UNIT – II CRYSTALSTRUCTURE ANALYSIS

Elementary Crystallography for X-Ray Diffraction

– analysis of Diffraction patterns – Inter planer spacing Crystallography originated as the science of the
study of macroscopic crystal forms, and the term “crystal” has been traditionally defined in terms of the
structure and symmetry of these forms. With the advent of the x-ray diffraction, the science has become
primarily concerned with the study of atomic arrangements in crystalline materials “a region of matter
within which the atoms are arranged in a three-dimensional translationally periodic pattern.” This orderly
arrangement in a crystalline material is known as the crystal structure. X-ray crystallography is concerned
with discovering and describing this structure. There is no way around it – effective application of x-ray
diffraction as an analytical tool in geology and materials science necessitates a basic understanding
crystallography. The purpose of this section is to provide that background. The material here is anything but
comprehensive. Crystallography is taught as a significant part of most Mineralogy courses, and multi-course
sequences in crystallography are taught in many physics, geology and materials science graduate programs.
What is presented here is skeletal treatment that is hopefully substantial enough to make sense of your
diffraction data. Description of the Crystal Structure A crystal structure is like a three-dimensional wallpaper
design in that it is an endless repetition of some motif (i.e., a group of atoms or molecules). The process of
creating the motif involves point-group operations (rotation, reflection, and inversion) that define it. The
process of creating the wallpaper involves translation (with or without rotation or reflection) to create the
complete structure (which we call the lattice). Real-world crystalline structures may be simple lattice
structures, or combinations of lattices to make complex crystalline application of x-ray diffraction.
Lattice Notation
Klein (2002) defines a lattice as “an imaginary pattern of points (or nodes) in which every point (node) has
an environment that is identical to that of any other point (node) in the pattern. A lattice has no specific
origin, as it can be shifted parallel to itself.” The figure at left (Fig 1-5) shows a method of notating lattice
points, rows, and planes on the basis of the crystal coordinate systems. A point in the lattice is chosen at the
origin and defined as 000. The a, b and c axes define the directions within the crystal structure with the
angular relations defined by the particular crystal system. Lattice points are specified without brackets –
100, 101, 102, etc. 100 is thus a point one unit along the a axis, 002 is a point two units along the c axis, and
101 is a point one unit along a and one unit along c.
Lattice planes are defined in terms of the Miller indices, which are defined as the reciprocals of the
intercepts of the planes on the coordinate axes cleared of fractions. In Fig. 1-5, the plane shown intercepts a
at 100, b at 010 and c at 002. The Miller index of the plane is thus calculated as 1/1(a), 1/1(b), 1/2(c), and
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reduced to integers as 2a,2b,1c. Miller indices are by convention given in parentheses, i.e., (221). If the
calculations result in indices with a common factor (i.e., (442)) the index is reduced to the simplest set
of integers (221). This means that a Miller index refers to a family of parallel lattice planes defined by a
fixed translation distance (defined as d) in a direction perpendicular to the plane. If directions are negative
along the lattice, a bar is placed over the negative direction, i.e. (2 21) Families of planes related by the
symmetry of the crystal system are enclosed in braces { }. Thus, in the tetragonal system {110} refers to

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the four planes (110), ( 1 10), ( 1 1 0) and (1 1 0). Because of the high symmetry in the cubic system, {110}
refers to twelve planes. As an exercise, write the Miller indices of all of these planes. Spacing of Lattice
Planes: The perpendicular distance separating each lattice plane in a stack is denoted by the letter d. Figure
1-7 shows several lattice planes and the associated d spacings. In a and c are in the plane of the paper, and b
is perpendicular to the plane of the page. The notation shown for the d spacing and the relationship to the
particular lattice plane (i.e., d001, d101, d103) with the Miller index for the particular plane shown in the
subscript (but usually without parentheses) are standard notation used in crystallography and x-ray
diffraction. The values of d spacings in terms of the geometry of the different crystal systems are shown in
Table 1-2 below The crystal systems (discussed in the next section) are listed in order of decreasing
symmetry. The calculations are increasingly complex as symmetry decreases. Crystal structure calculations
are relatively simple for the cubic system, and can be done with a good calculator for the tetragonal and
orthorhombic system. In actual practice, these calculations are usually done with the aid of specialized
computer programs specifically written for this purpose

