Valence Electron Energy Loss Spectroscopy Research Articles

Direct observation of spinodal decomposition phenomena in InAlN alloys during in-situ STEM heating

The spinodal decomposition and thermal stability of thin In0.72Al0.28N layers and In0.72Al0.28N/AlN superlattices with AlN(0001) templates on Al2O3(0001) substrates was investigated by in-situ heating up to 900 °C. The thermally activated structural and chemical evolution was investigated in both plan-view and cross-sectional geometries by scanning transmission electron microscopy in combination with valence electron energy loss spectroscopy. The plan-view observations demonstrate evidence for spinodal decomposition of metastable In0.72Al0.28N after heating at 600 °C for 1 h. During heating compositional modulations in the range of 2–3 nm-size domains are formed, which coarsen with applied thermal budgets. Cross-sectional observations reveal that spinodal decomposition begin at interfaces and column boundaries, indicating that the spinodal decomposition has a surface-directed component.

Valence EELS below the limit of inelastic delocalization using conical dark field EFTEM or Bessel beams

In this experimental work we present novel methods to increase the spatial resolution of valence electron energy loss spectrometry (VEELS) investigations below the limit given by the inelastic delocalization. For this purpose we analyse a layer stack consisting of silicon/silicon-oxide/silicon-nitride/silicon-oxide/silicon (SONOS) with varying layer thickness down to the 2nm level. Using a combination of a conical illumination and energy filtered transmission electron microscopy we are able to identify the layers by using low energy losses. Employing Bessel beams we demonstrate that VEELS can be performed in dark-field conditions while simultaneously the Bessel beam increases the spatial resolution of the elastic image due to less sensitivity to the spherical aberration of the condenser lens system. The dark-field conditions also guarantee that only electrons are collected that have neither undergone an energy loss being due to the Cˇerenkov effect, nor due to the excitation of transition radiation or light guiding modes. We consequently are able to measure the optical properties of a 2.5nm thin oxide being sandwiched by the silicon substrate and a silicon-nitride layer.

Signatures of distinct impurity configurations in atomic-resolution valence electron-energy-loss spectroscopy: Application to graphene

The detection and identification of impurities and other point defects in materials is a challenging task. Signatures for point defects are typically obtained using spectroscopies without spatial resolution. Here in this paper, we demonstrate the power of valence electron-energy-loss spectroscopy (VEELS) in an aberration-corrected scanning transmission-electron microscope (STEM) to provide energy-resolved and atomically resolved maps of electronic excitations of individual impurities which, combined with theoretical simulations, yield unique signatures of distinct bonding configurations of impurities. We report VEELS maps for isolated Si impurities in graphene, which are known to exist in two distinct configurations. We also report simulations of the maps, based on density functional theory and dynamical scattering theory, which agree with and provide direct interpretation of observed features. We show that theoretical VEELS maps exhibit distinct and unambiguous signatures for the threefold- and fourfold-coordinated configurations of Si impurities in different energy-loss windows, corresponding to impurity-induced bound states, resonances, and antiresonances. With the advent of new monochromators and detectors with high energy resolution and low signal-to-noise ratio, the present work ushers an atomically resolved STEM-based spectroscopy of individual impurities as an alternative to conventional spectroscopies for probing impurities and defects.

Band gap widening at random CIGS grain boundary detected by valence electron energy loss spectroscopy

Cu(In,Ga) Se2 (CIGS) thin film solar cells have demonstrated very high efficiencies, but still the role of nanoscale inhomogeneities in CIGS and their impact on the solar cell performance are not yet clearly understood. Due to the polycrystalline structure of CIGS, grain boundaries are very common structural defects that are also accompanied by compositional variations. In this work, we apply valence electron energy loss spectroscopy in scanning transmission electron microscopy to study the local band gap energy at a grain boundary in the CIGS absorber layer. Based on this example, we demonstrate the capabilities of a 2nd generation monochromator that provides a very high energy resolution and allows for directly relating the chemical composition and the band gap energy across the grain boundary. A band gap widening of about 20 meV is observed at the grain boundary. Furthermore, the compositional analysis by core-loss EELS reveals an enrichment of In together with a Cu, Ga and Se depletion at the same area. The experimentally obtained results can therefore be well explained by the presence of a valence band barrier at the grain boundary.

