and information transmission. To fully understand the properties of such phenomenon in nanoscale, we applied electron energy-loss spectroscopy (EELS) in scanning transmission electron microscope (STEM) to detect such modes in a well-defined ceria nanocube. Through spectra and mapping, we demonstrated a geometrical difference of mode excitation. By comparing various spectra taken at different location relative to the cube, we also showed the transmission properties of the mode. To confirm our observation, we performed EELS simulation with finite-element dielectric calculations in COMSOL Multiphysics. We also revealed the origin of the modes through the calculation. We purposed a simple analytical model to estimate the energy of photonic modes as well. In all, this work gave a fine description of the photonic modes' properties in nanostructures, while demonstrating the advantage of EELS in characterizing optical phenomena in nanoscale.

physics.optics↗

The role of surface spin polarization on ceria-supported Pt nanoparticles

In this work, we employ first-principles simulations to investigate the spin polarization of CeO$_2$-(111) surface and its impact on interactions between a ceria support and Pt nanoparticles. For the first time, we report that the CeO$_2$-(111) surface exhibits a robust surface spin polarization due to the internal charge transfer between atomic Ce and O layers. In turn, it can lower the surface oxygen vacancy formation energy and enhance the oxide reducibility. We show that the inclusion of spin polarization can therefore significantly reduce the major activation barrier in the proposed reaction pathway of CO oxidation on ceria-supported Pt nanoparticles. For metal-support interactions, surface spin polarization enhances the bonding between Pt nanoparticle and ceria surface oxygen, while CO adsorption on Pt nanoparticles weakens the interfacial interaction regardless of spin polarization.

cond-mat.mtrl-sci↗

Unsupervised Deep Video Denoising

Deep convolutional neural networks (CNNs) for video denoising are typically trained with supervision, assuming the availability of clean videos. However, in many applications, such as microscopy, noiseless videos are not available. To address this, we propose an Unsupervised Deep Video Denoiser (UDVD), a CNN architecture designed to be trained exclusively with noisy data. The performance of UDVD is comparable to the supervised state-of-the-art, even when trained only on a single short noisy video. We demonstrate the promise of our approach in real-world imaging applications by denoising raw video, fluorescence-microscopy and electron-microscopy data. In contrast to many current approaches to video denoising, UDVD does not require explicit motion compensation. This is advantageous because motion compensation is computationally expensive, and can be unreliable when the input data are noisy. A gradient-based analysis reveals that UDVD automatically adapts to local motion in the input noisy videos. Thus, the network learns to perform implicit motion compensation, even though it is only trained for denoising.

eess.IV↗

Adaptive Denoising via GainTuning

Deep convolutional neural networks (CNNs) for image denoising are usually trained on large datasets. These models achieve the current state of the art, but they have difficulties generalizing when applied to data that deviate from the training distribution. Recent work has shown that it is possible to train denoisers on a single noisy image. These models adapt to the features of the test image, but their performance is limited by the small amount of information used to train them. Here we propose "GainTuning", in which CNN models pre-trained on large datasets are adaptively and selectively adjusted for individual test images. To avoid overfitting, GainTuning optimizes a single multiplicative scaling parameter (the "Gain") of each channel in the convolutional layers of the CNN. We show that GainTuning improves state-of-the-art CNNs on standard image-denoising benchmarks, boosting their denoising performance on nearly every image in a held-out test set. These adaptive improvements are even more substantial for test images differing systematically from the training data, either in noise level or image type. We illustrate the potential of adaptive denoising in a scientific application, in which a CNN is trained on synthetic data, and tested on real transmission-electron-microscope images. In contrast to the existing methodology, GainTuning is able to faithfully reconstruct the structure of catalytic nanoparticles from these data at extremely low signal-to-noise ratios.

cs.CV↗

Deep Denoising For Scientific Discovery: A Case Study In Electron Microscopy

Denoising is a fundamental challenge in scientific imaging. Deep convolutional neural networks (CNNs) provide the current state of the art in denoising natural images, where they produce impressive results. However, their potential has barely been explored in the context of scientific imaging. Denoising CNNs are typically trained on real natural images artificially corrupted with simulated noise. In contrast, in scientific applications, noiseless ground-truth images are usually not available. To address this issue, we propose a simulation-based denoising (SBD) framework, in which CNNs are trained on simulated images. We test the framework on data obtained from transmission electron microscopy (TEM), an imaging technique with widespread applications in material science, biology, and medicine. SBD outperforms existing techniques by a wide margin on a simulated benchmark dataset, as well as on real data. Apart from the denoised images, SBD generates likelihood maps to visualize the agreement between the structure of the denoised image and the observed data. Our results reveal shortcomings of state-of-the-art denoising architectures, such as their small field-of-view: substantially increasing the field-of-view of the CNNs allows them to exploit non-local periodic patterns in the data, which is crucial at high noise levels. In addition, we analyze the generalization capability of SBD, demonstrating that the trained networks are robust to variations of imaging parameters and of the underlying signal structure. Finally, we release the first publicly available benchmark dataset of TEM images, containing 18,000 examples.

