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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 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 and neutron diffraction. Electron diffraction is most frequently used in solid state physics and chemistry to study the crystal structure of solids. Experiments are usually performed in a transmission electron microscope (TEM), or a scanning electron microscope (SEM) as electron backscatter diffraction. In these instruments, 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. Apart from the study of crystals i.e. electron crystallography, electron diffraction is also a useful technique to study the short range order of amorphous solids, and the geometry of gaseous molecules.

The de Broglie hypothesis, formulated in 1926, 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.

[edit] Theory
[edit] 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 Coulomb 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 nonzero, 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.

[edit] Intensity of diffracted beams
In the kinematical approximation for electron diffraction, the intensity of a diffracted beam is given by:


is the wavefunction of the diffracted beam and

is the so called structure factor which is given by:

also called the atomic form factor. We therefore need to take relativistic effects into account.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. taking into account the different scattering power of the elements through the term fi. The electrons are accelerated in an electric potential U to the desired velocity: m0 is the mass of the electron. The atomic form factor. and fi is the scattering power of the atom. The sum is over all atoms in the unit cell. the atomic form factors for the two cases are not the same.The electron wavelength is then given by: However.where is the scattering vector of the diffracted beam. the accelerating potential is usually several thousand volts causing the electron to travel at an appreciable fraction of the speed of light. there will be a difference in phase when considering the scattered amplitude from two atoms. We recognize the first term in this final expression as the non-relativistic expression derived above. and e is the elementary charge. An SEM may typically operate at an accelerating potential of 10. The structure factor describes the way in which an incident beam of electrons is scattered by the atoms of a crystal unit cell. Since the atoms are spatially distributed in the unit cell. of an element depends on the type of radiation considered. in an electron microscope. It can be shown that the electron wavelength is then modified according to: c is the speed of light. [edit] Wavelength of electrons The wavelength of an electron is given by the de Broglie equation Here h is Planck's constant and p the momentum of the electron. or scattering power. This phase shift is taken into account by the exponential term in the equation. The wavelength of the electrons in a 10 kV . Because electrons interact with matter though different processes than for example X-rays. while the last term is a relativistic correction factor. is the position of an atom i in the unit cell.

The resulting diffraction pattern is then observed on a fluorescent screen. electron diffraction in TEM can be combined with direct imaging of the sample. recorded on photographic film or using a CCD camera. chemical analysis of the sample composition through energy-dispersive X-ray spectroscopy.SEM is then 12. [edit] Practical aspects 1: Sketch of the electron beam-path in a TEM. including high resolution imaging of the crystal lattice. by converging the electrons in a cone onto the specimen. Furthermore. [edit] 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. one can in effect perform a diffraction experiment over several incident angles simultaneously. This allows the diffraction experiment to reveal more of the two dimensional distribution of reciprocal lattice points. and a range of other techniques. However. the wavelength of electron accelerated in a TEM is much smaller than that of the radiation usually used for X-ray diffraction experiments. and studies of the mean inner potential through electron holography.3 x 10-12 m (12. In a TEM. investigations of electronic structure and bonding through electron energy loss spectroscopy. These include solving and refining crystal structures by electron crystallography.5 pm. This technique is called Convergent Beam Electron Diffraction (CBED) and can reveal the full three dimensional symmetry of the crystal. A consequence of this is that the radius of the Ewald sphere is much larger in electron diffraction experiments than in X-ray diffraction. a single crystal grain or particle may be selected for the diffraction experiments.3 pm) while in a 200 kV TEM the wavelength is 2. . whereas other diffraction techniques would be limited to studying the diffraction from a multicrystalline or powder sample. the electron lenses allows the geometry of the diffraction experiment to be varied. Furthermore. The conceptually simplest geometry is that of a parallel beam of electrons incident on the specimen. This means that the diffraction experiments can be performed on single crystals of nanometer size. [edit] Benefits As mentioned above. 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).

