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Ciston, Jim

Publications and source records attributed to Ciston, Jim.

CuXASNet: Rapid and accurate prediction of copper L-edge x-ray absorption spectra using machine learning

In this work, we have developed CuXASNet, a dense neural network that predicts simulated Cu -edge x-ray absorption spectra (XAS) from atomic structures. Featurization of the Cu local environment is performed using a component of M3GNet, a graph neural network developed for predicting the potential energy surface. CuXASNet is trained on simulated spectra from FEFF9 at the multiple scattering level of theory, and can predict the and edges for Cu sites to quantitative accuracy. To validate our approach, we compare 14 experimental spectra extracted from the literature with the predictions of CuXASNet. The agreement of CuXASNet with experiments is shown by an average mean absolute error of 0.125 and an average Spearman's correlation coefficient of 0.891, which is comparable to FEFF9's values of 0.131 and 0.898 for the same metrics. As such, CuXASNet can rapidly predict a large number of -edge XAS spectra at the same accuracy as FEFF9 simulations. This can be used as a drop-in replacement for multiple scattering codes for fast screening of candidate atomic structure models of a measured system. This model establishes a general framework for Cu XAS prediction, and can be extended to more computationally expensive levels of theory and to other transition metal edges.

36 MATERIALS SCIENCE

In Situ Study of Resistive Switching in a Nitride‐Based Memristive Device

Abstract Resistive switching (RS) devices with ultra‐low‐voltage threshold and reliable switching repeatability exhibits great potential applications in energy‐efficient data storage and neuromorphic computing. Understanding switching mechanisms at nanoscale is critical to design RS devices with improved performance. In this work, a lamella memristive device using focused ion beam (FIB) method based on the metal/TiO x /TiN/Si structure device is fabricated. In situ transmission electron microscopy (TEM) and current–voltage ( I–V ) characteristic demonstrate that the lamella device shows a volatile RS behavior with a threshold switching at ≈ ± 0.4 V. In situ scanning transmission electron microscopy (STEM) experiments with electron energy loss spectroscopy (EELS) reveal that the charge carriers such as oxygen vacancies migrate under positive/negative DC bias and modulate Schottky barriers at the top and bottom metal/semiconductor interfaces. The RS mechanism of the lamella device is based on the Schottky barriers modulation and Joule heating assisted electric field triggered thermal runaway (FTTR) occurred at the metal/semiconductor interfaces. The fundamental insights gained from this study presents a perspective on interface‐type RS devices processing and opens up new technological opportunities of fabricating ultra‐low‐energy memristive devices.

36 MATERIALS SCIENCE

Improved Three-Dimensional Reconstructions in Electron Ptychography through Defocus Series Measurements

A detailed analysis of ptychography for three-dimensional (3D) phase reconstructions of thick specimens is performed. Here, we introduce multi-focus ptychography, which incorporates a 4D-STEM defocus series to enhance the quality of 3D reconstructions along the beam direction through a higher overdetermination ratio. This method is compared with established multi-slice ptychography techniques, such as conventional ptychography, regularized ptychography, and multi-mode ptychography. Additionally, we contrast multi-focus ptychography with an alternative method that uses virtual optical sectioning through a reconstructed scattering matrix (S-matrix), which offers more precise 3D structure information compared to conventional ptychography. Our findings from multiple 3D reconstructions based on simulated and experimental data demonstrate that multi-focus ptychography surpasses other techniques, particularly in accurately reconstructing the surfaces and interface regions of thick specimens.

3D reconstruction

Magnetic order in nanogranular iron germanium (Fe 0.53 Ge 0.47 ) films

We study the effect of strain on the magnetic properties and magnetization configurations in nanogranular Fe x Ge 1-x films (x = 0.53 ± 0.05) with and without B20 FeGe nanocrystals surrounded by an amorphous structure. Relaxed films on amorphous silicon nitride membranes reveal a disordered skyrmion phase while films near and on top of a rigid substrate favor ferromagnetism and an anisotropic hybridization of Fe d levels and spin-polarized Ge sp band states. The weakly coupled topological states emerge at room temperature and become more abundant at cryogenic temperatures without showing indications of pinning at defects or confinement to individual grains. These results demonstrate the possibility to control magnetic exchange and topological magnetism by strain and inform magnetoelasticity-mediated voltage control of topological phases in amorphous quantum materials.

