Crystal lattice image reconstruction from Moiré sampling scanning transmission electron microscopy.

A wide range of reconstruction methods exist nowadays to retrieve data from their undersampled acquisition schemes. In the context of Scanning Transmission Electron Microscopy (STEM), compressed sensing methods successfully demonstrated the ability to retrieve crystalline lattice images from undersampled electron micrographs. In this manuscript, an alternative method is proposed based on the principles of Moiré sampling by intentionally generating aliasing artifacts and correcting them afterwards. The interference between the scanning grid of the electron beam raster and the crystalline lattice results in the formation of predictable sets of Moiré fringes (STEM Moiré hologram). Since the aliasing artifacts are simple spatial frequency shifts applied on each crystalline reflection, the crystal lattices can be recovered from the STEM Moiré hologram by reverting the aliasing frequency shifts from the Moiré reflections. Two methods are presented to determine the aliasing shifts for all the resolved crystalline reflections. The first approach is a prior knowledge-based method using information on the spatial frequency distribution of the crystal lattices (a common case in practice). The other option is a multiple sampling approach using different sampling parameters and does not require any prior knowledge. As an example, the Moiré sampling recovery method detailed in this manuscript is applied to retrieve the crystalline lattices from a STEM Moiré hologram recorded on a silicon sample. The great interest of STEM Moiré interferometry is to increase the field of view (FOV) of the electron micrograph (up to several microns). The Moiré sampling recovery method extends the application of the STEM imaging of crystalline materials towards low magnifications.

Sampling optimization of Moiré geometrical phase analysis for strain characterization in scanning transmission electron microscopy.

A strain characterization technique in a Scanning Transmission Electron Microscope (STEM) called "STEM Moiré GPA" (SMG) emerged recently as an efficient method to map the deformation field on large field of views (up to few microns in length scale). The technique is based on the interference between the scanning grid of the STEM electron probe and the periodic lattice of a crystalline material. The interference pattern (STEM Moiré hologram) is the result of an undersampling artifact, commonly named aliasing, occurring when less than two pixels are used to record a lattice spacing. The phase of the STEM Moiré fringes embeds the crystalline structure of the sample, and the variation of the phase can be related to a deformation field. To acquire a STEM Moiré hologram, the current practice is limited to choosing the periodicity of the scanning grid (pixel spacing) close to one lattice spacing. Such empirical recommendations are, however, insufficient since multiple lattice spacings are undersampled at once. The aliased spatial frequencies can overlap with each other in Fourier space making the STEM Moiré hologram not suitable for Geometric Phase Analysis (GPA) processing. In this study, a procedure is proposed to choose the optimal sampling parameters (pixel spacing and scanning rotation) for the STEM Moiré GPA application on any single crystal material. The procedure is then applied on a InP/InAs1-xPx/InP stack grown by Molecular Beam Epitaxy (MBE). Deformation profiles from different sampling conditions are compared to the established High-Resolution STEM GPA method, highlighting the reliability of the SMG method following the optimization process. The optimization protocol and the limits of SMG are finally discussed, and a generalization of the coherent sampling concept is proposed.

Towards calibration-invariant spectroscopy using deep learning.

The interaction between matter and electromagnetic radiation provides a rich understanding of what the matter is composed of and how it can be quantified using spectrometers. In many cases, however, the calibration of the spectrometer changes as a function of time (such as in electron spectrometers), or the absolute calibration may be different between different instruments. Calibration differences cause difficulties in comparing the absolute position of measured emission or absorption peaks between different instruments and even different measurements taken at different times on the same instrument. Present methods of avoiding this issue involve manual feature extraction of the original signal or qualitative analysis. Here we propose automated feature extraction using deep convolutional neural networks to determine the class of compound given only the shape of the spectrum. We classify three unique electronic environments of manganese (being relevant to many battery materials applications) in electron energy loss spectroscopy using 2001 spectra we collected in addition to testing on spectra from different instruments. We test a variety of commonly used neural network architectures found in the literature and propose a new fully convolutional architecture with improved translation-invariance which is immune to calibration differences.

Nanoscale mechanism of the stabilization of nanoporous gold by alloyed platinum.

Nanoporous gold (NPG) is usually made by electrochemical dealloying of Ag from binary AgAu alloys. The resulting nanoscale ligaments are not very stable, and tend to coarsen with time by surface self-diffusion, especially in electrolyte, which may lead to inferior electrocatalytic properties. Addition of a small amount of Pt to the precursor alloy is known to refine and stabilize the nanoporous product (NPG-Pt). However, the mechanisms by which Pt serves to refine the microstructure remain poorly understood. The present study aims to expand our knowledge of the role of Pt by examining NPG-Pt at atomic resolution with Atom Probe Tomography (APT), as well as by aberration-corrected Transmission Electron Microscopy. Atomic level observation of Pt enrichment on ligament surfaces sheds light on the underlying mechanisms that give rise to Pt's refining effect. Owing to improved Ag retention with higher Pt content, NPG-Pt1 (made by dealloying Ag77Au22Pt1) was shown to have the highest surface area-to-volume ratio, compared to NPG-Pt3 (made by dealloying Ag77Au20Pt3). Quantitative estimates reveal up to 5-fold enrichment of Pt at nanoligament surfaces, compared to the precursor content, in NPG-Pt. The interface between the dealloyed layer and the substrate was captured by APT, for the first time. The findings of this investigation add insight into the functionality of NPG-Pt and its prospective catalytic performance.

2D strain mapping using scanning transmission electron microscopy Moiré interferometry and geometrical phase analysis.

A strain characterization technique based on Moiré interferometry in a scanning transmission electron microscope (STEM) and geometrical phase analysis (GPA) method is demonstrated. The deformation field is first captured in a single STEM Moiré hologram composed of multiple sets of periodic fringes (Moiré patterns) generated from the interference between the periodic scanning grating, fixing the positions of the electron probe on the sample, and the crystal structure. Applying basic principles from sampling theory, the Moiré patterns arrangement is then simulated using a STEM electron micrograph reference to convert the experimental STEM Moiré hologram into information related to the crystal lattice periodicities. The GPA method is finally applied to extract the 2D relative strain and rotation fields. The STEM Moiré interferometry enables the local information to be de-magnified to a large length scale, comparable to what can be achieved in dark-field electron holography. The STEM Moiré GPA method thus extends the conventional high-resolution STEM GPA capabilities by providing comparable quantitative 2D strain mapping with a larger field of view (up to a few microns).

Three-Dimensional Quantum Confinement of Charge Carriers in Self-Organized AlGaN Nanowires: A Viable Route to Electrically Injected Deep Ultraviolet Lasers.

We report on the molecular beam epitaxial growth and structural characterization of self-organized AlGaN nanowire arrays on Si substrate with high luminescence efficiency emission in the deep ultraviolet (UV) wavelength range. It is found that, with increasing Al concentration, atomic-scale compositional modulations can be realized, leading to three-dimensional quantum confinement of charge carriers. By further exploiting the Anderson localization of light, we have demonstrated, for the first time, electrically injected AlGaN lasers in the deep UV band operating at room temperature. The laser operates at ∼289 nm and exhibits a threshold of 300 A/cm(2), which is significantly smaller compared to the previously reported electrically injected AlGaN multiple quantum well lasers.

Atomic scale real-space mapping of holes in YBa2Cu3O(6+δ).

The high-temperature superconductor YBa2Cu3O(6+δ) consists of two main structural units--a bilayer of CuO2 planes that are central to superconductivity and a CuO(2+δ) chain layer. Although the functional role of the planes and chains has long been established, most probes integrate over both, which makes it difficult to distinguish the contribution of each. Here we use electron energy loss spectroscopy to directly resolve the plane and chain contributions to the electronic structure in YBa2Cu3O6 and YBa2Cu3O7. We directly probe the charge transfer of holes from the chains to the planes as a function of oxygen content, and show that the change in orbital occupation of Cu is large in the chain layer but modest in CuO2 planes, with holes in the planes doped primarily into the O 2p states. These results provide direct insight into the local electronic structure and charge transfers in this important high-temperature superconductor.

Analytical electron microscopy of a crack tip extracted from a stressed Alloy 800 sample exposed to an acid sulfate environment.

Alloy 800 (Fe-21Cr-33Ni) has been found susceptible to cracking in acid sulfate environments, but the mechanism is not well understood. Alloy 800 C-ring samples were exposed to an acid sulfate environment at 315°C and cracks were found with depths in excess of 300µm after 60h. Preparation of a TEM sample containing crack tips is challenging, but the ability to perform high-resolution microscopy at the crack tip would lend insight to the mechanism of acid sulfate stress corrosion cracking (AcSCC). The lift-out technique combined with a focused ion beam sample preparation was used to extract a crack tip along the cross-section of an acid sulfate crack in an Alloy 800 C-ring. TEM elemental analysis was done using EDS and EELS which identified a duplex oxide within the crack; an inner oxide consisting of a thin 3-4nm Cr-rich oxide and an outer oxide enriched in Fe and Cr. Preliminary conclusions and hypotheses resulted with respect to the mechanism of AcSCC in Alloy 800.

Sub-ångstrom experimental validation of molecular dynamics for predictive modeling of extended defect structures in Si.

In this Letter we present the detailed, quantitative comparison between experimentally and theoretically derived structures of the extended {311} defect in silicon. Agreement between experimental and theoretical column positions of better than ±0.05 nm has been achieved for all 100 atomic columns in the defect structure. This represents a calculated density of 5.5×10(14) silicon interstitials per cm(2) on {311} planes, in agreement with previous work [S. Takeda, Jpn. J. Appl. Phys., Part 2, 30, L639 (1991)]. We show that although the {311} defect is made up of five-, six-, seven-, and eight-member rings, the shape of these rings varies as a function of position along the defect, and these variations can be determined experimentally with high precision and accuracy. The excellent agreement between the calculated and experimentally derived structure, including the position of atomic columns and the shape of the distinct structural units of the defect, provides strong evidence for the quality and robustness of the molecular dynamics simulation approach for structural studies of defects. The experimental approach is straightforward, without the need for complicated image processing methods, and is therefore widely applicable.

Quantitative statistical analysis, optimization and noise reduction of atomic resolved electron energy loss spectrum images.

In this work we investigate methods of statistical processing and background fitting of atomic resolution electron energy loss spectrum image (SI) data. Application of principal component analysis to SI data has been analyzed in terms of the spectral signal-to-noise ratio (SNR) and was found to improve both the spectral SNR and its standard deviation over the SI, though only the latter was found to improve significantly and consistently across all data sets analyzed. The influence of the number of principal components used in the reconstructed data set on the SNR and resultant elemental maps has been analyzed and the experimental results are compared to theoretical calculations.

p-Type modulation doped InGaN/GaN dot-in-a-wire white-light-emitting diodes monolithically grown on Si(111).

Full-color, catalyst-free InGaN/GaN dot-in-a-wire light-emitting diodes (LEDs) were monolithically grown on Si(111) by molecular beam epitaxy, with the emission characteristics controlled by the dot properties in a single epitaxial growth step. With the use of p-type modulation doping in the dot-in-a-wire heterostructures, we have demonstrated the most efficient phosphor-free white LEDs ever reported, which exhibit an internal quantum efficiency of ∼56.8%, nearly unaltered CIE chromaticity coordinates with increasing injection current, and virtually zero efficiency droop at current densities up to ∼640 A/cm(2). The remarkable performance is attributed to the superior three-dimensional carrier confinement provided by the electronically coupled dot-in-a-wire heterostructures, the nearly defect- and strain-free GaN nanowires, and the significantly enhanced hole transport due to the p-type modulation doping.

Iron oxyhydroxide colloid formation by gamma-radiolysis.

Gamma-irradiation of deaerated aqueous solutions containing FeSO(4) leads to the formation of uniform-sized colloidal particles of γ-FeOOH. At short irradiation times, or in solutions with a low initial [Fe(2+)](0), spherical particles with a size less than 10 nm are formed. These primary particles grow to form a dendritic structure upon longer irradiation, and the final size of the large particles is ∼60 nm with a very narrow size distribution. Further prolonged irradiation does not change the final particle size. The narrow size distribution is attributed to rapid homogeneous radiolytic oxidation of soluble Fe(2+) to relatively insoluble Fe(3+) hydroxides [Fe(H(2)O)(6-n)(OH)(n)](3-n) leading to particle nucleation by spontaneous condensation. These primary particles then grow into γ-FeOOH particles with a dendritic structure. The final size reached at long times is regulated by the steady-state redox conditions established during long-term irradiation at the aqueous-solid interface.

Multipolar plasmonic resonances in silver nanowire antennas imaged with a subnanometer electron probe.

We detect short-range surface plasmon-polariton (SR-SPP) resonances setup in individual silver nanoantenna structures at high-spatial resolution with a scanning, subnanometer electron probe. Both even and odd multipolar resonant modes are resolved up to sixth order, and we measure their spatial distribution in relation to nanoantenna structures at energies down to 0.55 eV. Fabry-Perot type SR-SPP reflection phase shifts are calculated from direct measurements of antinode spacings in high-resolution plasmonic field maps. We observe resonant SR-SPP antinode bunching at nanoantenna terminals in high-order resonant modes, and antinode shifts in nonhomogeneous local environments. Finally, we achieve good agreement of our experimental SR-SPP maps with numerical calculations of photon excited near fields, using a novel integrated photon excitation geometry.

Interplay between structural, electronic, and magnetic degrees of freedom in Sr(3)Cr(2)O(8).

We present a theoretical investigation of the orbital ordering occurring in Sr(3)Cr(2)O(8) based on density functional theory calculations. We demonstrate that the strong electron correlation arising within the Cr-3d shell can clearly explain both the phase transition leading to the stabilization of its monoclinic C2/c space-group symmetry and its spin-singlet magnetic ground state. The relevance of the electronic structure determined theoretically is further established by comparison to high-resolution electron energy loss spectroscopy measurements.

Visualizing biointerfaces in three dimensions: electron tomography of the bone-hydroxyapatite interface.

A positive interaction between human bone tissue and synthetics is crucial for the success of bone-regenerative materials. A greater understanding of the mechanisms governing bone-bonding is often gained via visualization of the bone-implant interface. Interfaces to bone have long been imaged with light, X-rays and electrons. Most of these techniques, however, only provide low-resolution or two-dimensional information. With the advances in modern day transmission electron microscopy, including new hardware and increased software computational speeds, the high-resolution visualization and analysis of three-dimensional structures is possible via electron tomography. We report, for the first time, a three-dimensional reconstruction of the interface between human bone and a hydroxyapatite implant using Z-contrast electron tomography. Viewing this structure in three dimensions enabled us to observe the nanometre differences in the orientation of hydroxyapatite crystals precipitated on the implant surface in vivo versus those in the collagen matrix of bone. Insight into the morphology of biointerfaces is considerably enhanced with three-dimensional techniques. In this regard, electron tomography may revolutionize the approach to high-resolution biointerface characterization.

Investigation of the oxide shell forming on epsilon-Co nanocrystals.

This paper reports on the TEM characterization of the surface oxide layer forming on Co nanocrystals (NCs) prepared using a standard method [Puntes, V.F., Krishnan, K.M., Alivisatos, P., 2001. Synthesis, self-assembly, and magnetic behavior of a two-dimensional superlattice of single-crystal epsilon-Co nanoparticles. Appl. Phys. Lett. 78 (15), 2187-2189]. Complementary transmission electron microscopy (TEM)-related techniques presented direct evidence of a 1.5-3nm CoO shell forming on epsilon-Co NCs. The crystalline structure of the Co NCs was confirmed by selected area diffraction study while the nature of the shell was probed by energy-loss near-edge spectroscopy and energy-filtered TEM. Based on these results, we comment on the detection of nanoscale feature with energy-filtered imaging.

Electron inelastic scattering and anisotropy: The two-dimensional point of view.

The measurement of the electronic structure of anisotropic materials using energy loss near edge structure (ELNES) spectroscopy is an important field of microanalysis in transmission electron microscopy. We present a novel method to study the angular dependence of electron inelastic scattering in anisotropic materials. This method has been applied to the study of 1s-->pi* and sigma* transitions on the carbon K edge in pyrolitic graphite. An excellent agreement between experimental and theoretical two-dimensional scattering patterns has been found. In particular, the need of a fully relativistic calculation of the inelastic scattering cross-section to explain the experimental results is demonstrated.

Enhancement of resolution in core-loss and low-loss spectroscopy in a monochromated microscope.

The significant enhancement of the energy resolution in the new generation of commercially available monochromated transmission electron microscopes presents new challenges in term of selecting the correct experimental conditions and understanding the various effects that can potentially influence the quality of the EELS data. In this respect we investigated the effect of point spread function of the detector and spectrum-diffraction mixing on the energy resolution and the intensity of the zero loss peak tails. Alternative approaches to improve the energy resolution by mathematical methods have been tested. By using a simple and commonly available test case (Si L(2,3) edges) we assessed the efficiency of the deconvolution algorithms to improve the resolution. The results show that the deconvolution is not always successful in improving the resolution of the core loss EELS data and the results may not always be reliable. Contrary to this, the application of the Richardson-Lucy deconvolution algorithm on some bandgap measurements data appears to be very effective. The procedure proved successful in removing the contribution of the zero-loss peak tails and allows an easier access to spectroscopic information starting at energy losses as low as of 0.5 eV with monochromated spectra and 1 eV with the non-monochromated spectra.

A novel tool for high-resolution transmission electron microscopy of intact interfaces between bone and metallic implants.

A key feature in the understanding of the mechanisms of integration versus rejection of implanted materials is a deepened understanding of the elemental and molecular compositions of the interface zone between the surface of the synthetic man-made material and the biological components of tissue. Intact interfaces between metallic implants and tissues have not been able to image and analyse on the ultrastructural level with the common transmission electron microscopy (TEM) sample preparation techniques. By using focused ion beam microscopy for site-specific preparation of TEM samples, intact interfaces between metal implants and calcified tissue were imaged for the first time. The interface's elemental and crystallographic compositions were determined using energy dispersive X-ray mapping and electron diffraction. The developed technique fulfills a long-sought-for demand to correlate the surface properties of implanted metal prostheses with the fine structure and composition of preserved interfaces with tissues.