Development of electron energy-loss spectroscopy for nanoscience

Electron energy-loss spectroscopy (EELS) has been well established in providing the composition and chemical bonding information of materials, particularly for light elements. Its potential for structural determination has long been known but has yet to be fully explored. With the convergence of rapid development in computing power and improvement in the efficiency of the material specific electronic structure simulation, plus the recent breakthrough in the development of C(s)-corrected electron microscopy, the reconstruction of the local three dimensional structure of nanomaterial using EELS in conjunction with advanced structural imaging and diffraction techniques is becoming increasingly feasible. In this paper, we will review from our own examples the progress in EELS instrumentation, methods and simulation to illustrate the progress that has been made. They include the density-function-theory-based ab initio spectroscopic simulation for standard-less fingerprint applications for metastable polymorph identification, magic angle electron energy-loss spectroscopy as well as recent results from the dual-detectors EELS system which allows the energy instability of the spectrometer to be analyzed in real-time and eventually compensated on-line.     

Maximum-entropy deconvolution applied to electron energy-loss spectroscopy

In the present paper, we investigate the performance of maximum-entropy deconvolution, in removing the instrumental response function from electron energy-loss spectra. To this end we make use of spectra acquired from the carbon K-edge in graphite for a range of signal-to-noise ratios. The zero-loss peak is used as the instrumental profile. The resolution improvement obtained through the application of the deconvolution algorithm as a function of the signal-to-noise ratio is well described by a logarithmic dependency. The claimed resolution improvement is further substantiated by demonstrating the consistency between improvement obtained for the width of the instrumental response function, the width of the π¹ peak and the splitting of the σ¹ peaks for a range of signal-to-noise ratios.     

Scandium and lutetium surfaces studied by reflection electron energy-loss spectroscopy

The reflection electron energy-loss spectra of the (1 0 0) and (0 0 1) surfaces of Sc single crystals and the (0 0 1) surface of a Lu single crystal have been studied with primary energies in the range 50–2000 eV. Scandium is congeneric with lutetium and the loss spectra of the two elements are very similar in both the collective excitations and the interband transitions. Strong excitations observed at around 41 eV are attributed to 3p → 3d and 5p → 5d transitions in Sc and Lu, respectively. The loss data of Sc fit the characteristic energy-loss data of the other elements of the first group of transition metals. Oxygen adsorption and nitrogen adsorption on the (1 0 0) surface of Sc influence the loss spectra. The observed differences are correlated with density-of-states calculations for Sc, ScO and ScN.     

Investigation on optical properties of ZnO nanowires by electron energy-loss spectroscopy

Electron energy-loss spectroscopy (EELS) and ab initio band structure calculations have been performed to determine the optical properties of wurtzite structured zinc oxide (ZnO) nanowires. Compared with other techniques, EELS significantly extends the energy range and is a useful technique for analysis of the dielectric properties on a microstructure level. The first-principles calculations allow deep insight into the experimental results. Furthermore, the polarization dependencies of optical properties have been discussed. Our results give some reference to the thorough understanding of optical properties of ZnO.     

Reference energies for inner shell electron energy-loss spectroscopy

The energies of a number of selected inner shell atomic and molecular electronic transitions in the energy range 100–1000eV have been carefully remeasured for energy scale calibration in electron energy loss Spectroscopy. The measurements have been made using an inner shell electron energy loss spectrometer in conjunction with a digital voltmeter of high accuracy.     

Analysis of extraterrestrial particles using monochromated electron energy-loss spectroscopy

A monochromated (scanning) transmission electron microscope was used to analyze individual sub-micron grains within interplanetary dust particles (IDP). Using low-loss and core-loss electron energy-loss spectroscopy, we analyzed fluid and gas inclusions within vesiculated alumosilicate grains. It is shown that nanometer-sized vesicles contain predominantly molecular oxygen (O(2)) beside a small fraction of H(2)O. Low-loss spectra reveal the Schumann-Runge continuum peaking at 8.6 eV and absorption bands reflecting vibrational excitation states of O(2) molecules between the first (12.1 eV) and second (16.1 eV) ionization energy. The presence of oxygen gas is supported by the corresponding oxygen K-edge fine structure. The valence state of Fe in iron-oxide within the IDP was also studied. Low-loss spectra provide qualitative information about the oxidation state of iron consistent with the Fe(2+)/Fe(3+) ratio quantitatively derived from the Fe L(2,3) edge.     

