TRANSMISSION ELECTRON MICROSCOPY (TEM)

Transmission electron microscopy can provide microstructural, crystal structure as well as micro-chemical information with high spatial resolution from each of the microscopic phases individually. TEM is therefore a very powerful tool for materials characterization. TEM studies not only aid in improved insight into structure–property correlations, but also in alloy development for improved performance.

In 1924, de Broglie brought out the wave-character of electron rays, which has been the basis for the construction of the electron microscope. The origin of TEM can be traced to the development of magenetic solenoid coils to focus cathode rays in high-voltage CRT, mainly to understand the effect of high-voltage surges—such as those caused by lightening—on damage to transmission lines. Although Dennis Gabour from the Technical University, Berlin, was the first to use iron shrouded coils to focus cathode rays in the innovative CRT built in 1924–26 towards his PhD, he did not realise their magnetic lens effect until Hans Busch published a paper in 1926 on the effect of short solenoid coils in focussing electrons. Thus, though Dennis Gabour was the first to demonstrate the focussing effect of electrons, Busch is still considered as the father of electron optics.

To observe the image of electrons emitted from a cold cathode on a fluorescent screen, Ruska and Knoll succeeded in magnifying the image by 17X by using a second solenoid coil between the first lens and the final plate. This can be considered as the first prototype TEM to demonstrate the focussing effect of transmitted electrons to form magnified images. In 1935, Knoll, while studying television camera tubes, succeeded in forming a topographic image of solid substances using a scanned electron beam with a resolution of about 0.1 mm, thus establishing the framework for developing the scanning electron microscope.

5.4.1 Advanced techniques of TEM

From the first prototype TEM with an image magnification of 17X, developments in electronics, electron optics and lens fabrication have resulted in tremendous improvements, leading to the current dedicated high-resolution TEM capable of sub-Angstrom spatial resolution with the possibility of recording images of over a million times in magnification. With field emission gun electron sources and by using aberration corrected lenses, resolutions less than 0.1 nm have been achieved. In addition, computational abilities have improved to a point where materials properties can be predicted from computer models that contain a similar number of atoms, as is observable by high resolution TEM (HRTEM).

Transmission electron microscopes are improving rapidly to meet the current requirements of developing advanced materials for strategic applications and also by an equally fast evolution of nanotechnology and semiconductor technology. Apart from lattice imaging by HRTEM to study interfaces, defects and precipitation studies, crystal structure of the individual phases can also be obtained by selected area and microdiffraction techniques in TEM. Convergent beam electron diffraction (CBED) can be used to obtain information on symmetry, lattice, strains, thickness, etc., from localized regions of the crystal. Although symmetry information can also be obtained from X-ray diffraction, the advantage of CBED is that symmetry information of individual phases from localized sub-microscopic regions can be obtained along with their morphology, interface coherency/defect structure and micro-chemistry from associated techniques in TEM. Micro-chemical information can be obtained by either energy dispersive analysis of X-rays (EDAX) or by using electron energy loss spectroscopy (EELS). EELS is a highly sensitive micro-analytical tool with high spatial resolution that can identify low atomic number elements as well. Apart from elemental concentrations, information on electron density, density of states and electronic structure as well as site symmetry, radial distribution functions and specimen thickness can be obtained with high spatial resolution by EELS.

Using a technique called ALCHEMI (Atom Location by CHanelling Enhanced MIcroanalysis) based on electron channelling effect and used in association with analytical techniques like EDAX and EELS, it is also possible to identify individual element sites of occupation in ordered crystals. In fact, current technology has advanced to such a level that it is also possible to remotely operate the microscope from a control room situated away from the actual microscope via a computer supported with a web browser and necessary interface. With the feasibility to obtain information on the entire gamut of material including microstructure, crystal structure, symmetry, lattice strain, interface lattice structure, micro-chemistry, bonding state of constituent elements in the phase, etc., TEM is an inevitable tool in the development and characterization of advanced materials. TEM is commonly used for studying defects in crystals.

In contrast to X-rays, electron beams can be focussed using magnetic fields and can hence be used for imaging. Magnetic fields can be used as convex lenses for the electron waves. As with conventional optical lenses, the lens aberrations are difficult to correct even in magnetic lenses. However, the intensity distribution of the electron waves leaving the specimen can be magnified by an electron optical system and resolutions of < 0.1 nm are possible.

Inelastic and elastic scattering are two ways in which electrons interact with the material. Inelastic scattering (leading eventually to absorption) must be minimized to obtain good image contrast, since it contains no local information. The electron beam then gets elastically scattered (diffraction). The lattice defects modulate the amplitude and phase of the incident and diffracted beams.

In TEM, an electron beam with energy of 100 keV or more (up to 3 MeV) is allowed to go through a thin specimen (less than 200 nm). TEM offers special resolution down to an Angstrom, high magnifications up to 106 and it can work as a microscope and a diffractometer. Keeping inelastic scattering of the electrons small has supremacy; this demands specimen thickness between 10 nm and 1 μm. The resolution depends on the thickness; high-resolution TEM (HRTEM) demands specimen thickness in the nanometre region.

5.4.2 Quantitative analysis using TEM

Practically all detailed information about extended defects comes from TEM investigations which not only show the defects but, using proper theory, provides quantitative information about say, strain fields. The electron-optical system not only serves to magnify the intensity (and, in HRTEM, the phase) distribution of the electron waves leaving the specimen, but, at the press of a switch, provides electron diffraction patterns. Figure 5.4 (see Plate 5) shows the basic electro-optical design of a TEM.

