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Advances in the electron diffraction characterization of atomic clusters and nanoparticles

Nanoparticles and metallic clusters continue to make a remarkable impact on novel and emerging technologies. In recent years, there have been impressive advances in the controlled synthesis of clusters and their advanced characterization. One of the most common ways to determine the structures of nanoparticles and clusters is by means of X-ray diffraction methods. However, this requires the clusters to crystallize in a similar way to those used in protein studies, which is not possible in many cases. Novel methods based on electron diffraction have been used to efficiently study individual nanoparticles and clusters and these can overcome the obstacles commonly encountered during X-ray diffraction methods without the need for large crystals. These novel methodologies have improved with advances in electron microscopy instrumentation and electron detection. Here, we review advanced methodologies for characterizing metallic nanoparticles and clusters using a variety of electron diffraction procedures. These include selected area electron diffraction, nanobeam diffraction, coherent electron diffraction, precession electron diffraction, scanning transmission electron microcopy diffraction, and high throughput data analytics, which leverage deep learning to reduce the propensity for data errors and translate nanometer and atomic scale measurements into material data.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

X-ray linear dichroic ptychography

Biominerals such as seashells, coral skeletons, bone, and tooth enamel are optically anisotropic crystalline materials with unique nanoscale and microscale organization that translates into exceptional macroscopic mechanical properties, providing inspiration for engineering new and superior biomimetic structures. Using Seriatopora aculeata coral skeleton as a model, here, we experimentally demonstrate X-ray linear dichroic ptychography and map the c-axis orientations of the aragonite (CaCO 3 ) crystals. Linear dichroic phase imaging at the oxygen K-edge energy shows strong polarization-dependent contrast and reveals the presence of both narrow (<35°) and wide (>35°) c-axis angular spread in the coral samples. These X-ray ptychography results are corroborated by four-dimensional (4D) scanning transmission electron microscopy (STEM) on the same samples. Evidence of co-oriented, but disconnected, corallite subdomains indicates jagged crystal boundaries consistent with formation by amorphous nanoparticle attachment. We expect that the combination of X-ray linear dichroic ptychography and 4D STEM could be an important multimodal tool to study nano-crystallites, interfaces, nucleation, and mineral growth of optically anisotropic materials at multiple length scales.

4D scanning transmission electron microscopy↗

Tracking defect type and strain relaxation in patterned Ge/Si(001) islands by x-ray forbidden reflection analysis

Plastic relaxation and formation of defects are crucial issues in the epitaxial growth of nanoparticles and thin films. Indeed, defects generate local stress in the crystalline lattice, which affects their surroundings and may lead to undesired effects such as reduced charge-carrier lifetime or nonradiative recombinations. Here, we use a nondestructive method based on x-ray diffuse scattering close to forbidden reflections to identify the defect types with a high sensitivity and quantify their average size and strain field. Combined with transmission electron microscopy, it offers opportunities to track both ensemble average and single defects inside three-dimensional structures. These techniques have been applied to partially embedded and high-Ge-content (x{sub Ge}=0.87{+-}0.06) dots selectively grown in 20-nm-sized pits on Si(001) surfaces through openings in a SiO{sub 2} template. The stress in the 20-nm-wide Ge islands is relaxed not only by interfacial dislocations but also by microtwins and/or stacking faults located at the interface, proving the importance of {l_brace}111{r_brace} planes and twinning in the relaxation process of nanometer-size Ge dots.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Correlative image learning of chemo-mechanics in phase-transforming solids

We report constitutive laws underlie most physical processes in nature. However, learning such equations in heterogeneous solids (for example, due to phase separation) is challenging. One such relationship is between composition and eigenstrain, which governs the chemo-mechanical expansion in solids. Here we developed a generalizable, physically constrained image-learning framework to algorithmically learn the chemo-mechanical constitutive law at the nanoscale from correlative four-dimensional scanning transmission electron microscopy and X-ray spectro-ptychography images. We demonstrated this approach on Li X FePO 4 , a technologically relevant battery positive electrode material. We uncovered the functional form of the composition–eigenstrain relation in this two-phase binary solid across the entire composition range (0 ≤ X ≤ 1), including inside the thermodynamically unstable miscibility gap. The learned relation directly validates Vegard’s law of linear response at the nanoscale. Our physics-constrained data-driven approach directly visualizes the residual strain field (by removing the compositional and coherency strain), which is otherwise impossible to quantify. Heterogeneities in the residual strain arise from misfit dislocations and were independently verified by X-ray diffraction line profile analysis. Our work provides the means to simultaneously quantify chemical expansion, coherency strain and dislocations in battery electrodes, which has implications on rate capabilities and lifetime. Broadly, this work also highlights the potential of integrating correlative microscopy and image learning for extracting material properties and physics.