cs.CV↗

An $\textit{In Situ}$ Light Illumination System for an Aberration-Corrected Environmental Transmission Electron Microscope

In this work, an optic fiber based $\textit{in situ}$ illumination system integrated into an aberration-corrected environmental transmission electron microscope (ETEM) is designed, built, characterized and applied. With this illumination system, the dynamic responses of photoactive materials to photons can be directly observed at the atomic level, and other stimuli including heating and various gases can also be applied simultaneously. Either a broadband light source or a high power laser source aiming to expedite photoreactions can be utilized, fitting different application needs. The optic fiber enters the ETEM through the objective aperture port, with a carefully designed curvature and a 30° cut at the tip to orient the emitted light upwards onto the TEM specimen. The intensity distributions striking the sample from the broadband and laser sources are both measured, and due to the non-uniform distributions, an alignment procedure has been developed to align the bright spot with the electron optical axis of the TEM. The imaging and spectroscopy performances of the ETEM are proved to be maintained after incorporating this illumination system. Furthermore, Langmuir evaporation is observed when in situ laser light is applied to GaAs, demonstrating the phenomenon of optical heating on suitable semiconductor materials.

cond-mat.mtrl-sci↗

Fluxional Behavior at the Atomic Level and its Impact on Activity: CO Oxidation over CeO$_{2}$-supported Pt Catalysts

Reducible oxides are widely used catalyst supports that can increase oxidation reaction rates by transferring their lattice oxygen at the metal-support interface. The interfacial oxidation process is typically described in terms of a Mars-van Krevelen mechanism. However, many outstanding questions remain unanswered regarding the atomic-scale structure and dynamic meta-stability (i.e., fluxional behavior) of the interface $\textit{during catalysis}$. Here, we employ aberration-corrected $\textit{operando}$ electron microscopy to visualize the structural dynamics occurring at and near Pt/CeO$_{2}$ interfaces during CO oxidation. Finite element simulations are performed to develop a reaction rate analysis wherein the atomic-level structural observations are directly correlated with the catalyst's turnover frequency for CO oxidation. We show that the increasing frequency of catalytic turnover correlates with dynamic fluxional behavior that (a) destablizes the supported Pt particle, (b) marks an enhanced rate of oxygen vacancy creation and annihilation, and (c) leads to increased strain and reduction in the surface of the CeO$_{2}$ support. Overall, the results implicate the interfacial Pt-O-Ce bonds anchoring the Pt to the support as being involved also in the catalytically-driven oxygen transfer process, and they suggest that oxygen reduction takes place on the highly reduced nearby CeO2 surface before migrating to the interfacial perimeter for reaction with CO. The $\textit{operando}$ electron microscopy approach described here should be applicable to a large number of nanoparticle catalysts. This technique will enable the identification of catalytically functional surface structures and strengthen our ability to establish (dynamic) structure-activity relationships.

cond-mat.mtrl-sci↗

Developing and Evaluating Deep Neural Network-based Denoising for Nanoparticle TEM Images with Ultra-low Signal-to-Noise

A deep convolutional neural network has been developed to denoise atomic-resolution TEM image datasets of nanoparticles acquired using direct electron counting detectors, for applications where the image signal is severely limited by shot noise. The network was applied to a model system of CeO2-supported Pt nanoparticles. We leverage multislice image simulations to generate a large and flexible dataset for training and testing the network. The proposed network outperforms state-of-the-art denoising methods by a significant margin both on simulated and experimental test data. Factors contributing to the performance are identified, including most importantly (a) the geometry of the images used during training and (b) the size of the network's receptive field. Through a gradient-based analysis, we investigate the mechanisms learned by the network to denoise experimental images. This shows that the network exploits global and local information in the noisy measurements, for example, by adapting its filtering approach when it encounters atomic-level defects at the nanoparticle surface. Extensive analysis has been done to characterize the network's ability to correctly predict the exact atomic structure at the nanoparticle surface. Finally, we develop an approach based on the log-likelihood ratio test that provides a quantitative measure of the agreement between the noisy observation and the atomic-level structure in the network-denoised image.