This is the back focal plane of the microscope. the sample to be studied must be electron transparent. In this way. Careful and time consuming sample preparation may therefore be needed. and is where the diffraction pattern is formed. causing an image of the sample to be formed. electrons scattered in the same direction by the sample are collected into a single point. [edit] Limitations Electron diffraction in TEM is subject to several important limitations. the right experimental conditions may be difficult to obtain. the diffraction pattern may be observed by projecting it onto the screen instead of the image. . We note that at the dashed line in the figure.2: Typical electron diffraction pattern obtained in a TEM with a parallel electron beam 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. An example of what a diffraction pattern obtained in this way may look like is shown in figure 2. The study of magnetic materials is complicated by the fact that electrons are deflected in magnetic fields by the Lorentz force. they are scattered by the electrostatic potential set up by the constituent elements. meaning the sample thickness must be of the order of 100 nm or less. But there are also several examples where unknown crystal structures (both inorganic. organic and biological) have been solved by electron crystallography. Furthermore. As the electrons pass through the sample. but too inaccurate for determination of lattice parameters and atomic positions. After the electrons have left the sample they pass through the electromagnetic objective lens. electron diffraction is often regarded as a qualitative technique suitable for symmetry determination. and these procedures are often viewed as too time consuming and the data too difficult to interpret. relative errors less than 0.1% have been demonstrated. By manipulating the magnetic lenses of the microscope. X-ray or neutron diffraction are therefore often the preferred methods for determining lattice parameters and atomic positions. 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. one can obtain diffraction patterns from several crystal orientations. Lattice parameters of high accuracy can in fact be obtained from electron diffraction. the reciprocal lattice of the crystal can be mapped in three dimensions. If the sample is tilted with respect to the incident electron beam. First. Furthermore. This lens acts to collect all electrons scattered from one point of the sample in one point on the fluorescent screen. 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. However. many samples are vulnerable to radiation damage caused by the incident electrons.

From the strip of film we make measurements of the position of each diffraction line. to the centre of the hole for the transmitted direct beam.e. • For back reflections. We know that the distance between the holes in the film. Whereas both the execution of powder X-ray (and neutron) diffraction experiments and the data analysis are highly automated and routinely performed. • When the film is laid flat. from a diffraction line. So we can find θ from: or . The angle between the diffracted and the transmitted beams is always 2θ.However. This is the distance along the film. We remove the film strip from the Debye camera after exposure. • The distance S1 corresponds to a diffraction angle of 2θ. corresponds to a diffraction angle of θ = π. the main limitation of electron diffraction in TEM remains the comparatively high level of user interaction needed. S1 can be measured. From the results it is possible to associate the sample with a particular type of cubic structure and also to determine a value for its lattice parameter. where 2θ > 90° you can measure S2 as the distance from the beam entry point. The sample is known to have a cubic structure. electron diffraction requires a much higher level of user input X-Ray 6 of 7 We shall now consider the powder patterns from a sample crystal. but we don't know which one. W. i. then develop and fix it.

using the table shown below: . • We now multiply the values of sin2θ by some constant value to give nearly integer values for all the h2+ k2+ l2 values. θ and sin2θ. then the experimental values of sin2θ should form a pattern related to the values of h. k and l for the structure. • The integer values of h2+ k2+ l2 are then equated with their hkl values to index each arc. Integer values are then assigned. • If all the diffraction lines are considered. for cubic crystals is given by: where a is the lattice parameter this gives: • From the measurements of each arc we can now generate a table of S1. d.• We know Bragg's Law: nλ = 2dsinθ and the equation for interplanar spacing.

1 nanometer). • It is then possible to identify certain structures. When a beam of neutrons emanating from a reactor is slowed down and selected properly by their speed. bcc. If the wavelength of a quantum particle is short enough.• For some structures e. not all planes reflect.the planes have hkl values: all even. liquids or amorphous materials. fcc. it occurs when waves encounter obstacles whose size is comparable with the wavelength. but they are bound. Such a beam can then be used to perform a diffraction experiment. however. neutrons can be set free through nuclei decay particularly when fission occurs. The technique is similar to X-ray diffraction but the different type of radiation gives complementary information. Impinging on a crystalline sample it will scatter under a limited number of well-defined angles according to the same Bragg's law that describes X-ray diffraction. so some of the arcs may be missing. gasses. A sample to be examined is placed in a beam of thermal or cold neutrons and the intensity pattern around the sample gives information of the structure of theDescription [edit] Principle Neutrons are particles found in the atomic nucleus of almost all atoms. It can be equally well applied to study crystalline solids (see crystallography). the typical separation between atoms in a solid material. The technique requires free neutrons and these normally do not occur in nature. Diffraction is one of these phenomena. . In a nuclear reactor. Neutron diffraction is a form of elastic scattering where the neutrons exiting the experiment have more or less the same energy as the incident neutrons. or all odd in the table above).g. their wavelength lies near one Ångström (0. For greater accuracy the value is Neutron diffraction Neutron diffraction is a method for the determination of the atomic and/or magnetic structure of a material. because they have limited life-time. atoms or their nuclei can serve as diffraction obstacles. in this case fcc (. • For each line we can also calculate a value for a. the lattice parameter. All quantum particles can exhibit wave phenomena we typically associate with light or sound.

