Electron Diffraction Research Articles

Design of an atomic layer deposition system with in situ reflection high energy electron diffraction.

We report the design, fabrication, and testing of an atomic layer deposition (ALD) system that is capable of reflection high energy electron diffraction (RHEED) in a single chamber. The details and specifications of the system are described and include capabilities of RHEED at varied accelerating voltages, sample rotation (azimuthal) control, sample height control, sample heating up to set temperatures of 1050 °C, and either single- or dual-differential pumping designs. Thermal and flow simulations were used to justify selected system dimensions as well as carrier gas/precursor mass flow rates. Temperature calibration was conducted to determine actual sample temperatures that are necessary for meaningful analysis of thermally induced transitions in ALD thin films. Several demonstrations of RHEED in the system are described. Calibration of the camera length was conducted using a gold thin film by analyzing RHEED images. Finally, RHEED conducted at a series of increasing temperatures was used to monitor the crystallization of an ALD HfO2 thin film. The crystallization temperature and the ring pattern were consistent with the monoclinic structure as determined by separate x-ray diffraction-based measurements.

Ka-Band Rotational Spectroscopy of Succinimide and N-Chlorosuccinimide.

Succinimide and its derivatives are cyclic five-membered rings that appear in a variety of natural products and are widely used in organic synthesis. From a structural standpoint, succinimide contains an NH group in the ring which interacts with two adjacent carbonyl groups, pushing the ring structure toward planarity at the expense of increasing ring strain and eclipsing interactions among the out-of-plane hydrogen atoms in the two CH2 groups. Previous quantum chemical calculations at different levels of theory have predicted both a nonplanar C2 structure and a planar C2v structure, the latter of which is the most consistent with gas-phase electron diffraction measurements. Here, we report the pure rotational spectra of succinimide and N-chlorosuccinimide in the 26.5-40.0 GHz range using chirped-pulse Fourier transform microwave spectroscopy, supported by coupled cluster and density functional theory quantum chemical calculations. The spectra were fit to Watson's A-reduced effective Hamiltonian, including both 35Cl and 37Cl isotopologues of N-chlorosuccinimide as well as the N and Cl quadrupole hyperfine interactions. On the basis of the agreement with quantum chemical calculations and the measured inertial defects, we find that the rotational spectra are consistent with a planar ring structure, with a maximum out-of-plane angle of ≤5°.

Micro- to nano-sized solid inclusions in magnetite record skarn reactions

Abstract. Magnetite is a widespread ore mineral in skarn systems and usually hosts a wide variety of inclusions. Micro- to nano-sized solid inclusions in magnetite are unique tools to track the evolutionary processes of its host mineral and, subsequently, to constrain the timing of the mineralization event. In this study, we characterize micro- to nano-sized solid inclusions in magnetite from the La Víbora magnesian skarn (Málaga, Spain) using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). TEM energy-dispersive X-ray spectrometry (EDS) analyses and compositional mapping expose two types of nano-inclusions oriented along the (111) of magnetite: type 1 includes dolomite, spinel, and Mg–Fe–Al silicate, and type 2 is made up of Mg–Fe–Al silicates enveloping the Mg-bearing amorphous silica phase. High-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED), and fast Fourier transform (FFT) patterns reveal that the majority of the solid inclusions display non-oriented matrices compared to the host magnetite, precluding the possibility of sub-solidus processes. Instead, these inclusions are thought to preserve skarn mineral assemblages that were entrapped during the growth of magnetite. However, the local supersaturation of fluids trapped in the boundary layer of crystallizing magnetite is evidenced by coherent lattice orientation of precipitated and host magnetite and by the occurrence of an Mg-bearing amorphous silica phase. Our findings reveal that skarn reactions observed at field and microscopic scales are also recorded in nano-sized inclusions within magnetite. These observations underscore the significance of micro- to nano-scale solid inclusions in magnetite to decipher overprinted skarn reactions as well as constraining the timing of Fe mineralization events in skarns.

Pt12H24 -: A Cuboctahedral Platinum Hydride Cluster Cage.

The platinum hydride cluster Pt12H24 - is studied in gas phase by a combination of trapped ion electron diffraction and density functional theory computations. We find a cuboctahedral platinum cage with bridge bound hydrogen atoms. This unusual structure is stabilized by Pt-H-Pt multicenter bonds and shows characteristics of spherical aromaticity.

Harnessing Plasmonic Interference for Nanoscale Ultrafast Electron Sources.