Electron beam induced dehydrogenation of MgH2 studied by VEELS

AbstractNanosized or nanoconfined hydrides are promising materials for solid-state hydrogen storage. Most of these hydrides, however, degrade fast during the structural characterization utilizing transmission electron microscopy (TEM) upon the irradiation with the imaging electron beam due to radiolysis. We use ball-milled MgH2 as a reference material for in-situ TEM experiments under low-dose conditions to study and quantitatively understand the electron beam-induced dehydrogenation. For this, valence electron energy loss spectroscopy (VEELS) measurements are conducted in a monochromated FEI Titan3 80–300 microscope. From observing the plasmonic absorptions it is found that MgH2 successively converts into Mg upon electron irradiation. The temporal evolution of the spectra is analyzed quantitatively to determine the thickness-dependent, characteristic electron doses for electron energies of both 80 and 300 keV. The measured electron doses can be quantitatively explained by the inelastic scattering of the incident high-energy electrons by the MgH2 plasmon. The obtained insights are also relevant for the TEM characterization of other hydrides.

Band Gap Extraction from Individual Two-Dimensional Perovskite Nanosheets Using Valence Electron Energy Loss Spectroscopy

Rapid progress in the synthesis of nanostructures with tailor-made morphologies necessitates adequate analytical tools to unravel their physical properties. In our study, we investigate, on the nanometer scale, the band gap of individual [TBAxH1–x]+[Ca2Nb3O10]− nanosheets obtained through intercalation–exfoliation of the layered bulk phase KCa2Nb3O10 with tetra-n-butylammonium hydroxide (TBAOH) using valence electron energy loss spectroscopy (VEELS) in the scanning transmission electron microscope (STEM). The nanosheets consist of an anionically charged perovskite layer with cationic organic ligands surrounding it. Because of the hybrid nature, a careful acquisition and analysis protocol is required since the nanosheets disintegrate easily under electron beam irradiation. The VEELS data reveal a fundamental band gap of an individual freely suspended perovskite nanosheet to be 2.9 ± 0.2 eV and optically allowed transitions above 3.8 ± 0.2 eV (optical band gap). The spatial resolution of the measurements is...

An experimental investigation on the effective electron mass in InGaO3(ZnO)3 by valence electron energy-loss spectroscopy

In2−xGaxO3(ZnO)m are reported to exhibit an extremely high field-effect mobility, and therefore considered as the potential channel materials for transparent field-effect transistor. To gain a deep insight into the high mobility of In2−xGaxO3(ZnO)m, the effective electron mass, which is inherently related to the mobility of charge carriers as well as the density of states, is investigated by valence electron energy-loss spectroscopy. The effective electron masses in InGaO3(ZnO)3 nanobelts with the incident electron beam along the c axis and <112-0> are determined as 0.130m0 and 0.132m0, respectively. These results critically checked by a comparison with calculated values and values measured by others. It not only well validates the results acquired from theoretical investigations, but also shed a new light on the isotropy of the effective electron mass in InGaO3(ZnO)m.

Local heteroepitaxial growth to promote the selective growth orientation, crystallization and interband transition of sputtered NiO thin films

The room temperature growth of highly oriented sputtered NiO thin films on glass and silicon substrates previously covered with a oriented Cu2O film is reported. The results are compared to those obtained from single layer NiO thin films using the same deposition conditions. Electron microdiffraction analyses indicate that NiO columns are heteroepitaxially grown on the columns of a Cu2O seed layer. The well-matched atomic configurations between the Cu atoms in the {111} planes of Cu2O and the O atoms in the {111} planes of NiO may provide a strong driving force to promote this local heteroepitaxial growth. Such heteroepitaxial growth behavior in the columns can significantly improve crystallization. Moreover, valence electron energy loss spectroscopy has been employed to investigate the interband transition properties of the NiO films, which shows that the interband transition intensity can be tuned by this local heteroepitaxial growth.

