Nanometric crystal defects in transmission electron microscopy

Transmission electron microscopy (TEM) is revisited in order to define methods for the identification of nanometric defects. Nanometric crystal defects play an important role as they influence, generally in a detrimental way, physical properties. For instance, radiation-induced damage in metals strongly degrades mechanical properties, rendering the material stronger but brittle. The difficulty in using TEM to identify the nature and size of such defects resides in their small size. TEM image simulations are deployed to explore limits and possible ways to improve on spatial resolution and contrast. The contrast of dislocation loops, cavities, and a stacking fault tetrahedra (SFT) are simulated in weak beam, interfering reflections (HRTEM), and scanned condensed electron probe (STEM) mode. Results indicate that STEM is a possible way to image small defects. In addition, a new objective aperture is proposed to improve resolution in diffraction contrast. It is investigated by simulations of the weak beam imaging of SFT and successfully applied in experimental observations.     

Calculations and observations of the weak-beam contrast of small lattice defects

Dynamical many-beam calculations were performed for the investigation of the diffraction contrast of small lattice defects observed in the electron microscope under weak-beam conditions. A new computational method was developed with which the depth position z_o of the defect and the thickness t of the foil were eliminated from the integration procedure of the differential equations. The contrast figures for dislocation loops which were inclined to the foil plane and for spherical inclusions were calculated for various excitation errors of the weakly excited beam and for various combinations of t and z₀. The dependence of the contrast figures on z₀ (‘depth oscillations’) were studied in detail. The results of the calculations are compared with experimental observations.     

The use of a hybrid diffraction unit in the measurement of dislocation densities by electron microscopy

The expression used in the electron microscopical measurement of dislocation densities is ?=2N/Lt, where N is the number of intersections between the dislocation lines in a TEM image, L the total length of a set of sampling lines superimposed upon that image (corrected for magnification) and t the thickness of the thin foil containing the dislocation structure. During the estimation of ? it is therefore important to reduce errors in the measurements of all three variables. It is shown how calibration of the microscope magnification, careful consideration of diffraction conditions and use of the hollow cone and rocking beam facilities on the hybrid diffraction unit fitted to the Philips EM 400T can assist in increasing the speed and accuracy of the measurement procedure.     

Scanning electron microscopy imaging of dislocations in bulk materials, using electron channeling contrast

The imaging and characterization of dislocations is commonly carried out by thin foil transmission electron microscopy (TEM) using diffraction contrast imaging. However, the thin foil approach is limited by difficult sample preparation, thin foil artifacts, relatively small viewable areas, and constraints on carrying out in situ studies. Electron channeling imaging of electron channeling contrast imaging (ECCI) offers an alternative approach for imaging crystalline defects, including dislocations. Because ECCI is carried out with field emission gun scanning electron microscope (FEG-SEM) using bulk specimens, many of the limitations of TEM thin foil analysis are overcome. This paper outlines the development of electron channeling patterns and channeling imaging to the current state of the art. The experimental parameters and set up necessary to carry out routine channeling imaging are reviewed. A number of examples that illustrate some of the advantages of ECCI over thin foil TEM are presented along with a discussion of some of the limitations on carrying out channeling contrast analysis of defect structures.     

Weak beam under convergent beam illumination

The weak beam technique is now used widely for the determination of stacking fault energies, in particular for intermetallic alloys, and the accuracy of the approach is critically dependent upon the reliability of the relationship between the image and the actual position of the dissociated dislocations. Examining as a model case a dislocation dissociated into two Shockley partial dislocations in Cu at 100 kV for orientations ranging through the g(3g) weak beam condition, image simulations are used to explore the accuracy to which the true spacing between the partial dislocations can be determined from the spacing measured on the image as a function of the dislocation character, the foil thickness, the dislocation depth in the foil, the diffraction condition and the beam convergence. It appears that for image simulations and for the given conditions a beam convergence of about 5 mrad allows to greatly improve the accuracy, and that beam convergence must be taken into account quantitatively when deducing the true partial dislocation spacing as it is the principal parameter controlling the precision in this type of measurement.     

Reflection electron energy-loss spectroscopy and imaging for surface studies in transmission electron microscopes.

