The STEM approach to the imaging of surfaces and small particles

The characteristics of scanning transmission electron microsopy, which make it a particularly powerful tool for the study of surfaces and small crystals, include the serial nature of the image signal which makes it amenable to recording and image processing procedures, the possibility of correlating the image data with microdiffraction patterns and microanalysis of chosen small regions and the possibilities for combining several different image signals obtained simultaneously. Images obtained from surfaces using reflected diffraction beams may be very sensitive to variations of surface structure but the resolution, depth of focus and contrast of the images are strongly dependent on the nature of the surface and the aperture sizes used in the microsope. Microdiffraction patterns may be obtained from small surface features. Electron energy loss analyses of the diffracted beams provides sensitive indications on surface electron excitations. Microdiffraction patterns obtained in transmission from regions of 1–5 nm diameter provide valuable information on the structure and defects of small crystals, such as those of platinum and gold which are of interest in relation to the study of catalysts.     

Energy filtering transmission electron microscopy using the new JEM-2010FEF

The new JEM-2010FEF electron microscope provides useful techniques based on energy filtering as an omega-type energy filter is integrated into a thermal field-emission 200 kV transmission electron microscope. For example, the zero-loss imaging improves the contrast of high resolution lattice images as well as images of precipitates or lattice defects in alloys. The acquisition time for elemental mapping with core-loss electrons is one order in magnitude shorter than with energy-dispersive X-ray spectroscopy. The removal of inelastically scattered electrons enables us to observe weak lines in convergent-beam electron diffraction patterns from a thicker specimen with a probe size 1–2 nm in diameter. A combination of the field emission gun and sensitive recording media such as an imaging plate and a slow-scan CCD camera makes the energy filtering more powerful.     

In-situ observation of shape and atomic structure of Xe nanocrystals embedded in aluminium

An imaging technique to determine in situ the shape and atomic structure of nanosized Xe crystals embedded in Al is described using high-resolution transmission electron microscopy (HRTEM). The Xe nanocrystals, with sizes less than 5 nm were prepared by the implantation of 30 keV Xe⁺ into Al at room temperature. The fcc Xe nanocrystals are mesotactic with the Al lattice and have a lattice parameter ≈ 50% larger than that of Al. HRTEM images of the Xe were not clear in [110] zone axis illumination because of the small number of Xe atoms relative to Al atoms in any atom column. An off-axial imaging technique that consists of tilting the specimen several degrees from a zone axis and defocusing to suppress the Al lattice fringes is employed for the 110 projection of the Xe/Al system and the structure of the Xe nanocrystals is successfully imaged. The Xe images clearly represent projections of cuboctahedra with faces parallel to eight Al {111} planes truncated by six {100} planes. The results of multislice image simulations using a three-dimensional atomic model agreed well with the results obtained by the off-axial imaging technique. The usefulness of the technique is demonstrated with observations of crystal defects introduced into the Xe under intense 1000 keV electron irradiation.     

Identification of magnetic properties of few nm sized FePt crystalline particles by characterizing the intrinsic atom order using aberration corrected S/TEM

Hard-magnetic nanomaterials like nanoparticles of FePt are of great interest because of their promising potential for data storage applications. The magnetic properties of FePt structures strongly differ whether the crystal phases are face centered cubic (fcc) or face centered tetragonal (fct). We evaluated aberration corrected HRTEM, electron diffraction and aberration corrected HAADF-STEM as methods to measure the chemical degree of order S that describes the ordering of Pt and Fe atoms within the crystals unit cells. S/TEM experiments are accompanied by image calculations. The findings are compared with results obtained from X-ray diffraction on a FePt film. Our results show that STEM is a reasonable fast approach over HRTEM and electron diffraction to locally determine the chemical degree of order S.     

Ab-initio HRTEM simulations of ionic crystals: a case study of sapphire

Solving the atomistic structure of crystal defects by HRTEM often requires comparison of experimental images with simulated images of trial structures. Although many materials of interest exhibit a strong component of ionic bonding, HRTEM image simulations conventionally rely on the scattering factors of neutral atoms. In the present case study of sapphire we thus examine the influence of ionicity on dynamical electron scattering in the specimen and on the HRTEM image. For this purpose, we compare simulated images obtained with ion electron scattering factors with conventional simulated images, obtained with the scattering factors of neutral atoms. We introduce several approaches to include ionicity in image simulations. The most reliable results were obtained by means of self-consistent ab-initio electron bandstructure calculations. After converting the charge density distribution obtained by these calculations into electron scattering factors of the corresponding ions we have implemented the data in our HRTEM image simulation software and used it for simulating HRTEM images. It turned out that these 'realistic' simulated images do not differ significantly from simulated images of neutral atoms. At least for sapphire, this result justifies the usage of 'conventional' image simulations.     