Probing the size dependence on the optical modes of anatase nanoplatelets using STEM-EELS

Anatase titania nanoplatelets with predominantly exposed {001} facets have been reported to have enhanced catalytic properties in comparison with bulk anatase. To understand their unusual behaviour, it is essential to fully characterize their electronic and optical properties at the nanometer scale. One way of assessing these fundamental properties is to study the dielectric function. Valence electron energy-loss spectroscopy (EELS) performed using a scanning transmission electron microscope (STEM) is the only analytical method that can probe the complex dielectric function with both high energy (<100 meV) and high spatial (<1 nm) resolution. By correlating experimental STEM-EELS data with simulations based on semi-classical dielectric theory, the dielectric response of thin (<5 nm) anatase nanoplatelets was found to be largely dominated by characteristic (optical) surface modes, which are linked to surface plasmon modes of anatase. For platelets less than 10 nm thick, the frequency of these optical modes varies according to their thickness. This unique optical behaviour prompts the enhancement of light absorption in the ultraviolet regime. Finally, the effect of finite size on the dielectric signal is gradually lost by stacking consistently two or more platelets in a specific crystal orientation, and eventually suppressed for large stacks of platelets.

Inline electron holography and VEELS for the measurement of strain in ternary and quaternary (In,Al,Ga)N alloyed thin films and its effect on bandgap energy.

We present the use of (1) dark-field inline electron holography for measuring the structural strain, and indirectly obtaining the composition, in a wurtzite, 4-nm-thick InAlGaN epilayer on a AlN/GaN/AlN/GaN multinano-layer heterosystem, and (2) valence electron energy-loss spectroscopy to study the bandgap value of five different, also hexagonal, 20-50-nm-thick InAlGaN layers. The measured strain values were almost identical to the ones obtained by other techniques for similarly grown materials. We found that the biaxial strain in the III-N alloys lowers the bandgap energy as compared to the value calculated with different known expressions and bowing parameters for unstrained layers. By contrast, calculated and experimental values agreed in the case of lattice-matched (almost unstrained) heterostructures.

On the validity of the Čerenkov limit as a criterion for precise band gap measurements by VEELS

The generation of Čerenkov photons, contributions from retardation and surface effects, and the excitation of guided light modes can complicate the analysis of valence electron energy-loss spectroscopy (VEELS) data. In recent works it was argued that working below the so-called Čerenkov limit unwanted spectral contributions can be avoided, simplifying the reliable measurement of band gap energies and the extraction of the dielectric function by the Kramers–Kronig analysis. Here, relativistic simulations of valence electron energy-loss spectra of GaAs are employed in order to identify different spectral contributions. It is found that for electron energies below the Čerenkov limit the spectra can still be affected by the excitation of guided light modes and retardation effects. These spectral contributions can influence the position of the apparent band gap signal and can be problematic for the Kramers–Kronig analysis when working below or above the Čerenkov limit.

Water and organics in interplanetary dust particles

AbstractInterplanetary dust particles (IDPs) and larger micrometeorites (MMs) impinge on the upper atmosphere where they decelerate at 90 km altitude and settle to the Earths surface. Comets and asteroids are the major sources and the flux, 30,000-40,000 tons/yr, is comparable to the mass of larger meteorites impacting the Earths surface. The sedimentary record suggests that the flux was much higher on the early Earth. The chondritic porous (CP) subset of IDPs together with their larger counterparts, ultracarbonaceous micrometeorites (UCMMs), appear to be unique among known meteoritic materials in that they are composed almost exclusively of anhydrous minerals, some of them contain &gt;&gt; 50% organic carbon by volume as well as the highest abundances of presolar silicate grains including GEMS. D/H and 15N abundances implicate the Oort Cloud or presolar molecular cloud as likely sources of the organic carbon. Prior to atmospheric entry, IDPs and MMs spend 104-105 year lifetimes in solar orbit where their surfaces develop amorphous space weathered rims from exposure to the solar wind (SW). Similar rims are observed on lunar soil grains and on asteroid Itokawa regolith grains. Using valence electron energy-loss spectroscopy (VEELS) we have detected radiolytic water in the rims on IDPs formed by the interaction of solar wind protons with oxygen in silicate minerals. Therefore, IDPs and MMs continuously deliver both water and organics to the earth and other terrestrial planets. The interaction of protons with oxygen-rich minerals to form water is a universal process.