A review is given on the techniques and applications of high-energy reflection electron energy-loss spectroscopy (REELS) and reflection electron microscopy (REM) for surface studies in scanning transmission electron microscopes (STEM) and conventional transmission electron microscopes (TEM). A diffraction method is introduced to identify a surface orientation in the geometry of REM. The surface dielectric response theory is presented and applied for studying alpha-alumina surfaces. Domains of the alpha-alumina (012) surface initially terminated with oxygen can be reduced by an intense electron beam to produce Al metal; the resistance to beam damage of surface domains initially terminated with Al+3 ions is attributed to the screening effect of adsorbed oxygen. Surface energy-loss near-edge structure (ELNES), extended energy-loss fine structure (EXELFS), and microanalysis using REELS are illustrated based on the studies of TiO2 and MgO. Effects of surface resonances (or channeling) on the REELS signal-to-background ratio are described. The REELS detection of a monolayer of oxygen adsorption on diamond (111) surfaces is reported. It is shown that phase contrast REM image content can be significantly increased with the use of a field emission gun (FEG). Phase contrast effects close to the core of a screw dislocation are discussed and the associated Fresnel fringes around a surface step are observed. Finally, an in situ REM experiment is described for studying atomic desorption and diffusion processes on alpha-alumina surfaces at temperatures of 1,300-1,400 degrees C.     

Diffraction effects and inelastic electron transport in angle‐resolved microscopic imaging applications

We analyse the signal formation process for scanning electron microscopic imaging applications on crystalline specimens. In accordance with previous investigations, we find nontrivial effects of incident beam diffraction on the backscattered electron distribution in energy and momentum. Specifically, incident beam diffraction causes angular changes of the backscattered electron distribution which we identify as the dominant mechanism underlying pseudocolour orientation imaging using multiple, angle‐resolving detectors. Consequently, diffraction effects of the incident beam and their impact on the subsequent coherent and incoherent electron transport need to be taken into account for an in‐depth theoretical modelling of the energy‐ and momentum distribution of electrons backscattered from crystalline sample regions. Our findings have implications for the level of theoretical detail that can be necessary for the interpretation of complex imaging modalities such as electron channelling contrast imaging (ECCI) of defects in crystals. If the solid angle of detection is limited to specific regions of the backscattered electron momentum distribution, the image contrast that is observed in ECCI and similar applications can be strongly affected by incident beam diffraction and topographic effects from the sample surface. As an application, we demonstrate characteristic changes in the resulting images if different properties of the backscattered electron distribution are used for the analysis of a GaN thin film sample containing dislocations.     

Multiple-Shockley unfaulting of single-layer faulted defects

The general principles laid down by Swart & Kritzinger (1974a) in a paper dealing with the unfaulting of Frank dislocation loops by the simultaneous action of two shearing Shockley dislocations are applied to explain the structure and electron diffraction contrast behaviour of certain complex single-layer dislocation configurations observed in quenched aluminium and dilute Al-Mg alloys. In these cases the simultaneous operation of three Shockley dislocations is employed. It is also demonstrated that adequate stresses, such as those encountered during annealing at temperatures ～150°C, serve to transform butterfly hexagons to normal hexagonal prismatic dislocation loops, confirming the expectation that the butterfly defects are in a metastable state.     

带孔纳米单晶铜悬臂梁弯曲的分子动力学模拟

应用分子动力学方法模拟了带孔纳米单晶铜悬臂梁的弯曲过程。通过一端固定另一端施加横向作用力驱使原子运动,得到纳米单晶铜悬臂梁弯曲的变形图。对其不同于宏观连续介质理论的位移-载荷曲线进行分析,给出了合理的解释。结果表明:纳米尺度下的微缺陷对纳米单晶铜悬臂梁的性能具有明显的影响;尺寸效应和表面效应的影响,以及位错滑移和弛豫的综合作用,使得纳米单晶铜悬臂梁在纳米尺度下表现出与宏观尺度下不同的力学特性。     

Novel techniques of preparing TEM samples for characterization of irradiation damage

Focus ion beam preparation of transmission electron microscopy (TEM) samples has become increasingly popular due to the relative ease of extraction of TEM foils from specific locations within a larger sample. However the sputtering damage induced by Ga ion bombardment in focus ion beam means that traditional electropolishing may be a preferable method. First, we describe a special electropolishing method for the preparation of irregular TEM samples from ex‐service nuclear reactor components, spring‐shaped spacers. This method has also been used to prepare samples from a nonirradiated component for a TEM in situ heavy ion irradiation study. Because the specimen size is small (0.7 × 0.7 × 3 mm), a sandwich installation is adopted to obtain high quality polishing. Second, we describe some modifications to a conventional TEM cross‐section sample preparation method that employs Ni electroplating. There are limitations to this method when preparing cross‐section samples from either (1) metals which are difficult to activate for electroplating, or (2) a heavy ion irradiated foil with a very shallow damage layer close to the surface, which may be affected by the electroplating process. As a consequence, a novel technique for preparing cross‐section samples was developed and is described.     