36 MATERIALS SCIENCE

Random forest prediction of crystal structure from electron diffraction patterns incorporating multiple scattering

Diffraction is the most common method to solve for unknown or partially known crystal structures. However, it remains a challenge to determine the crystal structure of a new material that may have nanoscale size or heterogeneities. Here, in this study, we train an architecture of hierarchical random forest models capable of predicting the crystal system, space group, and lattice parameters from one or more unknown two-dimensional electron diffraction patterns. Our initial model correctly identifies the crystal system of a simulated electron diffraction pattern from a 20-nm-thick specimen of arbitrary orientation 67% of the time. We achieve a topline accuracy of 79% when aggregating predictions from ten patterns of the same material but different zone axes. The space group and lattice predictions range from 70% to 90% accuracy and median errors of 0.01-0.5Å, respectively, for cubic, hexagonal, trigonal, and tetragonal crystal systems while being less reliable on orthorhombic and monoclinic systems. We apply this architecture to a four-dimensional scanning transmission electron microscopy scan of gold nanoparticles, where it accurately predicts the crystal structure and lattice constants. These random forest models can be used to significantly accelerate the analysis of electron diffraction patterns, particularly in the case of unknown crystal structures. Additionally, due to the speed of inference, these models could be integrated into live transmission electron microscopy experiments, allowing real-Time labeling of a specimen.

36 MATERIALS SCIENCE

The 4D Camera: An 87 kHz Direct Electron Detector for Scanning/Transmission Electron Microscopy

We describe the development, operation, and application of the 4D Camera—a 576 by 576 pixel active pixel sensor for scanning/transmission electron microscopy which operates at 87,000 Hz. The detector generates data at ~480 Gbit/s which is captured by dedicated receiver computers with a parallelized software infrastructure that has been implemented to process the resulting 10–700 Gigabyte-sized raw datasets. The back illuminated detector provides the ability to detect single electron events at accelerating voltages from 30 to 300 kV. Through electron counting, the resulting sparse data sets are reduced in size by 10--300× compared to the raw data, and open-source sparsity-based processing algorithms offer rapid data analysis. The high frame rate allows for large and complex scanning diffraction experiments to be accomplished with typical scanning transmission electron microscopy scanning parameters.

47 OTHER INSTRUMENTATION

Steam‐Assisted Selective CO 2 Hydrogenation to Ethanol over Ru−In Catalysts

Abstract Multicomponent catalysts can be designed to synergistically combine reaction intermediates at interfacial active sites, but restructuring makes systematic control and understanding of such dynamics challenging. We here unveil how reducibility and mobility of indium oxide species in Ru‐based catalysts crucially control the direct, selective conversion of CO 2 to ethanol. When uncontrolled, reduced indium oxide species occupy the Ru surface, leading to deactivation. With the addition of steam as a mild oxidant and using porous polymer layers to control In mobility, Ru−In 2 O 3 interface sites are stabilized, and ethanol can be produced with superior overall selectivity (70 %, rest CO). Our work highlights how engineering of bifunctional active ensembles enables cooperativity and synergy at tailored interfaces, which unlocks unprecedented performance in heterogeneous catalysts.

Zhou, Chengshuang

Integrated rocksalt–polyanion cathodes with excess lithium and stabilized cycling

Co- and Ni-free disordered rocksalt cathodes utilize oxygen redox to increase the energy density of lithium-ion batteries, but it is challenging to achieve good cycle life at high voltages >4.5 V (versus Li/Li + ). Here, in this study, we report a family of Li-excess Mn-rich cathodes that integrates rocksalt- and polyanion-type structures. Following design rules for cation filling and ordering, we demonstrate the bulk incorporation of polyanion groups into the rocksalt lattice. This integration bridges the two primary families of lithium-ion battery cathodes—layered/spinel and phosphate oxides—dramatically enhancing the cycling stability of disordered rocksalt cathodes with 4.8 V upper cut-off voltage. The cathode exhibits high gravimetric energy densities above 1,100 Wh kg -1 and >70% retention over 100 cycles. This study opens up a broad compositional space for developing battery cathodes using earth-abundant elements such as Mn and Fe.