高分辨率电子能量损失谱在材料科学中的应用

简要介绍了FEI Titan80—300STEM扫描透射电镜中装配的Wien-filter型能量单色器(monochromator).文章特别指出,装配有能量单色器的FEI Titan80—300STEM扫描透射电镜,可以直接给出高能量分辨率（~0.1eV）的电子能量损失谱.利用高分辨电子能量损失谱,在高能损失区,对于K或L能级自然宽度(natural width of energy level)小于0.5eV的元素,可以获得更细致的的近限精细结构（energy-loss near-edge structure）,更有利于解析其电子结构;在低能损失区,可以用于精确地确定半导体材料的带隙（bandgap）以及p型掺杂引起的带隙能的变化.     

New techniques in electron energy-loss spectroscopy and energy-filtered imaging

This article is a survey of hardware and software advances that promise to increase the power and sensitivity of electron energy-loss spectroscopy (EELS) and energy-filtered imaging (EFTEM) in a transmission electron microscope. Recent developments include electron-gun monochromators, lens-aberration correctors, and software for spectral sharpening, spectral processing and interpretation of fine structure. Future improvements could include the deployment of new electron sources. The expected enhancements in energy and spatial resolution are compared with fundamental limitations that arise from the natural widths of spectral peaks, the delocalization of inelastic scattering and the problem of electron-irradiation damage.     

Inelastic electron irradiation damage in hexagonal boron nitride

We present a study of the inelastic effects caused by electron irradiation in monolayer hexagonal boron nitride (h-BN). The data was obtained through in situ experiments performed inside a low-voltage aberration-corrected transmission electron microscope (TEM). By using various specialized sample holders, we study defect formation and evolution with sub-nanometer resolution over a wide range of temperatures, between −196 and 1200 °C, highlighting significant differences in the geometry of the structures that form. The data is then quantified, allowing insight into the defect formation mechanism, which is discussed in comparison with the potential candidate damage processes. We show that the defect shapes are determined by an interplay between electron damage, which we assign to charging, and thermal effects. We additionally show that this damage can be avoided altogether by overlapping the samples with a monolayer of graphene, confirming this for h-BN and providing a way to overcome the well-known fragility of h-BN under the electron beam.     

Composition fluctuations in dilute nitride (Ga,In)(N,As)/GaAs heterostructures measured by low-loss electron energy-loss spectroscopy

We report on the investigation of composition fluctuations in epitaxially grown (Ga,In)(N,As) epilayers on GaAs(001) substrates by using electron energy-loss spectroscopy (EELS). The N and In concentrations are determined locally with a probe size of about 8 nm from the low-loss EELS measurements. We demonstrate that the small amount of N incorporating in dilute nitride alloys can be measured quantitatively by the plasmon energy shift with respect to a GaAs reference, and that the In content is analyzed simultaneously from the In 4d transitions, which have been isolated from the overlapping Ga 3d transitions. Our spatially resolved EELS results are utilized to discuss the origin of the inherent composition fluctuations and their influences on the morphological instabilities during epitaxial growth.     

Atom-scale ptychographic electron diffractive imaging of boron nitride cones

Ptychographic coherent diffractive imaging (CDI) has been extensively applied using both x rays and electrons. The extension to atomic resolution has been elusive. This Letter demonstrates ptychographic electron diffractive imaging at atomic resolution, permitting identification of structure in a boron nitride helical cone at a resolution of order 1 ?, beyond that of comparative Z-contrast images. A scanning transmission electron microscope is used to create a diverging illumination in a defocused Fresnel CDI geometry, providing a robust strategy leading to a unique solution.     