Static-charging mitigation and contamination avoidance by selective carbon coating of TEM samples

Prior to transmission electron microscopy (TEM) analyses, insulating specimens need to become coated with a charge-draining layer. Rather than coating the entire TEM foil with a thin film of homogeneous thickness, selective coating is proposed. Using a novel preparation tool, peripheral parts of the sample are coated with a relatively thick (4-8 nm) carbon film while the central, electron-transparent part of the sample is hidden behind a shape-adopted mask and thus not directly exposed to carbon deposition. Beneath the mask, an ultrathin (3-7 A) carbon film is formed that is (i) thick enough to drain charges evolving upon electron irradiation in the electron microscope and (ii) thin enough to avoid typical contamination effects caused by superficial carbon diffusion. Consequently, image quality is becoming enhanced in high-resolution imaging and sensitivity is significantly increased in all nano-beam related techniques including elemental analytics, convergent-beam and nano-beam electron diffraction, and spectral imaging.     

Determination of crystal polarity from bend contours in transmission electron microscope images

A new method for determining the polarity of crystals with sphalerite structure (GaAs, GaSb, InP, etc.) within the transmission electron microscope (TEM) is presented. The method is derived from an established convergent beam electron diffraction (CBED) method (J. Appl. Crystallogr. 15 (1982) 60) and exploits the effects of the dynamical scattering on the contrast of bend contour crossings in conventional TEM images. In contrast to the CBED method, the bend contour method is performed in the image mode of the TEM. The sample can, therefore, be viewed while performing the polarity analysis. Furthermore, in the presence of strong foil bending, the bend contour method has some advantages for practical work. A general contrast rule for the bend contour intersections is stated which allows to readily obtain the crystal polarity by comparing the contrast in experimental images with the prediction of the rule. Exemplarily, the polarity of GaAs in TEM samples prepared for investigation in the two frequently used projections < 001 > and < 110 > is determined. The validity of the rule for the cases studied is confirmed by simulations of the dynamical scattering process. Furthermore, an independent analysis of the crystal polarity by making use of a long-range-ordered (GaIn)P layer grown on top of the GaAs confirms the results obtained with the bend contour method. As an example, the usefulness of the method is demonstrated in an analysis of the alpha/beta-character of misfit dislocations at the interface between the GaAs substrate and the (GaIn)P layer.     

Effect of sample bending on diffracted intensities observed in CBED patterns of plan view strained samples

Convergent beam electron diffraction is used to study the effect of the sample bending on diffracted intensities as observed in transmission electron microscopy (TEM). Studied samples are made of thin strained semiconductor Ga(1-)(x)In(x)As epitaxial layers grown on a GaAs substrate and observed in plan view. Strong variations of the diffracted intensities are observed depending on the thinning process used for TEM foil preparation. For chemically thinned samples, strong bending of the substrate occurs, inducing modifications of both kinematical and dynamical Bragg lines. For mechanically thinned samples, bending of the substrate is negligible. Kinematical lines are unaffected whereas dynamical lines have slightly asymmetric intensities. We analyse these effects using finite element modelling to calculate the sample strain coupled with dynamical multibeam simulations for calculating the diffracted intensities. Our results correctly reproduce the qualitative features of experimental patterns, clearly demonstrating that inhomogeneous displacement fields along the electron beam within the substrate are responsible for the observed intensity modifications.     

A technique for the preparation of cross-sectional TEM samples of ZnSe/GaAs heterostructures which eliminates process-induced defects

