Practical spatial resolution of electron energy loss spectroscopy in aberration corrected scanning transmission electron microscopy

The resolution of electron energy loss spectroscopy (EELS) is limited by delocalization of inelastic electron scattering rather than probe size in an aberration corrected scanning transmission electron microscope (STEM). In this study, we present an experimental quantification of EELS spatial resolution using chemically modulated 2×(LaMnO(3))/2×(SrTiO(3)) and 2×(SrVO(3))/2×(SrTiO(3)) superlattices by measuring the full width at half maxima (FWHM) of integrated Ti M(2,3), Ti L(2,3), V L(2,3), Mn L(2,3), La N(4,5), La N(2,3) La M(4,5) and Sr L(3) edges over the superlattices. The EELS signals recorded using large collection angles are peaked at atomic columns. The FWHM of the EELS profile, obtained by curve-fitting, reveals a systematic trend with the energy loss for the Ti, V, and Mn edges. However, the experimental FWHM of the Sr and La edges deviates significantly from the observed experimental tendency.     

扫描透射电子显微镜及电子能量损失谱的原理及应用

扫描透射电子显微镜是透射电子显微镜的一种,近几年随着球差校正器的问世,扫描透射电子显微镜的分辨率达到亚埃级,结合能量分辨率为亚电子伏特的电子能量损失谱,可以对材料进行高空间分辨率及高能量分辨率的微结构和成分分析。文章简述了扫描透射电子显微镜的发展历程和工作原理,重点讲述了高角环形暗场像的成像机理以及基于高角环形暗场像对材料结构和成分进行分析的原理和应用;电子能量损失谱的成谱过程、谱的特征及其在材料化学和电子结构分析方面的优势和主要应用。     

高分辨扫描透射电子显微镜原理及其应用

扫描透射电子显微术是目前应用最广泛的电子显微表征手段之一,具有分辨率高、对化学成分敏感和图像直观易解释等特点。其中高分辨扫描电子显微镜可以直接获得原子分辨率的Z 衬度像,结合X射线能谱(EDS)和电子能量损失谱(EELS),可在亚埃尺度上对材料的原子和电子结构进行分析。文章简述了扫描透射电子显微镜的基本原理及其应用现状,重点论述了高角环形暗场(HAADF)和环形明场(ABF)像的成像原理、特征和应用。此外,文中还对原子尺度分辨率的X射线能谱及电子能量损失谱元素分析方法进行了简述。     

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.     

现代透射电子显微技术在多铁材料研究中的应用

文章简要介绍了材料科学研究中被广泛应用的透射电子显微(TEM)技术及其在多铁材料研究中的应用,并给出了几个典型案例：利用球差矫正原子分辨扫描透射电子显微术(STEM),并和电子能量损失谱(EELS)相结合,分析多铁异质结界面处的原子分布、离子价态和化学键的变化;结合球差矫正原子分辨透射电子显微图像(HRTEM)和STEM图像,分析多铁材料中的局域对称性破缺和电极化特性;利用原位变温及电/磁场加载技术,研究多铁材料中的结构相变和电畴/磁畴的动态演变特性。文章特别指出,现代透射电子显微学是全面分析理解多铁材料局域微结构,探讨多铁耦合机制及其物理根源的有效手段。     

Atomic resolution STEM analysis of defects and interfaces in ceramic materials

Atomic resolution scanning transmission electron microscopy (STEM) analysis, in particular the combination of Z-contrast imaging and electron energy-loss spectroscopy (EELS) has been successfully used to measure the atomic and electronic structure of materials with sub-nanometer spatial resolution. Furthermore, the combination of this incoherent imaging technique with EELS allows us to correlate certain structural features, such as defects or interfaces directly with the measured changes in the local electronic fine-structure. In this review, we will discuss the experimental procedures for achieving high-resolution Z-contrast imaging and EELS. We will describe the alignment and experimental setup for high-resolution STEM analysis and also describe some of our recent results where the combined use of atomic-resolution Z-contrast imaging and column-by-column EELS has helped solve important materials science problems.     