cond-mat.mtrl-sci↗

Simultaneous excitation of phonons at the center and boundaries of Brillouin zones with high energy electron beams

High energy electron beams can now be routinely focused to 1-2 Å and offer the ability to obtain vibrational information from materials using monochromated electron energy-loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM). Here it is shown that long and short wavelength phonons can be probed simultaneously with on-axis vibrational STEM EELS. The advantage of using focused electron beams is that the short wavelength phonons are probed via impact scattering while the long-wavelength modes are probed via dipole scattering. The localized character of the short-wavelength modes is demonstrated by scanning the electron beam across the edge of a hexagonal boron nitride nanoparticle. It is found that the condition required for high spatial resolution STEM imaging also correlates with the condition to enhance the short-wavelength phonon contribution to the vibrational energy-loss spectrum. Probing short-wavelength phonons at high spatial resolution with on-axis vibrational STEM EELS will help develop a fundamental connection between vibrational excitations and bonding arrangements at atomic scale heterogeneities in materials.

cond-mat.mtrl-sci↗

Chemical Kinetics for Operando Electron Microscopy of Catalysts: 3D Modeling of Gas and Temperature Distributions During Catalytic Reactions

$\textit{In situ}$ environmental transmission electron microscopy (ETEM) is a powerful tool for observing structural modifications taking place in heterogeneous catalysts under reaction conditions. However, to strengthen the link between catalyst structure and functionality, an $\textit{operando}$ measurement must be performed in which reaction kinetics and catalyst structure are simultaneously determined. To determine chemical kinetics for gas-phase catalysis, it is necessary to develop a reliable chemical engineering model to describe catalysis as well as heat and mass transport processes within the ETEM cell. Here, we establish a finite element model to determine the gas and temperature profiles during catalysis in an open-cell operando ETEM experiment. The model is applied to a $SiO_2$-supported Ru catalyst performing CO oxidation. Good agreement is achieved between simulated compositions and those measured experimentally across a temperature range of 25 - 350 °C. In general, for lower conversions, the simulations show that the temperature and gas are relatively homogeneous within the hot zone of the TEM holder where the catalyst is located. The uniformity of gas and temperature indicates that the ETEM reactor system behavior approximates that of a continuously stirred tank reactor. The large degree of gas-phase uniformity also allows one to estimate the catalytic conversion of reactants in the cell to within 10 percent using electron energy-loss spectroscopy. Moreover, the findings indicate that for reactant conversions below 30 percent, one can reliably evaluate the steady-state reaction rate of catalyst nanoparticles that are imaged on the TEM grid.

cond-mat.mtrl-sci↗

Impact of Aliovalent Alkaline-Earth Metal Solutes on Ceria Grain Boundaries: A Density Functional Theory Study

Ceria has proven to be an excellent ion-transport and ion-exchange material when used in polycrystalline form and with a high-concentration of aliovalent doped cations. Despite its widespread application, the impact of atomic-scale defects in this material are scarcely studied and poorly understood. In this article, using first-principles simulations, we provide a fundamental understanding of the atomic-structure, thermodynamic stability and electronic properties of undoped grain-boundaries (GBs) and alkaline-earth metal (AEM) doped GBs in ceria. Using density-functional theory simulations, with a GGA+U functional, we find the $Σ$3 (111)/[$\bar{1}$01] GB is thermodynamically more stable than the $Σ$3 (121)/[$\bar{1}$01] GB due to the larger atomic coherency in the $Σ$3 (111)/[$\bar{1}$01] GB plane. We dope the GBs with $\sim$20% [M]$_{GB}$ (M=Be, Mg, Ca, Sr, and Ba) and find that the GB energies have a parabolic dependence on the size of solutes, the interfacial strain and the packing density of the GB. We see a stabilization of the GBs upon Ca, Sr and Ba doping whereas Be and Mg render them thermodynamically unstable. The electronic density of states reveal that no defect states are present in or above the band gap of the AEM doped ceria, which is highly conducive to maintain low electronic mobility in this ionic conductor. The electronic properties, unlike the thermodynamic stability, exhibit complex inter-dependence on the structure and chemistry of the host and the solutes. This work makes advances in the atomic-scale understanding of aliovalent cation doped ceria GBs serving as an anchor to future studies that can focus on understanding and improving ionic-transport.

cond-mat.mtrl-sci↗