Optical spectra and electron structure of cubic boron nitride

On the basis of the known reflection spectrum, we calculate a complete set of fundamental optical functions for cubic boron nitride (c-BN) in the region of 2–23 eV. The integral spectrum of dielectric permeability is decomposed into 16 elementary components. Three main parameters (maximum energy, half-width, and oscillator force) for each of the components are determined. Using the well-known theoretical calculations for bands of boron nitride as the base we suggest a scheme of the nature of these dielectric permeability components. To whom correspondence should be addressed. Udmurtiya State University, 1, Universitetskaya Str., Izhevsk, 426034, Russia:e-mail: sobolev@matsim.udmurtia.su. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 4, pp. 579–583, July–August, 1999.     

Local thickness measurement through scattering contrast and electron energy-loss spectroscopy

Scattering contrast measurements were performed on thin films of amorphous carbon and polycrystalline Au, as well as single-crystal MgO nanocubes. Based on the exponential absorption law, mass-thickness can be obtained within 10% accuracy by measuring the incident and transmitted intensities in the same image. For mass-thickness measurement of a thin amorphous specimen, a small collection semiangle improves the measurement sensitivity, whereas for the measurement of polycrystalline or single-crystal specimens, a large collection semiangle should be used to reduce diffraction-contrast effects. EELS thickness measurements on MgO nanocubes suggest that the Kramers-Kronig sum-rule method (with correction for plural and surface scattering) gives 10% accuracy at medium collection semiangles but overestimates the thickness at small collection semiangles, due to underestimation of the surface-mode scattering. The log-ratio method, with a formula for inelastic mean free path proposed by Malis et al. (1988), provides 10% accuracy at small collection semiangle, while that proposed by Iakoubovskii et al. (2008a) is preferable for medium and large collection semiangles. As a result of this work, we provide recommendations of preferred methods and conditions for local-thickness measurement in the TEM.     

Evidence for localized excitations in MgO from electron energy-loss spectroscopy

The excited electronic states in the ionic crystal MgO have been studied by electron energy-loss spectroscopy. Structure observed above the thresholds for excitation from the Mg 2p, 2s and 1s core levels shows the final states to be predominantly excitonic levels of the Mg²⁺ ion. Comparison with the known states of the Mg²⁺ free ion indicates that solid-state shifts and splittings are small.     

Advantages of a monochromator for bandgap measurements using electron energy-loss spectroscopy

The practical advantages of a monochromator for electron energy-loss spectroscopy (EELS) in transmission electron microscopy are reviewed. The zero-loss peaks (ZLPs) of a monochromator and a cold field emission gun are compared in terms of bandgap measurement performance. The intensity of the ZLP tails at the bandgap energy is more important than the full-width at half maximum of the ZLP, and a monochromator is preferable to conventional electron sources. The silicon bandgap of 1.1eV is evaluated from the onset in the EEL spectrum obtained using the monochromator without a numerical procedure. We also show a high-speed instability-correction technique to realize the inherent energy resolution of the monochromator, in which instabilities of less than 335Hz are corrected using 512 EEL spectra obtained with an exposure time of 1.4ms. It will be useful in bandgap measurements and advanced studies for elucidating sub-eV EEL spectra.     

Polarity and inverse boundary of Sn-doped ZnO bicrystal nanobelts determined by electron energy-loss spectroscopy

Polarity in Sn-doped ZnO bicrystal nanobelts has been investigated using electron energy-loss spectroscopy. The nanobelts are composed of two domain boundaries extending along the axial direction. It is confirmed that the nanobelts are Zn terminated at both sides. Examinations of high-resolution transmission electron microscopy and electron energy-loss spectroscopy show that one domain boundary results from a stacking fault, and the other originates from Sn-ion insertion, which leads to an inverse domain boundary. A possible atomic stacking model is proposed.