Observation of human dentine by focused ion beam and energy-filtering transmission electron microscopy

Molar dentine was sliced into 100 nm ultrathin sections, by means of a focused ion beam, for observation by energy-filtering transmission electron microscopy (EFTEM). Within the matrix, crystals approximately 10 nm wide and 50–100 nm long were clearly observed. When carbon and calcium were mapped in electron spectroscopic images by EFTEM, carbon failed to localize in crystals. However, it was found in other regions, especially those adjacent to crystals. Because carbon localizations were thought to reflect the presence of organic components, carbon concentration in regions near crystals suggested the interaction of crystals and organics, leading to organic control of apatite formation and growth. Ca was present in almost all regions. The majority of Ca localizing in regions other than crystals may be bound to organic substances present in dentine matrix. These substances are thought to both accumulate Ca and act as reservoirs for crystallization of apatite in dentine.     

On the interpretation of the forbidden spots observed in the electron diffraction patterns of flat Au triangular nanoparticles

In many cases nanostructures present forbidden spots in their electron diffraction patterns when they are observed by transmission electron microscopy (TEM). To interpret their TEM and high resolution transmission electron microscopy (HRTEM) images properly, an understanding of the origin of these spots is necessary. In this work we comment on the origin of the forbidden spots observed in the [111] and [112] electron diffraction patterns of flat gold triangular nanoparticles. The forbidden spots were successfully indexed as corresponding to the first laue Zone (FOLZ) and the HRTEM images presented a contrast produced by the interference of the zero-order Laue zone (ZOLZ) and FOLZ spots. We discuss the use of the forbidden spots in the study of the structure of nanoparticles and show that they are related to the shape and incompleteness of layers in the very thin particles.     

Reduction of charging in protein electron cryomicroscopy

Charging causes a loss of resolution in electron cryomicroscopy with biological specimens prepared without a continuous carbon support film. Thin conductive films were deposited onto catalase crystals prepared across holes using ion-beam sputtering and thermal evaporation and evaluated for the effectiveness of charge reduction. Deposits applied by ion-beam sputtering reduced charging but concurrently resulted in structural damage. Coatings applied by thermal evaporation also reduced charging, and preserved the specimen structure beyond 5 Å resolution as judged from electron diffraction patterns and images of glucose-embedded catalase crystals tilted to 45° in the microscope. This study demonstrates for the first time the feasibility of obtaining high-resolution data from unstained, unsupported protein crystals with a conductive surface coating.     

TEM, HRTEM, electron holography and electron tomography studies of γ' and γ" nanoparticles in Inconel 718 superalloy

The aim of the study was the identification of γ' and γ" strengthening precipitates in a commercial nickel-base superalloy Inconel 718 (Ni-19Fe-18Cr-5Nb-3Mo-1Ti-0.5Al-0.04C, wt %) using TEM dark-field, HRTEM, electron holography and electron tomography imaging. To identify γ' and γ" nanoparticles unambiguously, a systematic analysis of experimental and theoretical diffraction patterns were performed. Using HRTEM method it was possible to analyse small areas of precipitates appearance. Electron holography and electron tomography techniques show new possibilities of visualization of γ' and γ" nanoparticles. The analysis by means of different complementary TEM methods showed that γ" particles exhibit a shape of thin plates, while γ' phase precipitates are almost spherical.     

Towards 1.0 Å resolution: taking advantage of dynamical scattering, and the benefits for structure retrieval

This paper is an exploration of the behaviour of high-resolution transmission electron microscope (HRTEM) images at up to 1 Å resolution. The ultimate limits to HRTEM (structure) resolution and the manner in which strong scattering may lead to weak diffraction in heavy fcc metals are discussed. A resolution of 1.0 Å is somewhat better than the ultimate resolution presently achievable in a 400-kV electron microscope. In heavy metals, such as platinum, it is found that the lattice fringe contrast is very low in the [011] projection, but that fringe contrast may be improved by imaging in the [111] projection. For atomic resolution imaging of the heavy metals in the [111] projection a resolution of 1.2 Å is required. For the study of oxygen position in high-temperature superconducting (HTS) oxides a resolution of between 1.2 and 1.4 Å is required. At better than 1.2 Å resolution the thick crystal images in HTS oxides remain simple and are easily interpreted. At such resolution all atomic columns are separated for the HTS [010] projection and the dynamical diffraction effects improve the contrast of oxygen atoms relative to the metal atoms.     