Core-level spectroscopy of point defects in single layer h-BN

Electron energy-loss spectroscopy (EELS) is used to analyze single-layered hexagonal boron-nitride with or without point defects. EELS profiles using a 0.1 nm probe clearly discriminate the chemical species of single atoms but show different delocalization of the boron and nitrogen K edges. A monovacancy at the boron site is unambiguously identified and the electronic state of its nearest neighboring nitrogen atoms is examined by energy-loss near edge fine structure analysis, which demonstrates a prominent defect state. Theoretical calculations suggest that the observed prepeak originates from the 1s to lowest unoccupied molecular orbital excitation of dangling nitrogen bonds, which is substantially lowered in energy with respect to the three coordinated nitrogen atoms.     

Inelastic electron scattering observation using energy filtered transmission electron microscopy for silicon -- germanium nanostructures imaging

This paper presents a new technique using energy filtered TEM (EFTEM) for inelastic electron scattering contrast imaging of Germanium distribution in Si-SiGe nanostructures. Comparing electron energy loss spectra (EELS) obtained in both SiGe and Si single crystals, we found a spectrum area strongly sensitive to the presence of Ge in the range [50-100 eV]. In this energy loss window, EELS spectrum shows a smooth steeply shaped background strongly depending on Ge concentration. Germanium mapping inside SiGe can thus be performed through imaging of the EELS background slope variation, obtained by processing the ratio of two energy filtered TEM images, respectively, acquired at 90 and 60 eV. This technique gives contrasted images strongly similar to those obtained using STEM Z-contrast, but presenting some advantages: elastic interaction (diffraction) is eliminated, and contrast is insensitive to polycrystalline grains orientation or specimen thickness. Moreover, since the extracted signal is a spectral signature (inelastic energy loss) we demonstrate that it can be used for observation and quantification of Ge concentration depth profile of SiGe buried layers.     

Two-dimensional quantitative mapping of arsenic in nanometer-scale silicon devices using STEM EELS–EDX spectroscopy

Field emission gun (FEG) nanoprobe scanning electron transmission microscopy (STEM) techniques coupled with energy dispersive X-ray (EDX) and electron energy loss spectroscopy (EELS) are evaluated for the detection of the n-type dopant arsenic, in silicon semiconductor devices with nanometer-scale. Optimization of the experimental procedure, data extraction and the signal-to-noise ratio versus electron dose, show that arsenic detection below 0.1% should be possible. STEM EDX and EELS spectrum profiles have been quantified and compared with secondary ion mass spectrometry (SIMS) analyses which show a good agreement. In addition, the arsenic doping level found inside large and small epitaxial devices have been compared using STEM EDX-EELS profiling. The average doping level is found to be similar but variable interface segregation has been observed. Finally, STEM EDX arsenic mapping acquired in a BiCMOS transistor cross-section shows strong heterogeneities and segregation in the epitaxially grown emitter part.     

Image resolution and sensitivity in an environmental transmission electron microscope

An environmental transmission electron microscope provides unique means for the atomic-scale exploration of nanomaterials during the exposure to a reactive gas environment. Here we examine conditions to obtain such in situ observations in the high-resolution transmission electron microscopy (HRTEM) mode with an image resolution of 0.10nm. This HRTEM image resolution threshold is mapped out under different gas conditions, including gas types and pressures, and under different electron optical settings, including electron beam energies, doses and dose-rates. The 0.10nm resolution is retainable for H(2) at 1-10mbar. Even for N(2), the 0.10nm resolution threshold is reached up to at least 10mbar. The optimal imaging conditions are determined by the electron beam energy and the dose-rate as well as an image signal-to-noise (S/N) ratio that is consistent with Rose's criterion of S/N≥5. A discussion on the electron-gas interactions responsible for gas-induced resolution deterioration is given based on interplay with complementary electron diffraction (ED), scanning transmission electron microscopy (STEM) as well as electron energy loss spectroscopy (EELS) data.     

Probing physical properties of confined fluids within individual nanobubbles

Spatially resolved electron energy-loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM) has been used to investigate a He fluidic phase in nanobubbles embedded in a metallic Pd(90)Pt(10) matrix. Using the 1s-->2p excitation of the He atoms, maps of the He density and pressure in bubbles of different diameters have been realized, to provide an indication of the bubble formation mechanism. Detailed local variations of the He K-line characteristics have been measured and interpreted as modifications of the electromagnetic properties of the He atom close to a metallic interface, which affects a correct estimation of the densities within the smallest bubbles.     