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 When translated in three dimensions, the plane lattices define an assemblage of points in space. By
selection of different groups of points in two dimensions, and “copying” that group in the third dimension,
The six crystal systems (table on following page) are defined by relationships between unit cell edge lengths
and the angles between those edges. The combination of centering and relationship between the angles
between lattice directions and axis length define the 14 lattice types within the 6 crystal systems. In the
primitive lattice (P) all atoms in the lattice are at the corners. In the body centered lattices (I) there is an
additional atom at the center of the lattice. There are two types of face centering, one in which the atoms are
centered on a pair of opposing plane lattices (C) and another in which an atom is centered on each face (F).
It is important to note that the choice of the planar replication unit and the direction of that replication in
three dimensions that determines the character of the lattice.

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Crystallography is the experimental science of the arrangement of atoms in solids. The word
"crystallography" derives from the Greek words crystallon = cold drop / frozen drop, with its meaning
extending to all solids with some degree of transparency, and grapho = write.
Before the development of X-ray diffraction crystallography (see below), the study of crystals was based on
their geometry. This involves measuring the angles of crystal faces relative to theoretical reference axes
(crystallographic axes), and establishing the symmetry of the crystal in question. The former is carried out
using a goniometer. The position in 3D space of each crystal face is plotted on a stereographic net, e.g.
Wulff net or Lambert net. In fact, the pole to each face is plotted on the net. Each point is labelled with its
Miller index. The final plot allows the symmetry of the crystal to be established.
Crystallographic methods now depend on the analysis of the diffraction patterns of a sample targeted by a
beam of some type. Although X-rays are most commonly used, the beam is not always electromagnetic
radiation. For some purposes electrons or neutrons are used. This is facilitated by the wave properties of the
particles. Crystallographers often explicitly state the type of illumination used when referring to a method,
as with the terms X-ray diffraction, neutron diffraction and electron diffraction.
These three types of radiation interact with the specimen in different ways. X-rays interact with the spatial
distribution of the valence electrons, while electrons are charged particles and therefore feel the total charge
distribution of both the atomic nuclei and the surrounding electrons. Neutrons are scattered by the atomic
nuclei through the strong nuclear forces, but in addition, the magnetic moment of neutrons is non-zero. They
are therefore also scattered by magnetic fields. When neutrons are scattered from hydrogen-containing
materials, they produce diffraction patterns with high noise levels. However, the material can sometimes be
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treated to substitute hydrogen for deuterium. Because of these different forms of interaction, the three types
of radiation are suitable for different crystallographic studies.

Theory
Generally, an image of a small object is made using a lens to focus the illuminating radiation, as is done
with the rays of the visible spectrum in light microscopy. However, the wavelength of visible light (about
4000 to 7000 angstroms) is three orders of magnitude longer than the length of typical atomic bonds and
atoms themselves (about 1 to 2 angstroms). Therefore, obtaining information about the spatial arrangement
of atoms requires the use of radiation with shorter wavelengths, such as X-rays or neutrons beam.
Employing shorter wavelengths implied abandoning microscopy and true imaging, however, because there
exists no material from which a lens capable of focusing this type of radiation can be created. (That said,
scientists have had some success focusing X-rays with microscopic Fresnel zone plates made from gold, and
by critical-angle reflection inside long tapered capillaries.)[1] Diffracted x-ray or neutrons beams cannot be
focused to produce images, so the sample structure must be reconstructed from the diffraction pattern. Sharp
features in the diffraction pattern arise from periodic, repeating structure in the sample, which are often very
strong due to coherent reflection of many photons from many regularly spaced instances of similar structure,
while non-periodic components of the structure result in diffuse (and usually weak) diffraction features.
Because of their highly ordered and repetitive structure, crystals give diffraction patterns of sharp Bragg
reflection spots, and are ideal for analyzing the structure of solids.