36 MATERIALS SCIENCE↗

Defect Formation in GaN Epitaxial Layers due to SHI Irradiation

GaN epitaxial layers were irradiated with 200 MeV swift heavy Ag ions at various fluences. These samples were then characterized by XRD and TEM. Increase in peak width (FWHM) with incident ion dose showed reduction in crystallinity of epitaxial layers. Cross sectional TEM images confirmed that at highest fluence (5x10{sup 12} ions/cm{sup 2}) electronic energy loss process caused structural defect formation in GaN layer.

36 MATERIALS SCIENCE↗

Present Status of the Nanotomography System at BL47XU at SPring-8 and Its Efficiency Improvement Using Double-Condenser Optics

Although imaging x-ray nanotomography developed at beamline BL47XU of SPring-8 has reached a spatial resolution less than 200 nm, poor intensity and low signal-to-noise ratio are more serious problems in the system using zone plate optics. Improvement of the diffraction efficiency of Koehler illumination optics is attempted by doubling two condenser zone plates, which have a constant grating pitch of 200 nm. Although a long longitudinal distance between two condensers is possible ({approx}100 mm), efficiency varies periodically as the distance is changed due to the Talbot effect. A maximum efficiency close to 0.3 is obtained with a periodic distance of approximately 500 {mu}m.

43 PARTICLE ACCELERATORS↗

Diffraction enhanced imaging utilizing a laser produced x-ray source

Image formation by Fresnel diffraction utilizes both absorption and phase-contrast to measure electron density profiles. The low spatial and spectral coherence requirements allow the technique to be performed with a laser-produced x-ray source coupled with a narrow slit. This makes it an excellent candidate for probing interfaces between materials at extreme conditions, which can only be generated at large-scale laser or pulsed power facilities. Here, we present the results from a proof-of-principle experiment demonstrating an effective ~2 μm laser-generated source at the OMEGA Laser Facility. This was achieved using slits of 1 × 30 μm 2 and 2 × 40 μm 2 geometry, which were milled into 30 μm thick Ta plates. Combining these slits with a vanadium He-like 5.2 keV source created a 1D imaging system capable of micrometer-scale resolution. The principal obstacles to achieving an effective 1 μm source are the slit tilt and taper—where the use of a tapered slit is necessary to increase the alignment tolerance. We demonstrate an effective source size by imaging a 2 ± 0.2 μm radius tungsten wire.

3D printing↗

Electronic-grade GaN(0001)/Al{sub 2}O{sub 3}(0001) grown by reactive DC-magnetron sputter epitaxy using a liquid Ga target

Electronic-grade GaN (0001) epilayers have been grown directly on Al{sub 2}O{sub 3} (0001) substrates by reactive direct-current-magnetron sputter epitaxy (MSE) using a liquid Ga sputtering target in an Ar/N{sub 2} atmosphere. The as-grown GaN epitaxial films exhibit low threading dislocation density on the order of {<=}10{sup 10} cm{sup -2} determined by transmission electron microscopy and modified Williamson-Hall plot. X-ray rocking curve shows narrow full-width at half maximum (FWHM) of 1054 arc sec of the 0002 reflection. A sharp 4 K photoluminescence peak at 3.474 eV with a FWHM of 6.3 meV is attributed to intrinsic GaN band edge emission. The high structural and optical qualities indicate that MSE-grown GaN epilayers can be used for fabricating high-performance devices without the need of any buffer layer.

36 MATERIALS SCIENCE↗

In‐Operando Spatiotemporal Imaging of Coupled Film‐Substrate Elastodynamics During an Insulator‐to‐Metal Transition

Abstract The drive toward non‐von Neumann device architectures has led to an intense focus on insulator‐to‐metal (IMT) and the converse metal‐to‐insulator (MIT) transitions. Studies of electric field‐driven IMT in the prototypical VO 2 thin‐film channel devices are largely focused on the electrical and elastic responses of the films, but the response of the corresponding TiO 2 substrate is often overlooked, since it is nominally expected to be electrically passive and elastically rigid. Here, in‐operando spatiotemporal imaging of the coupled elastodynamics using X‐ray diffraction microscopy of a VO 2 film channel device on TiO 2 substrate reveals two new surprises. First, the film channel bulges during the IMT, the opposite of the expected shrinking in the film undergoing IMT. Second, a microns thick proximal layer in the substrate also coherently bulges accompanying the IMT in the film, which is completely unexpected. Phase‐field simulations of coupled IMT, oxygen vacancy electronic dynamics, and electronic carrier diffusion incorporating thermal and strain effects suggest that the observed elastodynamics can be explained by the known naturally occurring oxygen vacancies that rapidly ionize (and deionize) in concert with the IMT (MIT). Fast electrical‐triggering of the IMT via ionizing defects and an active “IMT‐like” substrate layer are critical aspects to consider in device applications.

