INTRODUCTION TO X-RAY DIFFRACTION

To explore the structure of crystals we use the diffraction of waves which interact with atoms
and which have a wavelength comparable with the interatomic spacing in crystals. Radiation of
longer wavelength cannot resolve the details of structure on an atomic scale, and radiation of
much shorter wavelength is diffracted through inconveniently small angles.

The first kind of scatter process to be recognised was discovered by Max von Laue who was
awarded the Nobel prize for physics in 1914 "for his discovery of the diffraction of X-rays by
crystals". Max von Laue, in 1912, discovered that crystalline substances act as three-dimensional
diffraction gratings for X-rays of wavelengths similar to the spacing of planes in a crystal lattice.

Figure 1: The periodic lattice found in crystalline structures may act as a diffraction grating for
wave particles or electromagnetic radiation with wavelengths of a similar order of magnitude
(10‐10m / 1 Å).

Our present knowledge of crystal structures has been obtained mainly by x-ray diffraction
techniques that use x-rays about the same wavelength as the distance between crystal lattice
planes.

{Recall: The energy of an x-ray photon is related to its wavelength λ by:

o 12.4
 ( A) 
E (keV )

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We see from the above relation that for crystal studies we require photon energies in the 10 to 50
keV range; that is, x-rays. Other complementary techniques include diffraction by neutrons and,
less often, electrons.

However, before discussing the manner in which x-rays are diffracted in crystals, let us consider
how x-rays are produced for experimental purposes

Production of x-rays

X-rays are produced when highly energetic electrons interact with matter and convert their
kinetic energy into electromagnetic radiation. A device that accomplishes this task consists of:

– An electron source

– An evacuated path (vacuum) for electron acceleration

– An external energy source to accelerate the electrons

X-rays used for diffraction are electromagnetic waves with wavelengths in the range 0.05 to 0.25
nm (0.5 to 2.5 Å). By comparison, the wavelength of visible light is of the order of 600 nm (6000
Å). In order to produce x-rays for diffraction purposes, a voltage of about 35 kV is necessary and
is applied between a cathode and an anode target metal, both of which are contained in a vacuum
tube, as shown in Figure 2.

Figure 2: The x-ray tube

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When the tungsten filament of the cathode is heated, electrons are released by thermionic
emission and accelerated through the vacuum by the large voltage difference between the
cathode and anode, thereby gaining kinetic energy. The kinetic energy gained by an electron is
proportional to the potential difference between the cathode and the anode. The energies of
electrons accelerated by potential differences of 20 and 100 kilovolt peak (kVp) are 20 and 100
keV, respectively. When the electrons strike the target metal (e.g., molybdenum), x rays are
given off. However, most of the kinetic energy (about 98 percent) is converted into heat, so the
target metal must be cooled externally. The x-rays from its tube usually contain different
wavelengths and the plot of its intensity versus wavelength for spectrum of radiation emitted by
an x-ray tube is called x-ray spectrum.

The x-ray spectrum

X-ray spectra are composed of:
1. Continuous bremsstrahlung spectra
2. Discrete spectra peaks known as characteristic x-rays.
Bremsstrahlung radiation makes up approximately 80% of the x-ray beam

Figure 3: The X-ray spectrum

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The origin of the characteristic radiation is explained as follows: First, K electrons (electrons in
the n = 1 shell) are knocked out of the atom by highly energetic electrons bombarding the target,
leaving excited atoms. Next, some electrons in higher shells (that is, n = 2 or 3) drop down to
lower energy levels to replace the lost K electrons, emitting energy of a characteristic
wavelength. The transition of electrons from the L (n = 2) shell to the K (n = 1) shell creates
energy of the wavelength of the Kα line, as indicated in Figure 3

Figure 4: production of the characteristic x-ray radiation

Bremsstrahlung Spectrum

Bremsstrahlung (from bremsen "to brake" and Strahlung "radiation", i.e. "braking radiation" or
"deceleration radiation") is electromagnetic radiation produced by the deceleration of a charged
particle when deflected by another charged particle, typically an electron by an atomic nucleus.
The process is explained as follows: As electrons from the cathode travel to the anode, they are
accelerated by the electrical potential difference between these electrodes. On impact with the
target, the kinetic energy of the electrons is converted to other forms of energy. Majority of
interactions produce heat, heating limits the number of x-rays that may be produced in a given
time without destroying the target. About 0.5% of the time, an electron comes close to a nucleus
in the target electrode, Coulombic forces attract and decelerate the electron. Kinetic energy lost
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by the electron produces an x-ray photon with energy equal to that lost by the electron.
Bremsstrahlung has a continuous spectrum, which becomes more intense and whose peak
intensity shifts toward higher frequencies as the change of the energy of the accelerated particles
increases.