In this Letter we demonstrate the use of plasmonic focusing in conjunction with nonlinear photoemission to develop geometrically flat nanoscale electron sources with less than 40pm-rad root mean squared (rms) normalized transverse emittance. Circularly polarized light is incident on a gold Archimedean spiral structure to generate surface-plasmon polaritons that interfere coherently at the center resulting in a 50nm rms emission area. Such a nanostructured flat surface enables simultaneous spatiotemporal confinement of emitted electrons at the nanometer and femtosecond level and can be used as an advanced electron source for high-repetition-rate ultrafast electron diffraction and microscopy experiments as well as the next generation of miniaturized particle accelerators.

Mechanistic study of β-Ga2O3 nitridation by RF nitrogen plasma for GaN heteroepitaxy

The transformation of 2¯01β-Ga2O3 to h-GaN under exposure to RF nitrogen plasma was monitored in situ by reflection high-energy electron diffraction. Analysis of the reaction kinetics reveals that the nitridation process is initiated by the formation of an oxynitride phase and proceeds via two-dimensional nucleation and growth of wurtzite GaN grains. X-ray photoelectron spectra suggest a Ga−(NxO1−x) type configuration dominates the surface early in the nitridation process. The surface restructuring is followed by a diffusion-fed phase transformation, which propagates the wurzite GaN structure into the substrate upon reaching 70% nitrogen anion site occupation, corresponding to the oxygen solubility in h-GaN. A direct correlation is observed between the nitridated film morphology and the epitaxial film crystallinity, demonstrating control of the residual strain, lateral coherence, and mosaicity in subsequent GaN epitaxy by the nitridation conditions. This study provides mechanistic details of the nitridation reaction of 2¯01β-Ga2O3 facilitating the optimization of the nitridation process toward improving GaN-2¯01β-Ga2O3 heterojunctions.

Exploring the Crystal Structure and Electronic Properties of γ-Al2O3: Machine Learning Drives Future Material Innovations.

For decades, researchers have struggled to determine the precise crystal structure of γ-Al2O3 due to its atomic-level disorder and the challenges associated with obtaining high-purity, high-crystallinity γ-Al2O3 in laboratory settings. This study investigates the crystal structure and electronic properties of γ-Al2O3 coatings under the influence of an external electric field, integrating machine learning with density functional theory (DFT). A potential 160-atom supercell structure was identified from over 600,000 γ-Al2O3 configurations and confirmed through high-resolution transmission electron microscopy and selected area electron diffraction. The findings indicate that γ-Al2O3 deviates from the conventional spinel structure, suggesting that octahedral vacancies can reduce the system's energy. Under an external electric field, the material's band structure and density of states (DOS) undergo significant changes: the bandgap narrows from 3.996 to 0 eV, resulting in metallic behavior, while the projected density of states (PDOS) exhibits peak broadening and splitting of oxygen atom PDOS below the Fermi level. These alterations elucidate the variations in the electrical conductivity of alumina coatings under an electric field. These findings clarify the mechanisms of γ-Al2O3's electronic property modulation and offer insights into its covalent and ionic mixed bonding as a wide-bandgap semiconductor. This discovery is essential for understanding dielectric breakdown in insulating materials.

Defect crystal structure of α-Na0.5-xR0.5+xF2+2x (R = Dy-Lu, Y) on X-Ray and electron diffraction data. I. MethoD of Defect structure modelling on the α-Na0.35Dy0.65F2.30 example

For the first time, the crystal α-Na0.35Dy0.65F2.30 was studied using X-ray diffraction at 293 K and 85 K and electron diffraction at 293 K. A unified cluster model of the defective structure of nanostructured crystals with a fluorite-type structure, based on the polymorphism of ordered phases KR3F10 (R = Er, Yb), was expanded with a matrix part model based on the structure of the KYF4 compound. The unified cluster model was applied to construct the defective structure of α-Na0.35Dy0.65F2.30. It was found that the matrix part of the crystal contains Na+ и Dy3+ cations in a 1:1 ratio. Some of the anions in the matrix are displaced to the 32f positions (space group Fm3m). The excess Dy3+ forms octahedral-cubic clusters with Na+ [Na14–nDynF64+n] with cores in the form of distorted and regular cuboctahedrons {F12}. These are composed of interstitial anions in two 32f positions and one 48i position. The cluster component of the α-Na0.35Dy0.65F2.30 crystal contains octahedral-cubic clusters of f-, f–i- and i-types. Electron diffraction showed that α-Na0.35Dy0.65F2.30 is a nanostructured crystal. Its cluster component is in the form of plate-like inclusions about 5 nm thick with superstructural ordering and individual octahedral-cubic clusters. A model of their structure was proposed. Lowering the temperature to 85 K increases the number of interstitial F(32f)1 anions in the matrix component of the crystal.