36 MATERIALS SCIENCE↗

Study on mechanism of photocatalytic performance of La-doped TiO{sub 2}/Ti photoelectrodes by theoretical and experimental methods

TiO{sub 2} photoelectrodes with various nanostructures have been successfully prepared by the anodization method. The morphology, microstructure and optical properties of as-prepared photoelectrodes were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD), ultraviolet/visible light diffuse reflectance spectra (UV/vis/DRS), surface photovoltage spectroscopy (SPS) and photocurrent. The electronic structure and optical properties of La doped/undoped TiO{sub 2} photoelectrodes with different crystal structures were calculated by the density function theory. The photocatalytic and photoelectrocatalytic activities of as-prepared photoelectrodes were evaluated. The results showed that the anodization potentials played a crucial role in the surface morphology and microstructure. Both results of theoretical calculations and experimental tests demonstrated that La-doped photoelectrodes were more sensitive to light than undoped one. The difference of photoelectrodes performance was ascribed to the crystal configuration, impurity energy levels and long-range orientation moving of photogenerated carriers. - Graphical abstract: Photophysical chemistry processes in as-prepared TiO{sub 2} photoelectrodes. Overall scheme of TiO{sub 2} photoelectrodes: (A) movement of photoelectrons and holes without bias potentials; (B) movement of photoelectrons and holes at applied bias potentials; (a) and (b) were the transmission of photogenerated electrons and holes of local enlargement of (A) (black open circle): (a) photoelectrons movement in P-TiO{sub 2} photoelectrodes and La-TiO{sub 2} photoelectrodes, the red dot line denotes the top of valence band (VB) and the bottom of conduction band (CB) of pure photoelectrodes; (b) photoelectrons movement in P-160 and La-160 TiO{sub 2} photoelectrodes (mixed crystal phase). The number refers to as follows: (1) transmission process of photoelectrons and holes; (2) recombination process of photoelectrons and holes. Arrows represent the moving direction of photoelectrons. Highlights: Black-Right-Pointing-Pointer Morphology and structure of La-doped photoelectrodes. Black-Right-Pointing-Pointer Band gap and electric structure of La-doped and undoped photoelectrodes. Black-Right-Pointing-Pointer Optical, PECH, PC and PEC properties of La-TiO{sub 2} photoelectrodes. Black-Right-Pointing-Pointer Transmission process of photoelectron-hole pairs in La-TiO{sub 2} photoelectrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Imaging in real and reciprocal space at the Diamond beamline I13

The Diamond Imaging and Coherence beamline I13 consists of two independent branchlines for imaging in real and reciprocal space. Different microscopies are available providing a range of spatial resolution from 5µm to potentially 5nm. The beamline operates in the energy range of 6-35keV covering different scientific areas such as biomedicine, materials science and geophysics. Several original devices have been developed at the beamline, such as the EXCALIBUR photon counting detector and the combined robot arms for coherent X-ray diffraction.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Phase relations in a barium-rich high-temperature region (25-45 mol% CuO, 900-1100 deg. C) of the BaO-CuO{sub x} system

The phase relations have been studied in the BaO-CuO{sub x} system in the range of 25.0-45.0 mol% CuO at 900-1100 deg. C at P(O{sub 2})=21 kPa (air) by visual polythermal analysis (VPA), powder X-ray diffraction (XRD), electron diffraction (ED) with simultaneous energy-dispersive X-ray (EDX) elemental analysis in a transmission electron microscope (TEM), and iodometric chemical analysis. The discrete deviations 2.02 (101:50), 2.04 (102:50), 2.10 (105:50) of Ba/Cu (Ba:Cu) composition from the stoichiometric ratio 2:1 have been found for the known Ba{sub 2}CuO{sub 3+{delta}} oxides in the subsolidus region 900-970 deg. C. Unit cell parameters of the 101:50 orthorhombic oxide, 102:50 tetragonal one, 105:50 orthorhombic one are, respectively, a=4.049, b=3.899, c=13.034 A; a=3.985, c=12.968 A; a=4.087, b=3.897 and c=12.950 A. ED patterns of the 101:50, 102:50, 105:50 oxides show characteristic supercell reflections with the respective vector 1/60[5 4 0], {approx}2/11<1 1 0> and 1/6[2 0 0]. Oxides of the 2:1, 7:4, 5:3 and 23:20 compositions have been found in the crystallization region 970-1050 deg. C. Unit cell parameters of the 2:1 orthorhombic oxide are a=4.095, b=3.795, c=13.165 A. Interplanar spacings and X-ray characteristic peak intensities of the 7:4, 5:3 and 23:20 oxides are given. Oxides 2:1 and 7:4 melt pseudocongruently at 1020 and 1005 deg. C, oxides 5:3 and 23:20 melt incongruently at 995 and 980 deg. C, respectively. A diagram of the phase relations in the studied region of the BaO-CuO{sub x} system has been constructed, whose structure is considered as the total projection of phase states of the system existing for different x. - Graphical Abstract: A diagram of phase relations in the BaO-CuO{sub x} system in the range of 30.0-45.0 mol% CuO at 900-1050 deg. C at P(O{sub 2})=21 kPa (air) constructed on the data obtained by visual polythermal analysis (the liquidus line), XRD and ED with elemental analysis. Highlights: > A combination of physical-chemical and structural methods was used. > New discrete oxides have been found. > The diagram reflects the total projection of phase states at different x.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of Cu Nanowires with Polycarbonate Template