Dose-limited spectroscopic imaging of soft materials by low-loss EELS in the scanning transmission electron microscope

Spectroscopic imaging in the scanning transmission electron microscope (STEM) using spatially resolved electron energy-loss spectroscopy (EELS) provides one of the few ways to quantitatively measure the real-space nanoscale morphology of soft materials such as polymers and biological tissue. This paper describes the basic principles of this technique and outlines some of the important attributes that define the achievable spatial resolution. Many soft materials can be differentiated from each other as well as from solvents based on their EELS fingerprints. Applying a multiple least squares (MLS) fitting algorithm using such spectral fingerprints to analyze spatially resolved spectrum datasets enables the quantitative mapping of the different components in a specimen. However, in contrast to TEM studies of many inorganic materials where the spatial resolution is limited principally by the spherical aberration of the objective lens, the spatial resolution associated with the imaging of radiation-sensitive soft materials is limited by the total electron dose to which they can be exposed before suffering irrevocable chemical or structural damage. The Rose criterion provides a simple guide to enhance the so-called dose-limited spatial resolution relevant to soft-materials imaging. By using the low-loss portion of an EELS spectrum where the inelastic scattering cross-sections are highest together with improvements in data-collection efficiency and post-acquisition data processing, the dose-limited resolution in spectrum images of solvated polymers has moved into the sub 10nm regime. This resolution is sufficient to solve important applications-oriented problems associated with hetero interfaces, nanoscale mixing, and nanophase separation.     

Vanadium valency and hybridization in V-doped hafnia investigated by electron energy loss spectroscopy

The valency of vanadium, and thus indirectly the oxygen stoichiometry, of V-doped hafnia synthesized under different atmospheres have been investigated on a nanometer scale by means of electron energy loss spectroscopy (EELS). The EELS V L_2,3 spectra are compared with the results of crystal field multiplet calculations and experiments on reference vanadium oxides. The EELS spectra indicate that V-doped hafnia prepared under reducing (H₂) and neutral (Ar) atmosphere are unambiguously substituted with trivalent vanadium atoms leading to the creation of oxygen vacancies in the structure. On the contrary, stoichiometric (Hf, V)O₂ compound (i.e. V⁴⁺) is more likely to be stabilized under oxidative (air) atmospheres. We also show that the amount of hybridization alters for the different compounds studied but may in part be analyzed by high spatially resolved EELS. The crystal field multiplet calculations particularly indicate that a simple reduction of the Slater integrals gives a good account of the spectral modification induced by hybridization for the case of tetravalent vanadium atoms. Received 17 November 2000 and Received in final form 17 April 2001     

Adsorbate structure modeling based on electron energy loss spectroscopy and lattice dynamical calculations: Application to O/A1(111).

High-resolution electron energy loss spectroscopy (EELS) and lattice dynamical calculations based on pair interactions are used to investigate oxygen chemisorption on Al(111). The O/Al(111) System is complicated by the simultaneous formation of an oxygen overlayer and underlayer. Oxygen atoms at overlayer and underlayer sites near the Al(111) surface produce well-defined vibrational loss peaks in EELS spectra, however, dynamical coupling between the oxygen atoms and with the host lattice cause vibrational energies to shift with overlayer and underlayer concentrations. These shifts as well as structural parameters of the O/Al(111) complex can be deduced from a slab model of the surface lattice dynamics.     

Decisive factors for realizing atomic-column resolution using STEM and EELS

We demonstrate atomic-column imaging by scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS). The silicon atomic-columns of a beta-Si3N4 (0 0 1) specimen are clearly resolved. The atomic-site dependence and the energy-loss dependence of the spatial resolution are elucidated on the basis of the experimental results and multislice calculations. We describe two decisive factors for realizing atomic-column imaging in terms of localization in elastic and inelastic scattering. One is the channeling of the incident probe due to dynamical diffraction, which has atomic-site dependence. The other is the localization in inelastic scattering; in addition to the energy-loss dependence of delocalization, we point out its dependence on the offset energy from the ionization energy, i.e., an additional localization factor concerning the Bethe surface. The present atomic-column observation of the Si-L core-loss image indicates that the local approximation, which can be interpreted intuitively, is achievable under appropriate experimental conditions, such as high-energy-loss, a small convergence angle and a large collection angle (e.g., 400 eV, 15 and 30 mrad, respectively).     