Real-time four-dimensional scanning transmission electron microscopy through sparse sampling

Abstract Four-dimensional scanning transmission electron microscopy (4-D STEM) is a state-of-theart image acquisition mode used to reveal high and low mass elements at atomic resolution. The acquisition of the electron momenta at each real space probe location allows for various analyses to be performed from a single dataset, including virtual imaging, electric field analysis, as well as analytical or iterative extraction of the object induced phase shift. However, the limiting factor in 4-D STEM is the speed of acquisition which is bottlenecked by the read-out speed of the camera, which must capture a convergent beam electron diffraction (CBED) pattern at each probe position in the scan. Recent developments in sparse sampling and image inpainting (a branch of compressive sensing) for STEM have allowed for real-time recovery of sparsely acquired data from fixed monolithic detectors, Further developments in compressive sensing for 4-D STEM have also demonstrated that acquisition speeds can be increased i.e. live video rate 4D imaging is now possible. In this work, we demonstrate the first practical implementations of compressive 4-D STEM for real-time inference on two different scanning transmission electron microscopes.

Directing Charge Carriers and Ferroelectric Domains at Lateral Interfaces in van der Waals Heterostructures.

Emergent phenomena in traditional ferroelectrics are frequently observed at heterointerfaces. Accessing such functionalities in van der Waals ferroelectrics requires the formation of layered heterostructures, either vertically stacked (similar to oxide ferroelectrics) or laterally stitched (without equivalent in 3D-crystals). Here, we investigate lateral heterostructures of the ferroelectric van der Waals semiconductors SnSe and SnS. A two-step process produces ultrathin crystals comprising an SnSe core laterally joined to an SnS edge-band, as confirmed by Raman spectroscopy, transmission electron microscopy (TEM) imaging, and electron diffraction. TEM shows a moiré pattern across the SnSe core due to coverage by an ultrathin SnS layer. The ability of the lateral interface (IF) to direct excited carriers, probed by cathodoluminescence, shows electron transfer over 560 nm diffusion length from the SnS edge-band. Large, thin flakes supporting ferroelectricity allow investigating domains and domain wall interactions in uniform crystals and lateral heterostructures. Polarized optical microscopy of sub-20 nm flakes consistently shows ⟨110⟩ oriented stripe domains with mirror-twin domain walls. Heterostructures adopt two domain configurations, with domains either constrained to the SnSe core or propagating across the entire SnSe-SnS flakes. The combined results demonstrate multifunctional van der Waals heterostructures with high-quality IFs presenting extraordinary opportunities for manipulating carrier flows and ferroelectric domain patterns.

Response of fs-Laser-Irradiated Diamond by Ultrafast Electron Diffraction

Response of fs-Laser-Irradiated Diamond by Ultrafast Electron Diffraction

Ionisation of atoms determined by kappa refinement against 3D electron diffraction data.

Conventional refinement strategies used for three-dimensional electron diffraction (3D ED) data disregard the bonding effects between the atoms in a molecule by assuming a pure spherical model called the Independent Atom model (IAM) and may lead toan inaccurate or biased structure. Here we show that it is possible to perform a refinement going beyond theIAM with electron diffraction data. We perform kappa refinement which models charge transfers between atoms while assuming a spherical model. We demonstrate the procedure by analysing five inorganic samples; quartz, natrolite, borane, lutecium aluminium garnet, and caesium lead bromide. Implementation of kappa refinement improved the structure model obtained over conventional IAM refinements and provided information on the ionisation of atoms. The results were validated against periodic DFT calculations. The work presents an extension of the conventional refinement of 3D ED data for a more accurate structure model which enables charge density information to be extracted.