Copper nanowires were fabricated into arrays of pores on ion-track etched polycarbonate membrane, using electrodeposition technique. We coated Au thin film layer on one side of membrane in order to have electrical contact. X-ray diffraction analysis shows that the Au layer has a strong (111) texture. The pores which have cylindrical shape with 6 micron length and 30 nm diameter were filled by copper atoms, fabricating Cu nanowires. Energy Disperse Spectrometry (EDS) indicated the picks of copper which filled the pores of substrate. The morphology and structure of Cu nanowires were characterized by SEM, TEM and XRD, respectively. The results show that although all the nanowires do not have uniform diameter, but all of them are continuous along the length.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Laguerre–Gauss and Hermite–Gauss soft X-ray states generated using diffractive optics

Light’s capacity to carry angular momentum is integral to our knowledge of physics and ability to probe matter. In addition to spin, photons can occupy free-space orbital angular momentum eigenstates. Visible light orbital angular momentum is used in quantum information experiments, super-resolution microscopy, optical tweezers and angular momentum transfer to atoms in optical lattices. Soft X-ray orbital angular momentum applications, slowed by the lack of suitable optics and the rarity of coherent X-ray sources, could enable the direct alteration of atomic states through orbital angular momentum exchange, and methods to study the electronic properties of quantum materials. We have made soft X-ray diffractive optics that generate single Laguerre–Gauss modes, observed carrying up to 30$\hbar$ angular momentum per photon, or their superpositions. We also present Hermite–Gauss diffractive optics and a soft X-ray orbital angular momentum analyser. Finally, these tools could enable both the manipulation and finer characterization of topologically complex electronic matter, such as magnetic skyrmions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Glancing-incidence focussed ion beam milling: A coherent X-ray diffraction study of 3D nano-scale lattice strains and crystal defects

Here, this study presents a detailed examination of the lattice distortions introduced by glancing incidence Focussed Ion Beam (FIB) milling. Using non-destructive multi-reflection Bragg coherent X-ray diffraction we probe damage formation in an initially pristine gold micro-crystal following several stages of FIB milling. These experiments allow access to the full lattice strain tensor in the micro-crystal with ~25 nm 3D spatial resolution, enabling a nano-scale analysis of residual lattice strains and defects formed. Our results show that 30 keV glancing incidence milling produces fewer large defects than normal incidence milling at the same energy. However the resulting residual lattice strains have similar magnitude and extend up to ~50 nm into the sample. At the edges of the milled surface, where the ion-beam tails impact the sample at near-normal incidence, large dislocation loops with a range of Burgers vectors are formed. Further glancing incidence FIB polishing with 5 keV ion energy removes these dislocation loops and reduces the lattice strains caused by higher energy FIB milling. However, even at the lower ion energy, damage-induced lattice strains are present within a ~20 nm thick surface layer. These results highlight the need for careful consideration and management of FIB damage. They also show that low-energy FIB-milling is an effective tool for removing FIB-milling induced lattice strains. This is important for the preparation of micro-mechanical test specimens and strain microscopy samples.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Reuniting crystallography with real space: Ab initio structure elucidation with 4D-STEM

Structure elucidation via single-crystal methods has historically lacked experimental access to real-space information, instead relying exclusively on diffraction-space measurements of Bragg reflections. Here we exploit the dual-space imaging power of 4D scanning transmission electron microscopy to meaningfully integrate real-space information into the crystallographic workflow. We show that virtual apertures assembled by segmentation of high-angle annular dark-field images enable i) pixel-by-pixel separation of coherent Bragg signal from clusters of closely spaced nanocrystals and ii) selective extraction of integrated intensities from thinner subregions of individual specimens, facilitating retroactive tuning of multiple scattering artifacts. This strategy empowers us to simply pick and choose whichever nanoscale regions of interest generate the highest-quality diffraction patterns, allowing us to solve several independent structures of the metal-organic framework UiO-66 from specimens whose agglomerated morphology proved intractable for conventional microcrystal electron diffraction. Our method is compatible with both rotational and serial approaches to data processing, ultimately divulging the first scanning nanobeam electron diffraction structures determined by direct methods at subangstrom resolution.

Saha, Ambarneil↗