The technique is therefore mostly performed as powder diffraction. Some parts of the setup may also be movable. He was joined shortly thereafter by Clifford Shull. The contribution to the diffracted x-ray intensity is therefore larger for atoms with a large atomic number (Z) than it is for atoms with a small Z. On the other hand. Magnetic scattering does require an atomic form factor as it is caused by the much larger electron cloud around the tiny nucleus. high resolution) information means that the data can give very precise values for the atomic positions in the structure. and applied it successfully to many different materials. At a research reactor other components such as crystal monochromators or filters may be needed to select the desired neutron wavelength. Many neutron sources are equipped with liquid helium cooling systems that allow to collect data at temperatures down to 4. and together they established the basic principles of the technique. Wollan using the Graphite Reactor at Oak Ridge. addressing problems like the structure of ice and the microscopic arrangements of magnetic moments in materials. but its nuclei hardly scatter neutrons. Samples sizes are large compared to those used in X-ray diffraction. For this achievement .v.[edit] Instrumental requirements A neutron diffraction measurement requires a neutron source (e. Neutron diffraction can therefore reveal the microscopic magnetic structure of a material[1]. [edit] Magnetic scattering Although neutrons are uncharged. and the contribution to the diffracted intensity is different for each isotope. At a spallation source the time of flight technique is used to sort the energies of the incident neutrons. The scattering length varies from isotope to isotope rather than linearly with the atomic number. X-rays interact primarily with the electron cloud surrounding each atom. just a bunch of electronics. which is why it often used as a container material. including those arising from the electron cloud around an atom. [edit] History The first neutron diffraction experiments were carried out in 1945 by Ernest O. they carry a spin. On the other hand.2 K. An element like Vanadium is a strong scatterer of X-rays. for example. The superb high angle (i. regular hydrogen and deuterium contribute differently.g. A major difference with X-rays is that the scattering is mostly due to the tiny nuclei of the atoms. sometimes so much that the results are meaningless. That means that there is no need for a atomic form factor to describe the shape of the electron cloud of the atom and the scattering power of an atom does not fall off with the scattering angle as it does for X-rays.e. a sample (the material to be studied). Diffractograms therefore can show strong well defined diffraction peaks even at high angles. Non-magnetic neutron diffraction is directly sensitive to the positions of the nuclei of the atoms. particularly if the experiment is done at low temperatures. (Higher energy neutrons are faster . The intensity of the magnetic contribution to the diffraction peaks will therefore dwindle towards higher angles. and a detector. neutrons interact directly with the nucleus of the atom. so no monochromator is needed. and therefore interact with magnetic moments. Fourier maps (and to a lesser extent difference Fourier maps) derived from neutron data suffer from series termination errors. simple) [edit] Nuclear scattering Neutrons interact with matter differently than x-rays. It is also often the case that light (low Z) atoms contribute strongly to the diffracted intensity even in the presence of large Z atoms. a nuclear reactor or spallation source).