Spectroscopic evidence in the visible-ultraviolet energy range of surface functionalization sites in the multilayerTi3C2MXene

Valence electron energy-loss (VEEL) spectroscopy in the transmission electron microscope is combined to ab initio calculations to investigate the dielectric properties of multilayer (ML) two-dimensional ${\mathrm{Ti}}_{3}{\mathrm{C}}_{2}{T}_{2}$ ($T\ensuremath{\equiv}\text{OH}$ or F) MXene. Besides evidencing important similarities between the ${\mathrm{ML}\ensuremath{-}\mathrm{Ti}}_{3}{\mathrm{C}}_{2}{T}_{2}$ and TiC valence electron gas behaviors, a clear interband transition characteristic of the most stable site of the $T$ functionalization groups is identified in the VEEL spectrum. This signature, highly dependent on the $T$-group localization on the surface, has a prominent effect on the optical properties of the ML, leading to $40%$ variations in the optical conductivity in the middle of the visible spectrum. Such a dependence could be of crucial interest for optical transparent thin films or sensing applications.

Variation of energy density of states in quantum dot arrays due to interparticle electronic coupling.

Subnanometer-resolved local electron energy structure was measured in PbS quantum dot superlattice arrays using valence electron energy loss spectroscopy with scanning transmission electron microscopy. We found smaller values of the lowest available transition energies and an increased density of electronic states in the space between quantum dots with shorter interparticle spacing, indicating extension of carrier wave functions as a result of interparticle electronic coupling. A quantum simulation verified both trends and illustrated the wave function extension effect.

Local Band Gap Measurements by VEELS of Thin Film Solar Cells

This work presents a systematic study that evaluates the feasibility and reliability of local band gap measurements of Cu(In,Ga)Se2 thin films by valence electron energy-loss spectroscopy (VEELS). The compositional gradients across the Cu(In,Ga)Se2 layer cause variations in the band gap energy, which are experimentally determined using a monochromated scanning transmission electron microscope (STEM). The results reveal the expected band gap variation across the Cu(In,Ga)Se2 layer and therefore confirm the feasibility of local band gap measurements of Cu(In,Ga)Se2 by VEELS. The precision and accuracy of the results are discussed based on the analysis of individual error sources, which leads to the conclusion that the precision of our measurements is most limited by the acquisition reproducibility, if the signal-to-noise ratio of the spectrum is high enough. Furthermore, we simulate the impact of radiation losses on the measured band gap value and propose a thickness-dependent correction. In future work, localized band gap variations will be measured on a more localized length scale to investigate, e.g., the influence of chemical inhomogeneities and dopant accumulations at grain boundaries.

Detection of solar wind-produced water in irradiated rims on silicate minerals

The solar wind (SW), composed of predominantly ∼1-keV H(+) ions, produces amorphous rims up to ∼150 nm thick on the surfaces of minerals exposed in space. Silicates with amorphous rims are observed on interplanetary dust particles and on lunar and asteroid soil regolith grains. Implanted H(+) may react with oxygen in the minerals to form trace amounts of hydroxyl (-OH) and/or water (H2O). Previous studies have detected hydroxyl in lunar soils, but its chemical state, physical location in the soils, and source(s) are debated. If -OH or H2O is generated in rims on silicate grains, there are important implications for the origins of water in the solar system and other astrophysical environments. By exploiting the high spatial resolution of transmission electron microscopy and valence electron energy-loss spectroscopy, we detect water sealed in vesicles within amorphous rims produced by SW irradiation of silicate mineral grains on the exterior surfaces of interplanetary dust particles. Our findings establish that water is a byproduct of SW space weathering. We conclude, on the basis of the pervasiveness of the SW and silicate materials, that the production of radiolytic SW water on airless bodies is a ubiquitous process throughout the solar system.