A novel grain refinement of Ce-Fe-B magnets induced by magnetic field annealing

Magnetic field annealing-induced grain refinement usually occurs during the crystallization process of amorphous alloys. This work investigates the effects of magnetic field annealing on the microstructure and magnetic properties of crystalline Ce17Fe76Co1Zr0.5B6Mo0.5 alloys. The results indicate that magnetic field annealing below the Curie temperature (TC) of the Ce2Fe14B phase in the alloys reduces the alloy’s grain size. At an annealing temperature of 433 K, the average grain size of alloys decreased from 48.0 nm in the as-spun sample to 27.2 nm in the magnetic field annealing sample. Moreover, magnetic field annealing can effectively reduce the volume fraction of the CeFe2 phase in the alloy. After magnetic field annealing at 433 K, the alloy obtained the optimal comprehensive magnetic properties: the intrinsic coercivity (Hci = 441.1 kA/m), remanence (Br = 0.49 T), squareness (Hk/Hci = 0.53), and maximum energy product ((BH)max) = 35.5 kJ/m3), which were 0.2 %, 16.7 %, 6 %, and 29.1 % higher than the values of the as-spun sample, respectively. Precession electron diffraction (PED) analysis revealed that magnetic field annealing increased strain at grain and phase boundaries and a more uniform grain orientation spread (GOS), promoting recrystallization and grain refinement. This study provides new insights into the grain refinement mechanism of crystalline alloys under magnetic field annealing, contributing to further improving the magnetic properties of Ce-Fe-B magnets.

Synthesis and Structure Determination by 3D Electron Diffraction of the Extra‐large Pore Zeolite ITQ‐70

In this study, we present the synthesis, characterization, and structural analysis of a novel zeolite, ITQ‐70, using 3D electron diffraction tomography. This unique material was synthesized under alkaline conditions, employing tetrakis(diethylamino)phosphonium as organic structure‐directing agent, leading to the formation of a pure silica zeolite. ITQ‐70 is distinguished by its extra‐large pore apertures, which extend along all three axes and intersect one to each other. A notable feature of this zeolite is the presence of structurally ordered defects in very high concentration (38% of the silicon atoms). As a result, ITQ‐70 exhibits the lowest framework density (10.0 T/1000Å3) ever reported for any zeolite except RWY (7.6 T/1000Å3), which contains sulfur instead of oxygen connecting T‐atoms.

Synthesis and Structure Determination by 3D Electron Diffraction of the Extra-large Pore Zeolite ITQ-70.

In this study, we present the synthesis, characterization, and structural analysis of a novel zeolite, ITQ-70, using 3D electron diffraction tomography. This unique material was synthesized under alkaline conditions, employing tetrakis(diethylamino)phosphonium as organic structure-directing agent, leading to the formation of a pure silica zeolite. ITQ-70 is distinguished by its extra-large pore apertures, which extend along all three axes and intersect one to each other. A notable feature of this zeolite is the presence of structurally ordered defects in very high concentration (38% of the silicon atoms). As a result, ITQ-70 exhibits the lowest framework density (10.0 T/1000Å3) ever reported for any zeolite except RWY (7.6 T/1000Å3), which contains sulfur instead of oxygen connecting T-atoms.

Element-Specific Ultrafast Lattice Dynamics in Monolayer WSe2.

We study monolayer WSe2 using ultrafast electron diffraction. We introduce an approach to quantitatively extract atomic-site-specific information, providing an element-specific view of incoherent atomic vibrations following femtosecond excitation. Via differences between W and Se vibrations, we identify stages in the nonthermal evolution of the phonon population. Combined with a calculated phonon dispersion, this element specificity enables us to identify a long-lasting overpopulation of specific optical phonons and to interpret the stages as energy transfer processes between specific phonon groups. These results demonstrate the appeal of resolving element-specific vibrational information in the ultrafast time domain.

Acoustic shock wave-induced sp2-to-sp3-type phase transition-part II: Evidence of the presence of diamond from valance band spectra and electronic diffraction pattern

Here, we introduce a novel technique that utilizes repeated exposure to low-pressure (2.0 MPa) millisecond acoustic shock waves on a graphite sample to facilitate the successful transformation of graphite into diamond. This transformation is based on a martensitic nucleation mechanism verified through valance-band X-ray photoelectron spectroscopic and electron diffraction observations. Typically, diamond formation occurs only under pressures of 50–60 GPa or more in nanosecond dynamic compression experiments. The present work offers a new platform to make synthetic diamonds and a new scientific path for diamond formation.