Crystallography in materials engineering

Crystallography is a tool that is often employed by materials scientists. In single crystals, the effects of the
crystalline arrangement of atoms is often easy to see macroscopically, because the natural shapes of crystals
reflect the atomic structure. In addition, physical properties are often controlled by crystalline defects. The
understanding of crystal structures is an important prerequisite for understanding crystallographic defects.
Mostly, materials do not occur in a single crystalline, but poly-crystalline form, such that the powder
diffraction method plays a most important role in structural determination.
A number of other physical properties are linked to crystallography. For example, the minerals in clay form
small, flat, platelike structures. Clay can be easily deformed because the platelike particles can slip along
each other in the plane of the plates, yet remain strongly connected in the direction perpendicular to the
plates. Such mechanisms can be studied by crystallographic texture measurements.

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In another example, iron transforms from a body-centered cubic (bcc) structure to a face-centered cubic
(fcc) structure called austenite when it is heated. The fcc structure is a close-packed structure, and the bcc
structure is not, which explains why the volume of the iron decreases when this transformation occurs.
Crystallography is useful in phase identification. When performing any process on a material, it may be
desired to find out what compounds and what phases are present in the material. Each phase has a
characteristic arrangement of atoms. Techniques like X-ray or neutron diffraction can be used to identify
which patterns are present in the material, and thus which compounds are present.

INTRODUCTION
X-rays are electromagnetic radiation of wavelength about 1 Å (10-10 m), which is about the same size as an
atom. They occur in that portion of the electromagnetic spectrum between gamma-rays and the ultraviolet.
The discovery of X-rays in 1895 enabled scientists to probe crystalline structure at the atomic level. X-ray
diffraction has been in use in two main areas, for the fingerprint characterization of crystalline materials and
the determination of their structure. Each crystalline solid has its unique characteristic X-ray powder pattern
which may be used as a "fingerprint" for its identification. Once the material has been identified, X-ray
crystallography may be used to determine its structure, i.e. how the atoms pack together in the crystalline
state and what the interatomic distance and angle are etc. X-ray diffraction is one of the most important
characterization tools used in solid state chemistry amd materials science.
We can determine the size and the shape of the unit cell for any compound most easily using the diffraction
of x-rays.

Reflection of x-rays from two planes of atoms in a solid.

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The path difference between two waves:

2 x wavelength= 2dsin(theta)

For constructive interference between these waves, the path difference must be an integral number of
wavelengths:

n x wavelength= 2x

This leads to the Bragg equation:

n x wavelength = 2dsin(theta)

Figure 2 shows the x-ray diffraction pattern from a single crystal of a layered clay. Strong intensities can be
seen for a number of values of n; from each of these lines we can calculate the value of d, the interplanar
spacing between the atoms in the crystal.

2 X-ray diffraction pattern from a layered structure vermiculite clay.

EXAMPLE 1 Unit Cell Size from Diffraction Data

The diffraction pattern of copper metal was measured with x-ray radiation of wavelength of 1.315Å. The
first order Bragg diffraction peak was found at an angle 2theta of 50.5 degrees. Calculate the spacing
between the diffracting planes in the copper metal.

The Bragg equation is

n x wavelength = 2dsin(theta)

We can rearrange this equation for the unknown spacing d:

d = n x wavelength/2sin(theta).

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theta is 25.25 degrees, n =1, and wavelength = 1.315Å, and therefore
d= 1 x 1.315/(2 x 0.4266) = 1.541 Å
In this lab you will measure the x-ray powder diffraction pattern from a single crystal. Your TA will give
you the sample to be measured and show you how to set up the Miniflex x-ray diffractometer.

You should measure all the values of 2theta from the chart, and after converting them into d values calculate
the repeat distance in your unit cell. In your lab note book list all the 2theta values with their corresponding
values of n and d. Then calculate the mean and median values of the unit cell.

INSTRUMENTATION

The X-ray diffraction experiment requires an X-ray source, the sample under investigation and a detector to
pick up the diffracted X-rays. Fig 3 is a schematic diagram of a powder X-ray diffractometer.

Schematic of an X-ray powder diffractometer

The X-ray radiation most commonly used is that emitted by copper, whose characteristic wavelength for the
K radiation is =1.5418Å. When the incident beam strikes a powder sample, diffraction occurs in every
possible orientation of 2theta. The diffracted beam may be detected by using a moveable detector such as a
Geiger counter, which is connected to a chart recorder. In normal use, the counter is set to scan over a range
of 2theta values at a constant angular velocity. Routinely, a 2theta range of 5 to 70 degrees is sufficient to
cover the most useful part of the powder pattern. The scanning speed of the counter is usually 2theta of
2degrees min-1 and therefore, about 30 minutes are needed to obtain a trace.