Characterization of InGaN/GaN quantum well growth using monochromated valence electron energy loss spectroscopy

The early stages of InGaN/GaN quantum well growth for In-reduced conditions have been investigated for varying thickness and composition of the wells. The structures were studied by monochromated scanning transmission electron microscopy–valence electron energy loss spectroscopy spectrum imaging at high spatial resolution. It is found that beyond a critical well thickness and composition, quantum dots (width &amp;gt;20 nm) are formed inside the well. These are buried by compositionally graded InGaN, which is formed as GaN is grown while residual In is incorporated into the growing structure. It is proposed that these dots act as carrier localization centers inside the quantum wells.

Valence electron energy-loss spectroscopy study of ZrSiO4 and ZrO2

ZrSiO4 (zircon) and m-ZrO2 (zirconia) are fundamental and industrially important materials. This work reports the detailed valence electron energy-loss spectroscopy (VEELS) studies of these compounds. The dielectric response functions, as well as single-electron interband transition spectra, are derived from VEELS data for both ZrSiO4 and m-ZrO2, in the range 5–50 eV using the Kramers–Kronig analysis method. Our interpretation of the interband transitions is given with the aid of ab initio calculations of density of states. The bandgap energies for both materials are also measured using VEELS. The surface and bulk plasmons are identified: the surface plasmon peaks locate at around 12 eV, and two bulk plasmon peaks are ∼15–16 eV and ∼25–27 eV, respectively. Although similarities in the VEELS exist between ZrSiO4 and m-ZrO2, two major differences are also noticed and explained in terms of composition and structure differences.

Electron irradiation damage and color centers of MgO nanocube

Magnesium oxide (MgO) has been of interest for several decades as a promising tunable broadband laser due to its vacancy defects (color centers). In this work we introduced color centers into MgO nanocube by electron irradiation in a transmission electron microscope (TEM). Square nano-holes were formed from the electron-exit face using 100 and 300keV electrons, and a broad O-vacancy (color-center) absorption peak around 4.1–6.6eV was observed by valence-electron energy-loss spectroscopy (VEELS). We investigated the mechanism of MgO damage by high-energy electron beams. The hole formation is believed to involve a mixed removal of diatomic MgO molecules as well as Mg and O species in stoichiometric proportion. Observations using high-resolution transmission electron microscopy (HRTEM) and VEELS suggest that bulk O-vacancies are generated near the electron-exit face, due to the forward momentum transferred from fast-electron collisions and the Coulomb attraction of negative O-ions by the positively charged MgO surface.

Strong anisotropic influence of local-field effects on the dielectric response ofα-MoO3

Dielectric properties of {\alpha}-MoO3 are investigated by a combination of valence electron-energy loss spectroscopy and ab initio calculation at the random phase approximation level with the inclusion of local-field effects (LFE). A meticulous comparison between experimental and calculated spectra is performed in order to interpret calculated dielectric properties. The dielectric function of MoO3 has been obtained along the three axes and the importance of LFE has been shown. In particular, taking into account LFE is shown to be essential to describe properly the intensity and position of the Mo-N2,3 edges as well as the low energy part of the spectrum. A detailed study of the energy-loss function in connection with the dielectric response function also shows that the strong anisotropy of the energy-loss function of {\alpha}-MoO3 is driven by an anisotropic influence of LFE. These LFE significantly dampen a large peak in {\epsilon}2, but only along the [010] direction. Thanks to a detailed analysis at specific k-points of the orbitals involved in this transition, the origin of this peak has not only been evidenced but a connection between the inhomogeneity of the electron density and the anisotropic influence of local-field effects has also been established. More specifically, this anisotropy is governed by a strongly inhomogeneous spatial distribution of the empty states. This depletion of the empty states is localized around the terminal oxygens and accentuates the electron inhomogeneity.