Cross-sectional transmission electron microscopy (TEM) sample preparation of ZnSe/GaAs epitaxial films is investigated. Conventional argon ion milling is shown to produce a high density (～ 5–8 × 10¹¹/cm²) of small (diameter ～ 60–80 Å) extended defects (stacking faults, microtwins, double positioning twins, etc.). In addition, transmission electron diffraction results indicate a thin ZnO layer can also occasionally form upon ion milling or electron-beam irradiation although the exact conditions for ZnO formation are not well understood. Conventional TEM (amplitude contrast) and high-resolution TEM (phase contrast) imaging in combination with transmission electron diffraction studies were performed to determine the optimum method of removing the ion milling related damage and ZnO layers during sample preparation. HF/HCl, NaOH/H₂O, H₂SO₄/H₂O₂/H₂O and Br₂/CH₃OH etching mixtures as well as low voltage argon or iodine ion milling were studied. A low energy (2 ke V) iodine or argon ion milling step was shown to remove the ZnO layer and reduced the density of the extended defects associated with Ar⁺ ion milling, but was unsuccessful in removing all of the defects. Auger electron spectroscopy results indicate residual iodine was either left on the surface or implanted beneath the surface during iodine ion milling. Etching the XTEM samples in HF/HCl was shown to be effective in removing the ZnO layer but had little or no effect on the ion milling induced defects. Etching the samples in a 0.5% Br₂/CH₃OH solution resulted in complete elimination of the ion milling induced extended defects including the residual defects associated with iodine ion milling. In addition the Br₂/CH₃OH etch produced the best surface morphology. Thus a brief (1–2 seconds) Br₂/CH₃OH etch after conventional preparation (argon ion milling) of cross-sectional ZnSe/GaAs TEM samples appears to be an inexpensive and superior alternative to iodine ion milling.     

Retrieving overlapping crystals information from TEM nano‐beam electron diffraction patterns

The diffraction patterns acquired with a transmission electron microscope (TEM) contain Bragg reflections related to all the crystals superimposed in the thin foil and crossed by the electron beam. Regarding TEM‐based orientation and phase characterisation techniques, the nondissociation of these signals is usually considered as the main limitation for the indexation of diffraction patterns. A new method to identify the information related to the distinct but overlapped grains is presented. It consists in subtracting the signature of the dominant crystal before reindexing the diffraction pattern. The method is coupled to the template matching algorithm used in a standard automated crystal orientation mapping tool (ACOM‐TEM). The capabilities of the approach are illustrated with the characterisation of a NiSi thin film stacked on a monocrystalline Si layer. Then, a subtracting‐indexing cycle applied to a 70 nm thick thin foil containing polycrystalline tungsten electrical contacts shows the capability of the technique to recognise small nondominant grains.     

Preparation of lithium specimens for transmission electron microscopy

A method of preparing undeformed thin lithium specimens for TEM is described. A solution of dehydrated methanol and toluene is used both for initial dishing of the foil by chemical polishing and also for final thinning. Under electron beam irradiation in the TEM, new pure Li crystals can grow out of the existing Li specimen. These in situ crystals can be used for the study of the microstructure and electronic structure of Li using TEM and electron energy loss spectrometry.     

New developments in the characterization of dislocation loops from LACBED patterns

The characterization of the Burgers vector of dislocations from large‐angle convergent‐beam electron diffraction (LACBED) patterns is now a well‐established method. The method has already been applied to relatively large and isolated dislocation loops in semiconductors. Nevertheless, some severe experimental difficulties are encountered with small dislocation loops. By using a 2 µm selected‐area aperture and a carbon contamination point to mark the loop of interest, we were able to characterize both the plane and the Burgers vector of dislocation loops of a few tens of nanometres in size present in Al‐Cu‐Mg alloys.     

Images obtained in STEM of gold particles condensed on the top of thick single crystals of copper

It is proposed that when a thin sample is mounted on the top surface of a thick single crystal foil, this foil may function as a collector aperture with regard to the radiation transmitted through the thin sample. The detailed aspects of how the crystal foil may perform as an aperture are discussed in terms of the electron equivalent of the Borrmann effect in crystals. Experiments are presented which demonstrate that the image of the thin sample is sensitive to the thickness of the single crystal foil and to its orientation with regard to the beam axis. It is concluded from the experimental results that the crystal foil does perform a collector aperture-like function.     

Effects of surface relaxation on convergent-beam electron diffraction analysis of stress in silicon

Convergent‐beam electron diffraction on cross‐sectional transmission electron microscopy specimens can map strains in the silicon substrate of microelectronics devices with high spatial resolution. However, at shallow depths below the interface, most of the diffraction lines within a convergent‐beam electron diffraction pattern are split, rendering pattern interpretation impossible in the classic way. The splitting effect was systematically analysed for a variety of materials, and the same qualitative behaviour that can be explained by stress relaxation at the surfaces of the thin transmission electron microscopy specimen was observed. The effects of surface relaxation are modelled by finite elements simulations. The results predict well the experimental magnitude of the splitting for a variety of diffraction lines at different positions below the interface, but fail to simulate the intensity of the secondary lines. Possible reasons for such discrepancies are discussed and assessed.