Figure 4: production of Brehmstralung radiation

As the electrons pass through the target atom they slow down, with a loss in kinetic energy. This
energy is emitted as x-rays. The process is known as bremsstrahlung or “braking energy”.

Figure 5: Bremsstrahlung x-rays form a continuous energy spectrum: The frequency

distribution is continuous

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Bremsstrahlung xrays form a continuous energy spectra. The frequency distribution is
continuous and shows that the Bremsstrahlung process produces more low energy that higher
energy x-rays. The average energy is approximately 1/3 of the Emax

The x-ray spectrum emitted at 35 kV using a molybdenum target is shown in Fig. 3.26. The
spectrum shows continuous x-ray radiation in the wavelength range from about 0.2 to 1.4 Å
(0.02 to 0.14 nm) and two spikes of characteristic radiation that are designated the K α and Kβ
lines. The wavelengths of the Kα and Kβ lines are characteristic for an element. For molybdenum,
the Kα line occurs at a wavelength of about 0.7 Å (0.07 nm).

Different anode materials will produce different characteristic x-ray spectra and different
amounts of bremsstrahlung radiation.

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BASICS OF X-RAY DIFFRACTION

The father and son team of Sir William Henry and William Lawrence Bragg were awarded the
Nobel prize for physics "for their services in the analysis of crystal structure by means of Xrays“
in 1915. Bragg's law was an extremely important discovery and formed the basis for the whole of
what is now known as crystallography. This technique is one of the most widely used structural
analysis techniques and plays a major role in fields as diverse as structural biology and materials
science

Figure 6: The Bragg Spectrometer

Bragg’s Law of Diffraction

Bragg’s Law can be derived using simple geometry by considering the distances traveled by two
parallel X-rays reflecting from adjacent planes (We consider elastic scattering, so that the
wavelength of the photon or neutron is not changed on reflection. Inelastic scattering (scattering
accompanied by the excitation of elastic waves in the crystal is not considered). The X-ray
hitting the lower plane must travel the extra distance CB and BD. To remain in phase with the
first X-ray, this distance must be a multiple of the wavelength thus:

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 Figure 7

As the wave enters the crystal, some portion of it will be reflected by the first layer, while the
rest will continue through to the second layer, where the process continues. By the definition of
constructive interference, the separately reflected waves will remain in phase if the difference in
the path length of each wave is equal to an integer multiple of the wavelength.

In the figure 4.1 above, the path difference is given by 2dsin θ.

[The difference between the length of wave 1 and 2 = CB + BD = 2CB

But, sin = CB/d ]

Thus, according to the Bragg condition, for constructive interference

2d sin   n ---------4.1

Where:

 n is an integer,
 λ is the wavelength of electrons.
 d is the spacing between the planes in the atomic lattice, and

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  θ is the angle between the incident ray and the scattering planes

The reflection condition in equation 4.1, is called the Bragg condition. Waves that satisfy this
condition interfere constructively.

Bragg reflection can only occur for wavelengths λ ≤ 2d. this is why we cannot use visible light.

You may wonder why X-rays reflect in this way and what is causing them to “reflect” in the first
place. The actual interaction is between the X-rays and the ELECTRONS in the crystal and it is
a type of elastic scattering. The oscillating electric field of the X-rays causes the charged
particles in the atom to oscillate at the same frequency. Emission of a photon at that frequency
(elastic) returns the particles in the atom to a more stable state. The emitted photon can be in any
direction.

The Bragg law is a consequence of the periodicity of the space lattice. The law does not refer to
the arrangement or basis of atoms associated with each point. The composition of the basis
determines the relative intensity of the various orders n of diffraction from a given set of parallel
planes.

There are problems: the intensity of scattering of atoms goes like Z2; hence, if two species are
present, one such as hydrogen (Z = 1), and something higher, say Z = 18, then it will be very
hard to `see' the hydrogen.

This equation, known as Bragg’s law, gives the relationship among the angular positions of the
reinforced diffracted beams in terms of the wavelength λ of the incoming x-ray radiation and of
the inter planar spacings dhkl of the crystal planes. In most cases, the first order of diffraction
where n = 1 is used, and so for this case Bragg’s law takes the form
λ = 2dhkl sin θ
The Bragg equation is the fundamental equation, valid only for monochromatic X-rays,
that is used to calculate interplanar spacings used in XRD analysis.

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Using of Bragg Law:
• When a diffraction condition is met there can be a reflected X-ray
• Three variables λ, θ, and d
– λ is known
– θ is measured in the experiment (2θ)
– d is calculated
• From the planes (hkl)
– a is calculated from the relation

a  d h2  k 2  l 2

Example
A sample of BCC iron was placed in an x-ray diffractometer using incoming x-rays with a
wavelength λ = 0.1541 nm. Diffraction from the {110} planes was obtained at 2θ = 44.704◦ .
Calculate a value for the lattice constant a of BCC iron. (Assume first order diffraction with n =
1.)

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