Electron diffraction is most frequently used in solid state physics and chemistry to study the crystal structure of solids. These experiments are usually performed in a transmission electron microscope (TEM), or a scanning electron microscope (SEM) as electron backscatter diffraction. In these instruments, the electrons are accelerated by an electrostatic potential in order to gain the desired energy and determine their wavelength before they interact with the sample to be studied.
The periodic structure of a crystalline solid acts as a diffraction grating, scattering the electrons in a predictable manner. Working back from the observed diffraction pattern, it may be possible to deduce the structure of the crystal producing the diffraction pattern. However, the technique is limited by the phase problem.
In the kinematical approximation for electron diffraction, the intensity of a diffracted beam is given by:
Here is the wavefunction of the diffracted beam and is the so called structure factor which is given by:
where is the scattering vector of the diffracted beam, is the position of an atom in the unit cell, and is the scattering power of the atom, also called the atomic form factor. The sum is over all atoms in the unit cell.
The structure factor describes the way in which an incident beam of electrons is scattered by the atoms of a crystal unit cell, taking into account the different scattering power of the elements through the term . Since the atoms are spatially distributed in the unit cell, there will be a difference in phase when considering the scattered amplitude from two atoms. This phase shift is taken into account by the exponential term in the equation.
The atomic form factor, or scattering power, of an element depends on the type of radiation considered. Because electrons interact with matter though different processes than for example X-rays, the atomic form factors for the two cases are not the same.
Here is Planck's constant and the momentum of the electron. The electrons are accelerated in an electric potential to the desired velocity:
is the mass of the electron, and is the elementary charge.The electron wavelength is then given by:
However, in an electron microscope, the accelerating potential is usually several thousand volts causing the electron to travel at an appreciable fraction of the speed of light. An SEM may typically operate at an accelerating potential of 10,000 volts (10 kV) giving an electron velocity approximately 20% of the speed of light, while a typical TEM can operate at 200 kV raising the electron velocity to 70% the speed of light. We therefore need to take relativistic effects into account. It can be shown that the electron wavelength is then modified according to:
is the speed of light. We recognize the first term in this final expression as the non-relativistic expression derived above, while the last term is a relativistic correction factor. The wavelength of the electrons in a 10 kV SEM is then 12.3 x 10-12 m (12.3 pm) while in a 200 kV TEM the wavelength is 2.5 pm. In comparison the wavelength of X-rays usually used in X-ray diffraction is in the order of 100 pm (Cu kα: λ=154 pm).
Electron diffraction of solids is usually performed in a Transmission Electron Microscope (TEM) where the electrons pass through a thin film of the material to be studied. The resulting diffraction pattern is then observed on a fluorescent screen, recorded on photographic film or using a CCD camera.
As mentioned above, the wavelength of electron accelerated in a TEM is much smaller than that of the radiation usually used for X-ray diffraction experiments. A consequence of this is that the radius of the Ewald sphere is much larger in electron diffraction experiments than in X-ray diffraction. This allows the diffraction experiment to reveal more of the two dimensional distribution of reciprocal lattice points.
Furthermore, the electron lenses allows the geometry of the diffraction experiment to be varied. The conceptually simplest geometry is that of a parallel beam of electrons incident on the specimen. However, by converging the electrons in a cone onto the specimen, one can in effect perform a diffraction experiment over several incident angles simultaneously. This technique is called Convergent Beam Electron Diffraction (CBED) and can reveal the full three dimensional symmetry of the crystal.
In a TEM, a single crystal grain or particle may be selected for the diffraction experiments. This means that the diffraction experiments can be performed on single crystals of nanometer size, whereas other diffraction techniques would be limited to studying the diffraction from a multicrystalline or powder sample. Furthermore, electron diffraction in TEM can be combined with direct imaging of the sample, including high resolution imaging of the crystal lattice, and a range of other techniques. These include chemical analysis of the sample composition through energy-dispersive X-ray spectroscopy, investigations of electronic structure and bonding through electron energy loss spectroscopy, and studies of the mean inner potential through electron holography.
Figure 1 to the right is a simple sketch of the path of a parallel beam of electrons in a TEM from just above the sample and down the column to the fluorescent screen. As the electrons pass through the sample, they are scattered by the electrostatic potential set up by the constituent elements. After the electrons have left the sample they pass through the electromagnetic objective lens. This lens acts to collect all electrons scattered from one point of the sample in one point on the fluorescent screen, causing an image of the sample to be formed. We note that at the dashed line in the figure, electrons scattered in the same direction by the sample are collected into a single point. This is the back focal plane of the microscope, and is where the diffraction pattern is formed. By manipulating the magnetic lenses of the microscope, the diffraction pattern may be observed by projecting it onto the screen instead of the image. An example of what a diffraction pattern obtained in this way may look like is shown in figure 2.
If the sample is tilted with respect to the incident electron beam, one can obtain diffraction patterns from several crystal orientations. In this way, the reciprocal lattice of the crystal can be mapped in three dimensions. By studying the systematic absence of diffraction spots the Bravais lattice and any screw axes and glide planes present in the crystal structure may be determined.
Electron diffraction in TEM is subject to several important limitations. First, the sample to be studied must be electron transparent, meaning the sample thickness must be of the order of 100 nm or less. Careful and time consuming sample preparation may therefore be needed. Furthermore, many samples are vulnerable to radiation damage caused by the incident electrons.
The study of magnetic materials is complicated by the fact that electrons are deflected in magnetic fields by the Lorentz force. Although this phenomenon may be exploited to study the magnetic domains of materials by Lorentz force microscopy, it may make crystal structure determination virtually impossible.
Furthermore, electron diffraction is often regarded as a qualitative technique suitable for symmetry determination, but too inaccurate for determination of lattice parameters and atomic positions. In principle, this is not quite the case: lattice parameters of high accuracy can in fact be obtained from electron diffraction, relative errors less than 0.1% have been demonstrated. However, the right experimental conditions may be difficult to obtain, and these procedures are often viewed as too time consuming and the data too difficult to interpret. X-ray or neutron diffraction are therefore often the preferred methods for determining lattice parameters and atomic positions.
However, the main limitation of electron diffraction in TEM remains the comparatively high level of user interaction needed. Whereas both the execution of powder X-ray (and neutron) diffraction experiments and the data analysis are highly automated and routinely performed, electron diffraction requires a much higher level of user input.