Outstanding Activity and Durability of Supported NiCo2O4 Nanoparticles for Direct Ethanol Fuel Cells

ABSTRACTThe rational design of noble metal‐free electrocatalysts represents one of the basic stones for fuel cell development. With the exploration of eco‐friendly nanomaterials for the investigated alcohol oxidation process, nickel‐based electrodes have been recognized as the most auspicious anodes with promoted activity and stability. In this work, a series of NiCo2O4 nanoparticles were deposited onto graphite sheets (NiCo2O4/T) introducing varied proportions of cobalt oxide species. Co‐precipitation protocol of the respective metallic hydroxides onto the carbonaceous support was followed with consecutive annealing in an air atmosphere at 400°C. The fabricated mixed metallic oxide nanopowder was physically studied using X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X‐ray analysis (EDX), X‐ray photoelectron spectroscopy (XPS), and selected area electron diffraction (SAED). Uniformly arranged nanoparticles were observed on graphite surface as evidenced by SEM and TEM. The cubic lattice structure of formed NiCo2O4 crystals was also confirmed by XRD through the defined peaks of binary metallic oxides clarifying their successful preparation scheme. The electrocatalytic properties of these NiCo2O4/T nanocatalysts were evaluated for oxidizing ethanol molecules in basic solution. Pronounced oxidation current densities were remarkably measured at NiCo2O4/T electrodes in relation to that at NiO/T. Differing the introduced cobalt oxide content into the synthesized nanocatalyst significantly controlled its catalytic performance. NiCo2O4/T‐20 exhibited the highest activity and stability among the prepared nanomaterials. Much decreased charge transfer resistances were also recorded at this electrode demonstrating its promoted electron transfer characteristics. This work could provide a reasonable route for the simple synthesis of comparable transition metallic oxides with promising attitudes for energy generation purposes.

MicroED: Unveiling the Structural Chemistry of Plant Biomineralisation.

Plants are able to produce various types of crystals through metabolic processes, serving functions ranging from herbivore deterrence to photosynthetic efficiency. However, the structural analysis of these crystals has remained challenging due to their small and often imperfect nature, which renders traditional X-ray diffraction techniques unsuitable. This study explores the use of Microcrystal Electron Diffraction (microED) as a novel method for the structural analysis of plant-derived microcrystals, focusing on Armeria maritima (Milld.), a halophytic plant known for its biomineralisation capabilities. In this study, A. maritima plants were cultivated under controlled laboratory conditions with exposure to cadmium and thallium to induce the formation of crystalline deposits on their leaf surfaces. These deposits were analysed using microED, revealing the presence of sodium chloride (halite), sodium sulphate (thénardite), and calcium sulphate dihydrate (gypsum). Our findings highlight the potential of microED as a versatile tool in plant science, capable of providing detailed structural insights into biomineralisation processes, even from minimal and imperfect crystalline samples. The application of microED in this context not only advances the present understanding of A. maritima's adaptation to saline environments but also opens new avenues for exploring the structural chemistry of biomineralisation in other plant species. Our study advocates for the broader adoption of microED in botanical research, especially when dealing with challenging crystallographic problems.

Structural Integrities of Symmetric and Unsymmetric trans-Bis-pyridyl Ethylene Powders Exposed to Gamma Radiation: Packing and Electronic Considerations Assisted by Electron Diffraction.

Radiation detection (dosimetry) most commonly uses scintillating materials in a wide array of fields, ranging from energy to medicine. Scintillators must be able to not only fluoresce owing to the presence of a suitable chromophore but also withstand damage from radiation over prolonged periods of time. While it is inevitable that radiation will cause damage to the physical and chemical properties of materials, there is limited understanding of features within solid-state scintillators that afford increased structural integrity upon exposure to gamma (γ) radiation. Even fewer studies have evaluated both physical- and atomistic-level properties of organic solid-state materials. Previous work demonstrated cocrystalline materials afford radiation resistance in comparison to the single component counterparts, as realized by trans-1,2-bis(4-pyridyl)ethylene (4,4'-bpe). To support the rational design of radiation-resistant scintillators, we have examined all symmetric and unsymmetric isomers of trans-1-(n-pyridyl)2-(m-pyridyl)ethylene (n,m'-bpe, where n and/or m = 2, 3, or 4) solid-state crystalline materials. Experimental methods employed include single-crystal, powder, and electron diffraction as well as solid-state fluorimetry. Periodic density functional theory (DFT) calculations were used to understand the atomistic-level differences in bond lengths, bond orders, and packing. Electron diffraction was also utilized to determine the structure of a nanocrystalline sample. The results provide insights into possible trends involving factors such as molecular symmetry which provides radiation resistance as well as information for rationally designing single and multicomponent scintillators with the intent of minimizing changes upon γ-radiation exposure.