PROCEDURE

**Do not open the chamber while the alarm red light is on
**Never touch the detector (may result in signal off).

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 1. Obtain a sample from your instructor, place it onto the double-side tape which is then placed on an
aluminum sample holder; if you are preparing a powder sample, use a spatula to spread the powder
onto the double-side tape.
2. Read the instructions for the Miniflex X-ray diffractometer, which are on the wall above the
instrument. Your instructor will explain the operation.
3. Set the instrument at optimum setting as follows

time constant 2
range ?
chart speed: Low

4. Slide in the sample holder and adjust the beginning 2theta at 70 degree (It scans from high degrees to
low degrees)
5. Switch on the start knob and chart recorder (slow) simultaneously, run your sample on slow chart
speed.
6. Once scan gets down to 3 degree of 2theta , stop (switch start knob to off) and chart. TURN OFF X-
ray.
7. Locate all peaks on the chart and corresponding 2theta values and write their values into the data
chart below. Perform the necessary calculations in the table and calculate the repeat distance in your
unit cell.

Bragg’s law

The atoms in crystals interact with X-ray waves in such a way as to produce interference. The interaction can be
thought of as if the atoms in a crystal structure reflect the waves. But, because a crystal structure consists of an
orderly arrangement of atoms, the reflections occur from what appears to be planes of atoms. Let's imagine a beam
of X-rays entering a crystal with one of these planes of atoms oriented at an angle of q to the incoming beam of
monochromatic X-rays (monochromatic means one color, or in this case 1 discreet wavelength as produced by the
characteristic sprectra of the X-ray tube).

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 Two such X-rays are shown here,
where the spacing between the
atomic planes occurs over the
distance, d. Ray 1 reflects off of
the upper atomic plane at an
angle q equal to its angle of
incidence. Similarly, Ray 2
reflects off the lower atomic
plane at the same angle q. While
Ray 2 is in the crystal, however, it
travels a distance of 2a farther
than Ray 1. If this distance 2a is
equal to an integral number of
wavelengths (nl), then Rays 1
and 2 will be in phase on their
exit from the crystal and
constructive interference will
occur.
If the distance 2a is not an integral number of wavelengths, then destructive
interference will occur and the waves will not be as strong as when they entered the
crystal. Thus, the condition for constructive interference to occur is

nl = 2a

but, from trigonometry, we can figure out what the distance 2a is in terms of the
spacing, d, between the atomic planes.

a = d sin q

or 2a = 2 d sin q

thus, nl = 2d sin q

This is known as Bragg's Law for X-ray diffraction.

What it says is that if we know the wavelength ,l , of the X-rays going in to the
crystal, and we can measure the angle q of the diffracted X-rays coming out of the
crystal, then we know the spacing (referred to as d-spacing) between the atomic
planes.

d = nl /2 sin q

Again it is important to point out that this diffraction will only occur if the rays are in
phase when they emerge, and this will only occur at the appropriate value of n (1, 2,
3, etc.) and q.

In theory, then we could re-orient the crystal so that another atomic plane is exposed
and measure the d-spacing between all atomic planes in the crystal, eventually
leading us to determine the crystal structure and the size of the unit cell
Selection rules and practical crystallography
Bragg's law, as stated above, can be used to obtain the lattice spacing of a particular cubic system through
the following relation:

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where a is the lattice spacing of the cubic crystal, and h, k, and l are the Miller indices of the Bragg plane.
Combining this relation with Bragg's law:

Techniques of X-ray Crystallography

X-ray diffraction yields the atomic structure of materials and is based on the elastic scattering of X-rays
from the electron clouds of the individual atoms in the system. The most comprehensive description of
scattering from crystals is given by the dynamical theory of diffraction.[1]
Single-crystal X-ray diffraction is a technique used to solve the complete structure of crystalline materials,
ranging from simple inorganic solids to complex macromolecules, such as proteins.
Powder diffraction (XRD) is a technique used to characterise the crystallographic structure, crystallite size
(grain size), and preferred orientation in polycrystalline or powdered solid samples. Powder diffraction is
commonly used to identify unknown substances, by comparing diffraction data against a database
maintained by the International Centre for Diffraction Data. It may also be used to characterize
heterogeneous solid mixtures to determine relative abundance of crystalline compounds and, when coupled
with lattice refinement techniques, such as Rietveld refinement, can provide structural information on
unknown materials. Powder diffraction is also a common method for determining strains in crystalline
materials. 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.
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.
High-resolution X-ray diffraction is used to characterize thickness, crystallographic structure, and strain in
thin epitaxial films. It employs parallel-beam optics.
X-ray pole figure analysis enables one to analyze and determine the distribution of crystalline orientations
within a crystalline thin-film sample.
X-ray rocking curve analysis is used to quantify grain size and mosaic spread in crystalline materials.
Scattering techniques
Elastic scattering

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Materials that do not have long range order may also be studied by scattering methods that rely on elastic
scattering of monochromatic X-rays.
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, roughness, and density of single layer
and multilayer thin films.
Wide angle X-ray scattering (WAXS), a technique concentrating on scattering angles 2θ larger than 5°.
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.
Compton scattering
Resonant inelastic X-ray scattering (RIXS)
X-ray Raman scattering

Debye – Scherer camera

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The term Debye-Scherrer is named after the originators, Debye, Scherrer and Hull, and is one of the oldest
known powder diffraction geometries, though originally it was used only with photographic film on a
"powder diffraction camera". It uses a near-parallel incident beam of X-rays with sufficient cross-section to
bathe the whole powder-sample. One of its virtues is its simplicity as illustrated by the following schematic
of the Debye-Scherrer camera/diffractometer.
A Debye-Scherrer camera has been designed to accommodate apparatus for maintaining the specimen at
high or low temperatures. The specimen holder is at all times accessible, and the film holder is detachable.
An apparatus has been devised for accurately controlling the temperature of the specimen between room
temperature and -110° C. The specimen is enclosed in a chamber of still air, cooled externally by boiled
liquid oxygen conducted between a succession of concentric cellophane windows. Special provision is made
to prevent deposition of ice. Lattice spacing measurements of aluminium at temperatures down to -97.5° C.
are in agreement with those calculated from the coefficient of expansion of the bulk metal.

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If we translate this geometry into the context of a synchrotron powder diffractometer we get the
arrangement depicted in the schematic below. The sample is usually held in a glass capillary, which spins on
its axis to increase the number of crystallite orientations offered to the incident X-ray beam, and of course
the photographic film is replaced by a detector which scans around the full 2θ range by rotating around the
capillary; also shown is an example of a pattern collected this way from Aerinite, a completely new mineral
type discovered in Morocco in 1997.

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The main advantages of this method are that
it is relatively easy to use;
it produces a very good diffraction peak shape (the significance of peak shape will become more apparent
later during the course).
There are no real disadvantages to this method, though it is not practical to use it for high pressure work.
Also some purists do not like to have scattering in their pattern from the glass nor have the inconvenience of
loading their samples into a narrow capillary.

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Geiger Diffractometer

Introduction to x ray diffraction analysis

After the discovery of X-rays, scientist started working on the wave nature of these rays. To test the nature,
X-rays have to produce interference and diffraction patterns. For diffraction to occur, the wavelength should
be in the order of its slit width. But we know that X-ray have shorter wavelength and it is quite impossible
to make such a slit / grating of smaller dimension. So the wave nature was studied in atomic level. Scientist
by name Laue suggested that crystal can act like a space grating to observe diffraction. This experiment was
later supported by Bragg’s equation.
X Ray Diffraction Analysis : Bragg’s Law

Consider a plane lattice crystal with inter planar distance d. Suppose a beam of X-rays of wavelength λ is
incident on the crystal at an angle θ , the beam will be reflected in all possible atomic planes. The path
difference between any two reflected waves is equal to the integral multiple of wavelength. The ray P gets
reflected from the surface while the ray Q has to under go some path difference. The extra distance traveled
by the ray Q from the figure is
(BC +CD). From the diagram either BC or CD is equal to d sin theta. So the path difference is

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 d sin θ + d sin θ = n λ
2 d sin θ = n λ
Here n is the order = 1,2, 3 …… .This is Braggs law
X Ray Diffraction : Analysis of the Pattern
The crystal which is considered as the slit is placed in the Bragg spectrometer for investigation. X-rays are
incident on the crystal at different angles and its corresponding ionization current is noted. The below is the
plot of ionization current and incident angle

At a certain values of the angle of incidence, the ionization current is increases abruptly or at peak value.
Basing on the angle at maximum current, the planar distance can be calculated using Bragg’s law.

