Electron diffraction

Electron diffraction is a technique used to study matter by firing electrons at a sample and observing the resulting interference pattern. This phenomenon occurs due to the wave-particle duality, which states that a particle of matter (in this case the incident electron)can be described as a wave. For this reason, an electron can be regarded as a wave much like sound or water waves. This technique is similar to X-ray diffraction and neutron diffraction.

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 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.

Apart from the study of crystals, electron diffraction is also a useful technique to study the short range order of amorphous solids, and the geometry of gaseous molecules.

History

The de Broglie hypothesis, formulated in 1924, predicts that particles should also behave as waves. De Broglie's formula was confirmed three years later for electrons (which have a rest-mass) with the observation of electron diffraction in two independent experiments. At the University of Aberdeen George Paget Thomson passed a beam of electrons through a thin metal film and observed the predicted interference patterns. At Bell Labs Clinton Joseph Davisson and Lester Halbert Germer guided their beam through a crystalline grid. Thomson and Davisson shared the Nobel Prize for Physics in 1937 for their work.

Theory

Electron interaction with matter

Unlike other types of radiation used in diffraction studies of materials, such as X-rays and neutrons, electrons are charged particles and interact with matter through the Coloumb forces. This means that the incident electrons feel the influence of both the positively charged atomic nuclei and the surrounding electrons. In comparison, X-rays interact with the spatial distribution of the valence electrons, while neutrons are scattered by the atomic nuclei through the strong nuclear forces. In addition, the magnetic moment of neutrons is non-zero, and they are therefore also scattered by magnetic fields. Because of these different forms of interaction, the three types of radiation are suitable for different studies.

Intensity of diffracted beams

In the kinematical approximation for electron diffraction, the intensity of a diffracted beam is given by:

I_{\mathbf {g} }=\left|\psi _{\mathbf {g} }\right|^{2}\propto \left|F_{\mathbf {g} }\right|^{2}

Here $\psi _{\mathbf {g} }$ is the wavefunction of the diffracted beam and $F_{\mathbf {g} }$ is the so called structure factor which is given by:

F_{\mathbf {g} }=\sum _{i}f_{i}e^{-2\pi i\mathbf {g} \cdot \mathbf {r} _{i}}

where $\mathbf {g}$ is the scattering vector of the diffracted beam, $\mathbf {r} _{i}$ is the position of an atom $i$ in the unit cell, and $f_{i}$ 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 diffent scattering power of the elements through the term $f_{i}$ . 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.

Wavelength of electrons

The wavelength of an electron is given by the de Broglie equation

\lambda ={\frac {h}{p}}

Here $h$ is Planck's constant and $p$ the momentum of the electron. The electrons are accelerated in an electric potential $U$ to the desired velocity:

v={\sqrt {\frac {2eU}{m_{0}}}}

$m_{0}$ is the mass of the electron, and $e$ is the elementary charge.The electron wavelength is then given by:

\lambda ={\frac {h}{p}}={\frac {h}{m_{0}v}}={\frac {h}{\sqrt {2m_{0}eU}}}

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:

\lambda ={\frac {h}{\sqrt {2m_{0}eU}}}{\frac {1}{\sqrt {1+{\frac {eU}{2m_{0}c^{2}}}}}}

$c$ is the speed of light. We recognize the first term in this final expression as the non-relativistc 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 in a TEM

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.

Benefits

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 parallell 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 tree 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 perfomed 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.

Practical aspects

1: Sketch of the electron beam-path in a TEM.

Figure 1 to the right is a simple sketch of the path of a parallell 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 maniplulating the magnetic lenses of the microscope, the diffraction pattern may 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 abscence of diffraction spots the Bravais lattice and any screw axis and glide planes present in the crystal structure may be determined.

Limitations

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 by 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 vitually impossible.

References

Leonid A. Bendersky and Frank W. Gayle, "Electron Diffraction Using Transmission Electron Microscopy", Journal of Research of the National Institute of Standards and Technology, 106 (2001) pp. 997–1012.
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