this is called null-scattering. (The other half of the 1994 Nobel Prize for Physics went to Bert Brockhouse for development of the inelastic scattering technique at the Chalk River facility of AECL. null-scattering and contrast variation Neutron diffraction can be used to establish the structure of low atomic number materials like proteins and surfactants much more easily with lower flux than at a synchrotron radiation source. This can easily be converted to the stress field experienced by the material. Nevertheless. Hydrogen is inexpensive and particularly interesting because it plays an exceptionally large role in biochemical structures and is difficult to study structurally in other ways. This is even more serious when the technique is used for the study of liquid structure. however. Because the data a typically a 1D powder diffractogram they are usually processed using Rietveld refinement. which allows contrast variation. may well change this picture. Wollan had passed away in the 1990s. The variation of other elements is possible but usually rather expensive. such as the ENGIN-X instrument at the ISIS neutron source. This also involved the invention of the triple axis spectrometer). They tend to drown in the inelastic background. [edit] Uses Neutron diffraction is closely related to X-ray powder diffraction[2]. Together with an accurately aligned micropositioner a map of the lattice constant through the metal can be derived. by preparing samples with different isotope ratios it is possible to vary the scattering contrast enough to highlight one element in an otherwise complicated structure. One major advantage of neutron diffraction over X-ray diffraction is that the latter is rather insensitive to the presence of hydrogen in a structure. This means that the position of hydrogen in a crystal structure and its thermal motions can be determined far more precisely with neutrons. The elastic pattern typically consists of sharp Bragg reflections if the sample is crystalline. The scatter by H-nuclei has a large ineleastic component and this creates a large continuous background that is more or less independent of scattering angle. This technique has led to the development of dedicated stress diffractometers. In practice however it is not desirable to work with the relatively high concentration of H in such a sample. Future developments. [edit] Hydrogen. . In addition the scattering lengths (structure factors in x-ray parlance) of H and D have opposite sign. This has been used to analyse stresses in aerospace and automotive components to give just two examples. Brockhouse and Shull jointly take the somewhat dubious distinction of the longest gap between the work being done (1945) and the Nobel Prize being awarded (1994). In fact there is a particular isotope ratio for which the contribution of the element would cancel. One practical application of elastic neutron scattering/diffraction is that the lattice constant of metals and other crystalline materials can be very accurately measured. In fact the latter found its origin in neutron diffraction (at Petten in the Netherlands) and was later extended for use in X-ray diffraction. whereas the nuclei 1H and 2H=D are strong scatterers for neutrons. This is because some low atomic number materials have a higher cross section for neutron interaction than higher atomic weight materials.Shull was awarded one half of the 1994 Nobel Prize in Physics. In fact the single crystal version of the technique is less commonly used because currently available neutron sources require relatively large samples and large single crystals are hard or impossible to come by for most materials.

A cylindrical film is placed around it and the crystal is rotated about the chosen axis. . sets of lattice planes will at some point make the correct Bragg angle for the monochromatic incident beam. The film intersects the cone. One side of the cone of Laue reflections is defined by the transmitted beam. that lie on curves on the film. White radiation is reflected from.X-Ray 3 of 7 In the rotating crystal method. The spots lying on any one curve are reflections from planes belonging to one zone. The chief use of the rotating crystal method is in the determination of unknown crystal structures X-Ray 4 of 7 The Laue method is mainly used to determine the orientation of large single crystals. When the film is laid out flat. with the diffraction spots generally lying on an hyperbola. Laue reflections from planes of the same zone all lie on the surface of an imaginary cone whose axis is the zone axis. the back-reflection and the transmission Laue method. The diffracted beams form arrays of spots. Each set of planes picks out and diffracts the particular wavelength from the white radiation that satisfies the Bragg law for the values of d and θ involved. Each curve therefore corresponds to a different wavelength. The reflected beams are located on the surface of imaginary cones. or transmitted through. Explore the rotating crystal method by clicking on the start button repeatedly. The Bragg angle is fixed for every set of planes in the crystal. and at that point a diffracted beam will be formed. a single crystal is mounted with an axis normal to a monochromatic xray beam. Experimental There are two practical variants of the Laue method. a fixed crystal. the film is placed between the x-ray source and the crystal. the diffraction spots lie on horizontal lines. The beams which are diffracted in a backward direction are recorded. As the crystal rotates. You can study these below: Back-reflection Laue In the back-reflection method.

Each spot can be indexed. the spots become distorted and smeared out. X-Ray 5 of 7 . The film intersects the cone. If the crystal has been bent or twisted in anyway. The Greninger chart is used for back-reflection patterns and the Leonhardt chart for transmission patterns.e. using special charts. attributed to a particular plane. The Laue technique can also be used to assess crystal perfection from the size and shape of the spots. the film is placed behind the crystal to record beams which are transmitted through the crystal. One side of the cone of Laue reflections is defined by the transmitted beam.Transmission Laue In the transmission Laue method. i. Crystal orientation is determined from the position of the spots. with the diffraction spots generally lying on an ellipse.