When the angle increases i.e. order of the spectrum, the intensity of the X- rays decreases
Ionization current will never fall to zero.

Thus we can say the diffraction analysis of X-rays helped us to study the crystal structure.

CRYSTAL STRUCTURE

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Elements of El ectron Diffraction

Demonstration

The electron diffraction tube consists of a heated filament which emits electrons. These electrons are
accelerated; then they strike a graphite target, before passing through to a fluorescent screen. Students can
see diffraction rings on the screen, showing the wave behaviour of electrons.

Apparatus and materials

• Electron diffraction tube

• Power supply, 0 - 5 kV (Extra High Tension, EHT)

Technical notes

The electron beam strikes a target of a thin deposit of graphitized carbon on a metal grid situated in the exit
aperture of the anode. It is the wave nature of electrons passing through the carbon lattice that produces the
diffraction pattern.

The cathode is indirectly heated, so it may take a few moments to warm up.

The wavelength, λ, of the electrons is given by De Broglie’s equation λ=h/p where h is Planck's constant and
p is the momentum of an electron.

Safety

For use with a diffraction tube, the 50 MΩ safety resistor can be left in the circuit. This will reduce the
maximum shock current to less than 0.1 mA.

The power supply for the heater MUST have adequate insulation.

Leads used MUST have shrouded connectors and insulation capable of withstanding 5 kV.

Make all connections with the power supply turned off. Do not adjust connections while the EHT is
switched on.

Electron beam tubes are fragile. Because they are evacuated, they will implode if they break. The tubes are
also expensive, so handle them with great care. Use the purpose-designed holders during practical work.
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Note that when switching the EHT supply off, it can take a little while for the voltage output to fall to zero.
Allow sufficient time before disconnecting.

Procedure

Setting up

a Connect the heater supply of 6.3 volts to the filament.

b Connect the filament to the negative terminal of the EHT supply. Earth this terminal.

c Connect the positive terminal of the EHT supply to the anode of the diffraction tube. Set the accelerating
voltage to about 4,500 volts.

Carrying out
d Switch on the heater supply and the accelerating voltage. Rings should appear on the screen.

e Bring a strong magnet close to the tube. Show that the rings are distorted.

f Show how the rings change as the voltage is varied between 3,500 and 5,000 volts.

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Teaching notes

1 The diffraction rings are caused by the electrons diffracting and interfering as they pass through the
regular crystal structure of the graphite. They are behaving like waves and the graphite’s crystal structure
acts as a grating. As the crystals are arranged at any angle, each crystal produces a diffraction pattern, and
their diffraction patterns combine around 360° to form rings. This is the same as the microscope slide made
from the cut up pieces of a plastic diffraction grating in the Two-dimensional diffraction grating experiment.

2 Deflecting the pattern with a magnet shows that the pattern is being produced by moving charged
particles, rather than light or some other form of radiation. It introduces the dual nature of the electrons: they
behave like particles when they are accelerated, like waves as they pass through the graphite foil, and like
particles again as they are deflected in the magnetic field. This is an example of complementarity. See
guidance note Electrons behaving like waves.

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3 The diameter of the rings will change as the accelerating voltage changes. It seems that the more energy
the electrons have, the shorter their wavelength.

4 The pattern resulting from the passing of a beam of electrons through graphite is very similar to a beam of
X-rays passing through the powdered potassium alum crystal. It suggests that electrons undergo diffraction,
and will therefore interfere in the same way as X-rays and other waves.

Electron diffraction refers to the wave nature of electrons. However, from a technical or practical
point of view, it may be regarded as a technique used to study matter by firing electrons at a sample and
observing the resulting interference pattern. This phenomenon is commonly known as the wave-particle
duality, which states that the behavior of a particle of matter (in this case the incident electron) can be
described by 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.

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, on imaging plates 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
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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, 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 solving and
refining crystal structures by electron crystallography, 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.

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 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.

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