By tilting the specimen relative to the incident electron beam, it is possible to satisfy the Bragg condition either for many or just two or none of the reciprocal lattice vectors g. The preferred condition for regular imaging is the ‘two-beam’ case with only one ‘reflex’ excited—the Bragg condition is only satisfied for one point in the reciprocal lattice or one diffraction vector g [usually with small Miller indices, e.g., {111} or {220}]. The main challenge in any TEM investigation is specimen preparation. Obtaining specimens thin enough and containing the defects to be investigated in the right geometry (e.g., in cross section) is a big task. TEMs are patterned after transmission light microscopes and will yield the following information.

Morphology: The size, shape and arrangement of the particles which make up the specimen as

well as their relationship to each other on the scale of atomic diameters.

Crystallographic information: The arrangement of atoms in the specimen and their degree of

order, detection of atomic-scale defects in areas a few nanometres in diameter.

Compositional information: The elements and compounds the sample is composed of and

their relative ratios, in areas a few nanometres in diameter. 5.4.3 Functioning of a TEM

The functioning of a TEM is similar to a slide projector in some respects. A projector shines (transmits) a beam of light through the slide; as the light passes through it is affected by the structures and objects on the slide. This causes only some part of the light beam to be transmitted through some part of the slide. This transmitted beam is then projected on the viewing screen, forming an enlarged image of the slide. A more technical explanation of the working of a typical TEM is as follows (Fig. 5.4, see Plate 5):

1. The electron gun at the top of the microscope produces a stream of monochromatic electrons.

2. This stream is focussed to a small, thin, coherent beam by the use of condenser lenses 1 and 2. The first lens determines the spot size, the size of the electron beam that strikes the sample. The second lens changes the size of the spot from a wide dispersed spot to a pinpoint beam on the sample.

3. The beam is restricted by the condenser aperture (usually user selectable), knocking out high-angle electrons (those far from the optic axis, the dotted line down the centre). 4. A part of the beam that strikes the specimen is transmitted.

6. Optional objective and selected area metal apertures can restrict the beam—the objective aperture enhancing contrast by blocking out high-angle diffracted electrons, and the selected area aperture enabling the user to examine the periodic diffraction of electrons by ordered arrangements of atoms in the sample.

7. The image is passed down the column through the intermediate and projector lenses, being enlarged all the way.

8. When the beams strike the phosphor image screen light is generated, which causes the image to be visible to the operator. The area through which very few electrons are transmitted look darker (they are thicker or denser). The lighter areas of the image represent those areas of the sample through which more electrons were transmitted (they are thinner or less dense).

When the electron beam passes through the specimen, its interaction with the electrons present in the specimen generates a variety of radiation, which can give a lot of information about the specimen. Elastic scattering gives diffraction patterns and no energy is lost in this process. Inelastic interaction of the electron beam with the electrons at dislocations, grain boundaries, and second-phase particles, in the sample can lead to changes in the intensity of the transmitted electrons. Both elastic and inelastic scattering can give immense information about the sample.

The high magnification or resolution of TEM is a result of the small effective electron wavelengths, λ, which is given by the de Broglie relationship:

λ = h

√2mqV

where m and q are the electron mass and charge, h is Planck’s constant, and V is the potential difference through which electrons are accelerated. For example, electrons of 100 keV energy have wavelengths of 0.37 nm and are capable of effectively transmitting through ~ 0.6 μm of silicon. The higher the operating voltage of a TEM instrument, the greater its lateral spatial resolution. The theoretical instrumental point-to-point resolution is proportional to λ3/4. High-voltage TEM instruments (for example, 400 kV) have point-to-point resolutions better than 0.2 nm. High-voltage TEM instruments have the additional advantage of greater electron penetration, because high-energy electrons interact less strongly with matter than lower energy electrons. So it is possible to work with thicker samples on a high-voltage TEM. Unfortunately, the depth resolution of TEM is poor. Electron scattering information in a TEM image originates from a three-dimensional sample, but is projected on a two-dimensional detector.

5.4.4 TEM specimen preparation

Preparation of samples that are thin enough for electron transparency is a difficult task; however, it is much easier for nanomaterials. Selected area diffraction (SAD) offers a unique capability to determine the crystal structure of individual nanomaterials, such as nanocrystals and nanorods, and the crystal structures of different parts of a sample. In SAD, the condenser lens is defocussed to produce parallel illumination at the specimen and a selected area aperture

is used to limit the diffracting volume. SAD patterns are often used to determine the Bravais lattices and lattice parameters of crystalline materials by the same procedure used in XRD. Although TEM has no inherent ability to distinguish atomic species, electron scattering is exceedingly sensitive to the target element and various spectroscopy techniques are developed for the analysis of chemical composition.

TEM has also been used to determine the melting points of nanocrystals. Heating of a nanocrystal by the electron beam can

cause melting, which can be identified by the disappearance of crystalline diffraction. TEM has also been used to measure the mechanical and electrical properties of individual nanowires and nanotubes. Thus, one can develop structure– property correlations in nanomaterials. Figure 5.5 shows nano-quasicrystalline particles in a Zr alloy.

High-resolution TEM (HRTEM) is the ultimate tool for imaging atomic-scale defects. In favourable cases, it shows a two-dimensional projection of the crystal with defects and other features. Of course, this only makes sense if the two-dimensional projection is down some low-index direction, when atoms are exactly on top of each other. Consider a very thin slice of a crystal that has been tilted such that a low-index direction is exactly perpendicular to the electron beam. All lattice planes nearly parallel to the electron beam will be close enough to the Bragg position and will diffract the primary beam. The diffraction pattern can be considered as the Fourier transform of the periodic electron potential in crystals. In the objective lens, all diffracted beams and the primary beam are brought together again; their interference provides a back- transformation and leads to an enlarged image of the periodic potential. This image is magnified by the following electron-optical system and is finally seen on the screen at typical magnifications of 106 (Fig. 5.6) or higher.