An efficient approach to characterize pseudo-merohedral twins by precession electron diffraction: Application to the LaGaO3 perovskite

Pseudo-merohedral twins are frequently observed in crystals displaying pseudo-symmetry. In these crystals, many [u v w] zone axis electron diffraction patterns are very close and can only be distinguished from intensity considerations. On conventional diffraction patterns (selected-area electron diffraction or microdiffraction), a strong dynamical behaviour averages the diffracted intensities so that only the positions of the reflections on a pattern can be considered. On precession electron diffraction patterns, the diffracted beams display an integrated intensity and a “few-beam” or “systematic row” behaviour prevails which strongly reduces the dynamical interactions. Therefore the diffracted intensity can be taken into account. A procedure based on observation of the weak extra-reflections connected with the pseudo-symmetry is given to identify without ambiguity any zone axis. It is successfully applied to the identification and characterization of {1 2 1} reflection twins present in the LaGaO₃ perovskite.     

Observation of microdiffraction patterns with a dedicated STEM instrument

A two-dimensional detector system, designed for the observation and recording of microdiffraction patterns formed in an HB 5 scanning transmission electron microscope (STEM) is described and discussed. Possibilities are described and demonstrated for the simultaneous or successive recording of microdiffraction patterns from regions of diameter 3 å or more, bright- or dark-field STEM images, EELS spectra, secondary electron images, and in-line holograms. Applications of the system have been made to studies of catalyst particles, reflection-mode imaging of bulk surfaces, and image reconstruction from microdiffraction patterns obtained from each point of a STEM image.     

LACDIF, a new electron diffraction technique obtained with the LACBED configuration and a C(s) corrector: comparison with electron precession

By combining the large-angle convergent-beam electron diffraction (LACBED) configuration together with a microscope equipped with a C(s) corrector it is possible to obtain good quality spot patterns in image mode and not in diffraction mode as it is usually the case. These patterns have two main advantages with respect to the conventional selected-area electron diffraction (SAED) or microdiffraction patterns. They display a much larger number of reflections and the diffracted intensity is the integrated intensity. These patterns have strong similarities with the electron precession patterns and they can be used for various applications like the identification of the possible space groups of a crystal from observations of the Laue zones or the ab-initio structure identifications. Since this is a defocused method, another important application concerns the analysis of electron beam-sensitive materials. Successful applications to polymers are given in the present paper to prove the validity of this method with regards to these materials.     

Interactions of electron beams with surfaces of MgO crystals

The strong interaction of electrons with the flat surfaces of small crystals has been investigated by high resolution CTEM and STEM instruments. When cubic crystals of MgO smoke with edges 20–300 nm are oriented so that the ?001? or ?011? zone axis is parallel to the optical axis, then two kinds of external fringes are observed at (100) surfaces. One kind is parallel to the surface, having spacings up to 0.4 nm. These are caused by interference among the electron channelled along the surface. Fresnel-diffracted ones and the remnant of the incident beam. Fringes of the other kind, which appear as fine structure in the first kind of fringes, are perpendicular to the crystal edge. When an electron beam is parallel to the ?011? axis, the second kind of fringe, whose spacing is 0.3 nm corresponding to d₀₁₁, shows the difference of the surface potential between magnesium atoms and oxygen atoms. Selected area diffraction patterns and microdiffraction patterns also show the same periodicities as in the two kinds of fringes. Simulated images, using the scattering amplitudes for ions, are compared with observations.     

High-resolution imaging of organic pharmaceutical crystals by transmission electron microscopy and scanning moiré fringes

Formulation processing of organic crystalline compounds can have a significant effect on drug properties, such as dissolution rate or tablet strength/hardness. Transmission electron microscopy (TEM) has the potential to resolve the atomic lattice of these crystalline compounds and, for example, identify the defect density on a particular crystal face, provided that the sensitivity of these crystals to irradiation by high-energy electrons can be overcome. Here, we acquire high-resolution (HR) lattice images of the compound furosemide using two different methods: low-dose HRTEM and bright-field (BF) scanning TEM (STEM) scanning moiré fringes (SMFs). Before acquiring HRTEM images of furosemide, a model system of crocidolite (asbestos) was used to determine the electron flux/fluence limits of low-dose HR imaging for our scintillator-based, complementary metal-oxide semiconductor (CMOS) electron camera by testing a variety of electron flux and total electron fluence regimes. An electron flux of 10 e⁻/(Ų s) and total fluence of 10 e⁻/Ų was shown to provide sufficient contrast and signal-to-noise ratio to resolve 0.30 nm lattice spacings in crocidolite at 300 kV. These parameters were then used to image furosemide which has a critical electron fluence for damage of ≥10 e⁻/Ų at 300 kV. The resulting HRTEM image of a furosemide crystal shows only a small portion of the total crystal exhibiting lattice fringes, likely due to irradiation damage during acquisition close to the compound's critical fluence. BF-STEM SMF images of furosemide were acquired at a lower electron fluence (1.8 e⁻/Ų), while still indirectly resolving HR details of the (001) lattice. Several different SMFs were observed with minor variations in the size and angle, suggesting strain due to defects within the crystal. Overall BF-STEM SMFs appear to be more useful than BF-STEM or HRTEM (with a CMOS camera) for imaging the crystal lattice of very beam-sensitive materials since a lower electron fluence is required to reveal the lattice. BF-STEM SMFs may thus prove useful in improving the understanding of crystallization pathways in organic compounds, degradation in pharmaceutical formulations and the effect of defects on the dissolution rate of different crystal faces. Further work is, however, required to quantitatively determine properties such as the defect density or the amount of relative strain from a BF-STEM SMF image.     