36 MATERIALS SCIENCE

Prediction of the Cu Oxidation State from EELS and XAS Spectra Using Supervised Machine Learning

Electron energy loss spectroscopy (EELS) and X-ray absorption spectroscopy (XAS) provide detailed information about distributions and locations of atoms, their coordination numbers and oxidation states, and the bonding characteristics [1]. However, analysis of XAS/EELS data often relies on matching the spectra of an unknown experimental sample to a series of simulated or experimental spectra of standard samples. Here, this limits analysis throughput and the ability to extract quantitative information from a sample.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Random Forest Prediction of Crystal Structure from Electron Diffraction Patterns

Transmission electron microscopy (TEM) diffraction patterns are regularly used to determine the structure of crystalline materials. Electron diffraction is the most common method to solve for unknown or partially known crystal structures, as it provides direct and interpretable feedback on the orientation of crystal grains under the beam [1]. However, it remains a challenge to determine the crystal structure of a new material or even a new phase of an existing material. Analysis of such materials commonly requires manual exploration and comparison with simulated diffraction patterns. This is often a time consuming process with no obvious start point when many similar structures are possible, and this method cannot be used to determine crystal structure or orientation from structures not included in the diffraction libraries. Therefore, we have developed a machine learning model to determine the crystal structure of a material from its electron diffraction pattern.

36 MATERIALS SCIENCE

Steam-Assisted Selective CO 2 Hydrogenation to Ethanol over Ru–In Catalysts

Multicomponent catalysts can be designed to synergistically combine reaction intermediates at interfacial active sites, but restructuring makes systematic control and understanding of such dynamics challenging. In this work, we unveil how reducibility and mobility of indium oxide species in Ru-based catalysts crucially control the direct, selective conversion of CO 2 to ethanol. When uncontrolled, reduced indium oxide species occupy the Ru surface, leading to deactivation. With the addition of steam as a mild oxidant and using porous polymer layers to control In mobility, Ru–In 2 O 3 interface sites are stabilized, and ethanol can be produced with superior overall selectivity (70 %, rest CO). Our work highlights how engineering of bifunctional active ensembles enables cooperativity and synergy at tailored interfaces, which unlocks unprecedented performance in heterogeneous catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Atomic-scale identification of active sites of oxygen reduction nanocatalysts

Heterogeneous nanocatalysts play a crucial role in both the chemical and energy industries. Despite substantial advancements in theoretical, computational and experimental studies, identifying their active sites remains a major challenge. Here we utilize atomic electron tomography to determine the three-dimensional atomic structure of PtNi and Mo-doped PtNi nanocatalysts for the electrochemical oxygen reduction reaction. We then employ the experimental atomic structures as input to first-principles-trained machine learning to identify the active sites of the nanocatalysts. Through the analysis of the structure–activity relationships, we formulate an equation termed the local environment descriptor, which balances the strain and ligand effects to provide physical and chemical insights into active sites in the oxygen reduction reaction. The ability to determine the three-dimensional atomic structure and chemical composition of realistic nanoparticles, combined with machine learning, could transform our fundamental understanding of the active sites of catalysts and guide the rational design of optimal nanocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Three-dimensional structure of buried heterointerfaces revealed by multislice ptychography

Here, we report on the three-dimensional (3D) structure determination of a twisted hexagonal boron nitride (h-BN) heterointerface from a single-view dataset using multislice ptychography. We identify the buried heterointerface between two twisted h-BN flakes with a lateral resolution of 0.57 Å and a depth resolution of 2.5 nm. The latter represents a significant improvement (∼2.7 times) over the aperture-limited depth resolution of incoherent imaging modes, such as annular-dark-field scanning transmission electron microscopy. This improvement is attributed to the diffraction signal extending beyond the aperture edge, with the depth resolution set by the curvature of the Ewald sphere. Future advancements in this approach could enhance the depth resolution to the subnanometer level and enable the identification of individual dopants, defects, and color centers in twisted heterointerfaces and other materials.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC