Energy-filtered Imaging Research Articles

Tailoring the surface density of silicon nanocrystals embedded in SiOx single layers

In this article, we explore the possibility of modifying the silicon nanocrystal areal density in SiOx single layers, while keeping constant their size. For this purpose, a set of SiOx monolayers with controlled thickness between two thick SiO2 layers has been fabricated, for four different compositions (x = 1, 1.25, 1.5, or 1.75). The structural properties of the SiOx single layers have been analyzed by transmission electron microscopy (TEM) in planar view geometry. Energy-filtered TEM images revealed an almost constant Si-cluster size and a slight increase in the cluster areal density as the silicon content increases in the layers, while high resolution TEM images show that the size of the Si crystalline precipitates largely decreases as the SiOx stoichiometry approaches that of SiO2. The crystalline fraction was evaluated by combining the results from both techniques, finding a crystallinity reduction from 75% to 40%, for x = 1 and 1.75, respectively. Complementary photoluminescence measurements corroborate the precipitation of Si-nanocrystals with excellent emission properties for layers with the largest amount of excess silicon. The integrated emission from the nanoaggregates perfectly scales with their crystalline state, with no detectable emission for crystalline fractions below 40%. The combination of the structural and luminescence observations suggests that small Si precipitates are submitted to a higher compressive local stress applied by the SiO2 matrix that could inhibit the phase separation and, in turn, promotes the creation of nonradiative paths.

Measurements of local chemistry and structure in Ni(O)–YSZ composites during reduction using energy-filtered environmental TEM

Energy-filtered transmission electron microscopy images are acquired during the reduction of a NiO-YSZ composite in H2 up to 600 °C. Temperature-resolved quantitative information about both chemistry and structure is extracted with nm spatial resolution from the data, paving the way for the development of detailed reduction models.

Oxidation State Imaging of Ceria Island Growth on Re(0001)

High resolution X-ray photoemission electron microscopy (XPEEM) and low energy electron microscopy (LEEM) have been used to investigate the growth of ultrathin CeOx(111) on Re(0001), a model catalyst system. Rotational domains of CeOx(111) are identified with microprobe low energy electron diffraction (LEED) and dark-field LEEM. In the regions not covered by the ceria islands, a surface rhenium-oxide layer has been observed using energy-filtered XPEEM imaging and spectroscopy. The oxidation state of the ceria is key to its catalytic activity. For this reason we have employed resonant photoelectron spectroscopy of the Ce 4f contributions to the valence band to monitor the relative Ce3+ and Ce4+ concentrations. The overall stoichiometry of the moderately reduced film was CeO1.63. Resonant energy-filtered XPEEM imaging of the Ce oxidation state allowed us to confirm the uniformity of this stoichiometry across the ceria islands that constituted the film.

Extended planar defects and the rapid incorporation of Ti4+ into olivine

The formation of extended planar defects in minerals such as olivine is related to high point defect concentration and can be driven by large gradients in chemical potential, where the energy of the system is lowered by the ordering of defects along specific planes in the crystal. The presence of extended defects has the potential to create the (apparently) anomalous ionic diffusion in olivine as reported recently (Spandler and O’Neill in Contrib Mineral Petrol 159(6):791–818, 2010). High-resolution transmission electron microscopy and energy-filtered imaging were done using experimental samples designed to examine the impact of a TiO2 and f O2 on the potential to form such defects in ferromagnesian olivine. Doped basalt (5 wt% TiO2)–olivine reaction couple experiments were run at 1 atm and 1,310 and 1,410 °C for 50 h at various f O2, ranging from 102 below to 102 above the quartz–fayalite–magnetite buffer. Our results show that extended planar defects in olivine, parallel to {101}ol and occurring in ordered “clusters” with a prolate spheroid geometry ~5–25 nm across and extending up to 150 nm into the olivine, are present near the olivine–glass interfaces in all of our experimental high-TiO2 basalt–olivine samples. Increased Ti content in the olivine is associated with the defects; ordering of Ti4+ and octahedral site vacancies leads to a two- or three-layer superstructure in the olivine. Defect nucleation and growth is driven by the large TiO2 chemical potential gradient across the phase boundary at the start of the experiments, which provides access to microstructures not otherwise present.

Study on Gallium Nitride-Based Metal–Oxide–Semiconductor Capacitors With RF Magnetron Sputtered $\hbox{Y}_{2}\hbox{O}_{3}$ Gate

Effects of postdeposition annealing (PDA) temperatures (200°C-1000°C) in argon ambient on radio-frequency magnetron sputtered Y <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> film on n-type GaN substrate were studied. As-deposited Y <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> film was amorphous as no Y <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> phase was detected by X-ray diffraction. A transformation of the amorphous to polycrystalline phase happened when PDA (≥ 200°C) was carried out. The detection of β-Ga <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> phase for samples annealed beyond 400°C denoted the formation of interfacial layer (IL) consisting of an Y <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> and β-Ga <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> mixture. The formation of IL was revealed by cross-sectional energy-filtered transmission electron microscopy images. Metal-oxide-semiconductor characteristics of Y <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> /GaN structure annealed at different temperatures were correlated with structural and surface morphology analysis. The 400-°C-annealed sample demonstrated the highest electric breakdown field (~ 10.7 MV/cm) due to the attainment of the lowest effective oxide charge, semiconductor-oxide interface-trap density, and total interface-trap density.

Three-Dimensional Chemistry of Multiphase Nanomaterials by Energy-Filtered Transmission Electron Microscopy Tomography

A three-dimensional (3D) study of multiphase nanostructures by chemically selective electron tomography combining tomographic approach and energy-filtered imaging is reported. The implementation of this technique at the nanometer scale requires careful procedures for data acquisition, computing, and analysis. Based on the performances of modern transmission electron microscopy equipment and on developments in data processing, electron tomography in the energy-filtered imaging mode is shown to be a very appropriate analysis tool to provide 3D chemical maps at the nanoscale. Two examples highlight the usefulness of analytical electron tomography to investigate inhomogeneous 3D nanostructures, such as multiphase specimens or core-shell nanoparticles. The capability of discerning in a silica-alumina porous particle the two different components is illustrated. A quantitative analysis in the whole specimen and toward the pore surface is reported. This tool is shown to open new perspectives in catalysis by providing a way to characterize precisely 3D nanostructures from a chemical point of view.

Energy-Filtered Secondary-Electron Imaging for Nanoscale Dopant Mapping by Applying a Reverse Bias Voltage

We observed the dopant contrast of an InP structure with magnifications as high as 250,000 by simultaneously applying secondary electron energy-filtering and a reverse bias voltage. The detection modes without energy-filtering and without a bias voltage did not generate a clear contrast. This was because the reverse bias increased the contrast and relatively decreased the sensitivity to the contamination layer while the energy-filtering reduced the influence of the contamination layer, even at a high magnification. This method can be widely used for semiconductor devices and enables practical nanoscale dopant mapping with a high data acquisition rate, and is therefore expected to greatly assist in extending the frontiers of the semiconductor industry.

Energy-Filtered Secondary-Electron Imaging for Nanoscale Dopant Mapping by Applying a Reverse Bias Voltage

Energy-Filtered Secondary-Electron Imaging for Nanoscale Dopant Mapping by Applying a Reverse Bias Voltage

Direct functionalization of pristine single-walled carbon nanotubes by diazonium-based method with various five-membered S- or N- heteroaromatic amines

Reactivity of five-membered, variously substituted, heteroaromatic diazonium salts was studied toward pristine single-walled carbon nanotubes (SWCNTs), prepared by high-pressure CO conversion (HiPCO) method. Average size range of individual HiPCO SWCNTs was 0.8–1.2 nm (diameter) and 100–1,000 nm (length). Functionalizations were performed by a one-pot diazotization–dediazotization method with methyl-2-aminothiophene-3-carboxylate, 2-aminothiophene-3-carbonitrile, 2-aminoimidazole sulfate, or 3-aminopyrazole in acetic acid using sodium nitrite at room temperature or by heating. According to Raman and Fourier transform infrared spectroscopy, all used heterocyclic diazonium salts formed a covalent bond with SWCNTs and yielded new kinds of five-membered heterocycle-functionalized SWCNTs. Methyl-2-thiophenyl-3-carboxylate-functionalized SWCNTs formed a highly soluble, stable dispersion in tetrahydrofuran (THF), 3-pyrazoyl-functionalized SWCNTs in ethanol, and 2-imidazoyl- or 2-thiophenyl-3-carbonitrile-functionalized SWCNTs in ethanol and THF. The thermogravimetric analysis as well as energy-filtered transmission electron microscopy imaging of the products confirmed the successful functionalization of SWCNTs.

3D Analysis of the Morphology and Spatial Distribution of Nitrogen in Nitrogen-Doped Carbon Nanotubes by Energy-Filtered Transmission Electron Microscopy Tomography

We present here the application of the energy-filtered transmission electron microscopy (EFTEM) in the tomographic mode to determine the precise 3D distribution of nitrogen within nitrogen-doped carbon nanotubes (N-CNTs). Several tilt series of energy-filtered images were acquired on the K ionization edges of carbon and nitrogen on a multiwalled N-CNT containing a high amount of nitrogen. Two tilt series of carbon and nitrogen 2D maps were then calculated from the corresponding energy-filtered images by using a proper extraction procedure of the chemical signals. Applying iterative reconstruction algorithms provided two spatially correlated C and N elemental-selective volumes, which were then simultaneously analyzed with the shape-sensitive reconstruction deduced from Zero-Loss recordings. With respect to the previous findings, crucial information obtained by analyzing the 3D chemical maps was that, among the two different kind of arches formed in these nanotubes (transversal or rounded ones depending on their morphology), the transversal arches contain more nitrogen than do the round ones. In addition, a detailed analysis of the shape-sensitive volume allowed the observation of an unexpected change in morphology along the tube axis: close to the round arches (with less N), the tube is roughly cylindrical, whereas near the transversal ones (with more N), its shape changes to a prism. This relatively new technique is very powerful in the material science because it combines the ability of the classical electron tomography to solve 3D structures and the chemical selectivity of the EFTEM imaging.

Interfacial plasmon at a singular solid-liquid interface in a partially molten aluminum alloy

Nanoplasmonics is an important emerging research area in technologies, such as energy conversion using photovoltaic devices and hydrogen sensing using Pd nanoparticles. So far, plasmon excitations are only known to exist at the interface between two different dielectric media, such as two solids or at solid-vacuum surfaces. There has been no evidence for the presence of a plasmon at a solid-liquid interface. This paper presents results on the existence and nature of the plasmon resonance between a semiconducting solid and a liquid metal, investigated in a transmission electron microscope having sub-eV and sub-$\AA{}$ resolutions. The results are compared with calculations of the plasmon based on dielectric theory and are corroborated with energy-filtered imaging analyses. The unique plasmon resonance observed at the solid-liquid interface provides new insight into the behavior of plasmons in research areas from biomedical imaging to liquid crystals, including the technologies mentioned above.

Development of epithermal neutron camera based on resonance-energy-filtered imaging with GEM

An epithermal neutron camera based on energy-filtered imaging with gas electron multipliers was developed. Epithermal neutron imaging is achievable without time-of-flight detection of neutrons by using a resonance filter and a thermal neutron absorber. This technique is applicable to compact accelerator-based neutron sources. Blurring of epithermal neutron images caused by neutron scattering in the Ag resonance filter and the B4C sheet (used as a thermal neutron absorber) was investigated experimentally. The spatial resolution for epithermal neutrons with energies in the range 4.2 to 6.3 eV (corresponding to the resonance peak of 109Ag) was estimated to be 1.9±0.5 mm in a prototype detector.

Highly Reproducible Secondary Electron Imaging under Electron Irradiation Using High-Pass Energy Filtering in Low-Voltage Scanning Electron Microscopy

The reproducibility of contrast in secondary electron (SE) imaging during continuous electron irradiation, which caused surface contamination, was investigated using SE high-pass energy filtering in low-voltage scanning electron microscopy (SEM). According to high-pass energy-filtered imaging, dopant contrast in an indium phosphide remained remarkably stable during continuous electron irradiation although the contrast in unfiltered SE images decreased rapidly as a contamination layer was formed. Charge neutralization and the SE energy distributions indicate that the contamination layer induces a positive charge. This results in a decrease of low-energy SE emissions and reduced dopant contrast in unfiltered SE images. The retention of contrast was also observed in high-pass energy-filtered images of a gold surface. These results suggest that this imaging method can be widely used when SE intensities decrease under continuous electron irradiation in unfiltered SE images. Thus, high-pass energy-filtered SE imaging will be of a great assistance for SEM users in the reproducibility of contrast such as a quantitative dopant mapping in semiconductors.

Time-of-flight-photoelectron emission microscopy on plasmonic structures using attosecond extreme ultraviolet pulses

We report on the imaging of plasmonic structures by time-of-flight-photoemission electron microscopy (ToF-PEEM) in combination with extreme ultraviolet (XUV) attosecond pulses from a high harmonic generation source. Characterization of lithographically fabricated Au structures using these ultrashort XUV pulses by ToF-PEEM shows a spatial resolution of ∼200 nm. Energy-filtered imaging of the secondary electrons resulting in reduced chromatic aberrations as well as microspectroscopic identification of core and valence band electronic states have been successfully proven. We also find that the fast valence band electrons are not influenced by space charge effects, which is essentially important for attosecond nanoplasmonic-field microscopy realization.