Low voltage TEM: Influences on electron energy loss spectrometry experiments

We discuss the advantages and disadvantages of electron energy loss spectrometry (EELS) a transmission electron microscope (TEM) at different high tensions. Instrumental effects such as energy resolution, spatial resolution, and point spread function of the detecting system, as well as physical effects like inelastic (Coloumb) delocalization and Cerenkov losses are dealt with. It is found that the actually available equipment is suitable for performing low voltage experiments. The energy resolution of a thermo-ionic emitter can be tremendously improved at lower energies, and the detector also has advantageous behaviour.     

Decisive factors for realizing atomic-column resolution using STEM and EELS

We demonstrate atomic-column imaging by scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS). The silicon atomic-columns of a β-Si₃N₄ (0 0 1) specimen are clearly resolved. The atomic-site dependence and the energy-loss dependence of the spatial resolution are elucidated on the basis of the experimental results and multislice calculations. We describe two decisive factors for realizing atomic-column imaging in terms of localization in elastic and inelastic scattering. One is the channeling of the incident probe due to dynamical diffraction, which has atomic-site dependence. The other is the localization in inelastic scattering; in addition to the energy-loss dependence of delocalization, we point out its dependence on the offset energy from the ionization energy, i.e., an additional localization factor concerning the Bethe surface. The present atomic-column observation of the Si-L core-loss image indicates that the local approximation, which can be interpreted intuitively, is achievable under appropriate experimental conditions, such as high-energy-loss, a small convergence angle and a large collection angle (e.g., 400 eV, 15 and 30 mrad, respectively).     

Nanoscale EELS analysis of dielectric function and bandgap properties in gaN and related materials

The low loss region of an EEL spectrum (<50 eV) contains information about excitations of outer shell electrons and thus the electronic structure of a specimen which determines its optical properties. In this work, dedicated electron energy loss spectroscopy (EELS) methods for the experimental acquisition and analysis of spectra are described, which give improved information about the electronic structure near the bandgap region at a spatial resolution in the range of nanometers. For this purpose, we made use of a cold field emission scanning transmission electron microscope (STEM) equipped with a dedicated EELS system. This device provides a subnanometer electron probe and offers an energy resolution of 0.35 eV. Application of suitable deconvolution routines for removal of the zero loss peak extracts information on the bandgap region while the Kramers-Kronig transformation deduces the dielectric properties from the measured energy loss function. These methods have been applied to characterize the optical properties of wide-bandgap materials for the case of III-nitride compounds, which are currently the most promising material for applications on optoelectronic devices working in the blue and ultraviolet spectral range. The obtained results are in excellent agreement with experimental measurements by synchrotron ellipsometry and theoretical studies. The potential of the superior spatial resolution of EELS in a STEM is demonstrated by the analysis of dielectric properties of individual layers of heterostructures and individual defects within wurtzite GaN.     

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.     

Elemental electron energy loss mapping of a precipitate in a multi-component aluminium alloy

The elemental distribution of a precipitate cross section, situated in a lean Al-Mg-Si-Cu-Ag-Ge alloy, has been investigated in detail by electron energy loss spectroscopy (EELS) and aberration corrected high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). A correlative analysis of the EELS data is connected to the results and discussed in detail. The energy loss maps for all relevant elements were recorded simultaneously. The good spatial resolution allows elemental distribution to be evaluated, such as by correlation functions, in addition to being compared with the HAADF image.The fcc-Al lattice and the hexagonal Si-network within the precipitates were resolved by EELS. The combination of EELS and HAADF-STEM demonstrated that some atomic columns consist of mixed elements, a result that would be very uncertain based on one of the techniques alone. EELS elemental mapping combined with a correlative analysis have great potential for identification and quantification of small amounts of elements at the atomic scale.