A circle of film is used to record the diffraction pattern as shown. The cones may emerge in all directions. one or more crystals will be in the correct orientation to give the correct Bragg angle to satisfy Bragg's equation. Each cone intersects the film giving diffraction lines. a powdered sample) show that the diffracted beams form continuous cones. If the sample consists of some tens of randomly orientated single crystals. Each diffraction line is made up of a large number of small spots. If a monochromatic x-ray beam is directed at a single crystal. by chance. Lattice parameters are the magnitudes of the unit vectors a. Each spot is so small as to give the . For every set of crystal planes. Every crystal plane is thus capable of diffraction. the diffracted beams are seen to lie on the surface of several cones. then only one or two diffracted beams may result. b and c which define the unit cell for the crystal.The powder method is used to determine the value of the lattice parameters accurately. A sample of some hundreds of crystals (i. The lines are seen as arcs on the film. forwards and backwards.e. each from a separate crystal.

white radiation). Powder diffraction (XRD) is a technique used to characterize the crystallographic structure. With monochromatic radiation. Diffraction can occur whenever Bragg's law is satisfied.. By selecting combinations of x-ray ranges and specimen types. ranging from simple inorganic solids to complex macromolecules. an arbitrary setting of a single crystal in an x-ray beam will not generally produce any diffracted beams. and physical properties of materials and thin films.[1] • • Single-crystal X-ray diffraction is a technique used to solve the complete structure of crystalline materials. If the crystal is not ground finely enough.. The most comprehensive description of scattering from crystals is given by the dynamical theory of diffraction. polarization. the diffraction lines appear speckled. and wavelength or energy. to satisfy Bragg's law. or • by rotating the crystal or.appearance of a continuous line. X-ray diffraction finds the geometry or shape of a molecule using X-rays. Powder diffraction is commonly used to identify unknown substances. There would therefore be very little information in a single crystal diffraction pattern from using monochromatic radiation. Practically this is done by: • using a range of x-ray wavelengths (i. discover the different techniques used in x-ray diffraction. X-ray diffraction techniques are based on the elastic scattering of X-rays from structures that have long range order. This arrangement is achieved practically in the Debye Scherrer camera illustrated here. X ray methods This problem can be overcome by continuously varying λ or θ over a range of values. X-ray diffraction techniques X-ray scattering techniques are a family of non-destructive analytical techniques which reveal information about the crystallographic structure. and preferred orientation in polycrystalline or powdered solid samples. chemical composition. It may also be used to characterize . by comparing diffraction data against a database maintained by the International Centre for Diffraction Data. These techniques are based on observing the scattered intensity of an X-ray beam hitting a sample as a function of incident and scattered angle. using a powder or polycrystalline specimen. such as proteins. crystallite size (grain size).e.

can provide structural information on unknown materials. such as Rietveld refinement. It employs parallel-beam optics. Wide angle X-ray scattering (WAXS). High-resolution X-ray diffraction is used to characterize thickness. when coupled with lattice refinement techniques. Scattering techniques Elastic scattering Materials that do not have long range order may also be studied by scattering methods that rely on elastic scattering of monochromatic X-rays. Powder diffraction is also a common method for determining strains in crystalline materials. • • • • Compton scattering Resonant inelastic X-ray scattering (RIXS) X-ray Raman scattering X-ray diffraction pattern . • • • Small angle X-ray scattering (SAXS) probes structure in the nanometer to micrometer range by measuring scattering intensity at scattering angles 2θ close to 0°.[2] X-ray reflectivity is an analytical technique for determining thickness. and strain in thin epitaxial films. An effect of the finite crystallite sizes is seen as a broadening of the peaks in an X-ray diffraction as is explained by the Scherrer Equation. a technique concentrating on scattering angles 2θ larger than 5°. Thin film diffraction and grazing incidence X-ray diffraction may be used to characterize the crystallographic structure and preferred orientation of substrate-anchored thin films. X-ray rocking curve analysis is used to quantify grain size and mosaic spread in crystalline materials. and density of single layer and multilayer thin films. Inelastic scattering When the energy and angle of the inelastically scattered X-rays are monitored scattering techniques can be used to probe the electronic band structure of materials. X-ray pole figure analysis enables one to analyze and determine the distribution of crystalline orientations within a crystalline thin-film sample.• • • • heterogeneous solid mixtures to determine relative abundance of crystalline compounds and. roughness. crystallographic structure.