Extended electron energy-loss fine structure and selected-area electron diffraction studies of small palladium clusters

Extended electron energy-loss fine structure (EXELFS) and selected-area electron diffraction (SAED) techniques have both been applied to the study of the crystalline structure of Pd clusters of average diameters ranging from bulk to 24 Å. The combined use of these techniques gives complementary information about the crystalline structure of Pd clusters. Both techniques show the same lattice parameter expansion, about 4% for the smallest Pd cluster, with respect to the bulk. The EXELFS analysis performed on the Pd-M_4,5 edge shows a sizeable increase of structural disorder in the smallest cluster. SAED gives additional information about the Pd bulk sample, showing the occurrence of crystalline regions about 50 Å in diameter.     

An electron microscopy study of the phase Al3Fe

The phase Al₃Fe (monoclinic C2/m, a = 1·549 nm, b = 0·808 nm, c = 1·248 nm, β = 107·8°) has been studied by transmission electron microscopy (TEM) and high resolution electron microscopy (HREM). Crystals were obtained from a direct chill-cast ingot of an Al-0·25 wt% Fe-0·13 wt% Si alloy. Extracted crystals were prepared by dissolving the aluminium phase in butanol and filtering off the particles. The extracted Al₃Fe crystals were mainly (100) platelets. The monclinic lattice was confirmed by tilt experiments and the mirror plane was confirmed by convergent beam electron diffraction. Experimental HREM images from the [100] and [110] projection agreed with images calculated by the multislice method. The interpretation of images in terms of a projected crystal structure is discussed. Common defects in Al₃Fe crystals were: twins on (100) and faults on (001). The (001) faults could be described by a displacement 1/2·[100] on a fault plane at z = 0·5 in the unit cell. A model for (001) faults, based on multiple twinning, is proposed.     

Effect of crystal and beam tilt on simulated high-resolution TEM images of interfaces.

The effects of crystal and beam tilt on high-resolution transmission electron microscope (HRTEM) images of planar coherent interfaces were investigated by multislice image simulations. It was found that a beam tilt of 0.5 Bragg angle (theta B) was sufficient to introduce detrimental artifacts into most images of interfaces in crystals only 1/8 xi 000 thick, while crystal tilt had a much smaller effect even for crystals 1 xi 000 thick. Effects produced in HRTEM images of interfaces by crystal and beam tilt included the introduction of additional periodicities and loss of compositional detail across a boundary, translation of a boundary from its actual position, and apparent mismatch of atomic planes across a perfectly coherent interface. These results indicate that alignment of the electron beam parallel to the optic axis is critical for reliable HRTEM imaging of interfaces in materials. Techniques for obtaining accurate alignment are also discussed.     

Microdiffraction and analysis

The intensity distribution in the microdiffraction pattern depends strongly on the coherence of the illuminated source. The coherence width at the specimen level is considered as a parameter to check the coherence of an electron microscope. Two application examples are illustrated. A small interphase precipitate of MgNi₂ in an Ni superalloy has been identified by a combination of microdiffraction and energy dispersive spectrum (EDS) techniques, though it can not be found by conventional transmission electron microscopy (TEM) and selected area diffraction (SAD). By means of microdiffraction as well as high-resolution electron microscopy (HREM) imaging a defect structure has been determined. Such a defect makes the lattice extinction spots appear with various intensities in the selected area diffraction and microdiffraction patterns.     

Electron microdiffraction from very small gold particles

By use of a scanning transmission electron microscope equipped with a two-dimensional detection system, microdiffraction patterns have been obtained from gold crystals of diameter 15–20 Å dispersed in a thin polyester film. Comparison with diffraction patterns calculated for various models suggests that only a small proportion of the particles have the multiply twinned form which has been proposed as the equilibrium state from very small particles, although some twinning is common. It is shown to be difficult to determine, on the basis of the form of the diffraction pattern, whether multiply twinned particles have localized or distributed strains to accommodate the misfit of assemblies of tetrahedral twinned component crystal regions.