The SmartEFTEM-SI method: Development of a new spectrum-imaging acquisition scheme for quantitative mapping by energy-filtering transmission electron microscopy

Abstract A new acquisition scheme for energy-filtering transmission electron microscopy (EFTEM) spectrum-imaging (SI), named SmartEFTEM-SI, has been developed. The new method reduces the influence of CCD dark-current modulations on energy-filtered images and enables improved spatial-drift correction. In conventional EFTEM approaches, elemental maps are significantly degraded especially when these issues are not addressed. The new scheme also offers multiple-frame acquisition at individual energy planes, and the acquisition of a low-loss SI dataset immediately following the high-loss SI dataset recorded for a particular characteristic edge, enabling advanced spectral processing such as multiple-scattering deconvolution and thickness correction. After spectral processing of the high-loss SI datasets using the corresponding low-loss information, the absolute number of atoms of the particular element of interest can be determined. The SmartEFTEM-SI method thus offers absolute elemental quantification of a thin specimen over a large field of view.

Energy-filtered phase retrieval using the transport of intensity equation

Energy-filtered imaging was combined with phase retrieval to study plasmon scattering contributions to electron phase shifts surrounding gold nanoparticles. Spectral windows with sufficient energy resolution to exclude plasmon scattering were used to measure through-focal intensity derivatives and retrieve phase maps via the transport of intensity equation. Phase excursions in the phase maps that included plasmon scattering were found to disagree with theory by at least an order of magnitude. This discrepancy was attributed to subtle particle instabilities under the electron beam, which lead to systematic errors in the retrieved phase maps.

Synthesis and electron microscopic analysis of the self‐assembly of polymer and ferritin core‐shell structures

Self-assembly of poly(4-vinylpyridine) (P4VP) and ferritin produced a spherical core-shell structure, which was analyzed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In particular, for better understanding, the organization of such core-shell nanostructures, an optimal protocol for preparation of TEM thin sectioning of ferritin-P4VP composites, was developed. It entails fixing the ferritin-P4VP complex with 2.5% glutaraldehyde and infiltrating it with a mixture of acetone/resin while omitting the OsO(4) postfixation and ethanol dehydration steps of the conventional protocol. Using this method, a round-shaped thin section structure with unevenly distributed dark and white components was observed. The dark component from the thin section structure was determined to contain ferritin by energy-filtered TEM imaging and iron element mapping, whereas the white part was identified as P4VP by its energy dispersive X-ray spectroscopy (EDS) spectrum.

Controlled Synthesis of Tuned Bandgap Nanodimensional Alloys of PbSxSe1−x

Truly alloyed PbS(x)Se(1-x) (x = 0-1) nanocrystals (∼5 nm in size) have been prepared, and their resulting optical properties are red-shifted systematically as the sulfur content of the materials increases. Their optical properties are discussed using a modified Vegard's approach and the bowing parameter for these nanoalloys is reported for the first time. The alloyed structure of the nanocrystals is supported by the energy-filtered transmission electron microscope images of the samples, which show a homogeneous distribution of sulfur and selenium within the nanocrystals. X-ray photoelectron spectroscopy studies on ligand-exchanged nanocrystals confirmed the expected stoichiometry and various oxidized species.

A quantitative model for doping contrast in the scanning electron microscope using calculated potential distributions and Monte Carlo simulations

This paper describes the use of a Monte Carlo model incorporating a finite-element method computing the electrostatic fields inside and outside a semiconductor, plus a ray-tracing algorithm for determining the doping contrast observed in a scanning electron microscope (SEM). This combined numerical method also enables the effects on the doping contrast of surface band-bending to be distinguished from those of external patch fields outside the specimen, as well as any applied macroscopic external fields from the detection system in the SEM. Good agreement of our new theory with experiment is obtained. The contrast characteristics in energy-filtered secondary electron images are also explained. The results of this work lead to a more advanced understanding of the doping contrast mechanisms, thereby enabling quantitative dopant profiling using the SEM.

Superstructure formation and variation in Ni–GDC cermet anodes in SOFC

The microstructures and spatial distributions of constituent elements at the anode in solid oxide fuel cells (SOFCs) have been characterized by analytical transmission electron microscopy (TEM). High resolution TEM observations demonstrate two different types of superstructure formation in grain interiors and at grain boundaries. Energy-filtered TEM elemental imaging qualitatively reveals that mixture zones exist at metal-ceramic grain boundaries, which is also quantitatively verified by STEM energy dispersive X-ray spectroscopy. It was apparent that both metallic Ni and the rare-earth elements Ce/Gd in gadolinium-doped ceria can diffuse into each other with equal diffusion lengths (about 100 nm). This will lead to the existence of mutual diffusion zones at grain boundaries, accompanied by a change in the valence state of the diffusing ions, as identified by electron energy-loss spectroscopy (EELS). Such mutual diffusion is believed to be the dominant factor that gives rise to superstructure formation at grain boundaries, while a different superstructure is formed at grain interiors, as a consequence solely of the reduction of Ce(4+) to Ce(3+) during H(2) treatment. This work will enhance the fundamental understanding of microstructural evolution at the anode, correlating with advancements in sample preparation in order to improve the performance of SOFC anodes.