X-Ray Diffraction

Content of Lecture
1. Diffraction
2. Bragg law of light diffraction
3. X-Ray diffraction (XRD)
4. Instrumentation - How x-ray is generated?
5. Powder X-ray Diffraction
6. Instrumentation (X-Ray diffractometer)
7. How waves reveal the atomic structure of crystals
8. Experimental X-Ray Diffraction Patterns

114
 Diffraction is a wave property of electromagnetic radiation
that causes the radiation to bend as it passes by an edge or
through an aperture. Diffraction effects will increase as the
dimension of the aperture approaches the wavelength of the
radiation.
Diffraction of radiation gives rise to interference that
produces dark and bright rings, lines, or spots, depending on
the geometry of the object causing the diffraction. Common
interference effects for visible light are the rainbow pattern
produced by an oil-film on wet pavement , and the diffraction of
light from a narrow-slit or a diffraction grating.

Diffraction Methods
Wavelength will constructively interfere when it is
partially reflected between surfaces that produce a “path
difference” equal to “an integral number of wavelengths”.
This condition is described by the Bragg law (see later).

Schematic of crystal-structure determination by diffraction

115
 Interference of radiation between atomic planes in a crystal

sin = opposite BC/hypotenuse AC (i.e. the basal-spacing d)

d sin = opposite BC
2 d sin = 2 opposite BC
= path difference (V-shaped blue-line in graphic)
n =
n = 2 d sin
nsin = d
where
n an integer
 wavelength of the radiation
d basal-pacing between surfaces
 angle between the radiation and the surfaces.
n2 d sin is called the path difference
This relation demonstrates that interference effects are
observable only when radiation interacts with physical
116
dimensions that are approximately the same size as the
wavelength of the radiation. These interference effects are useful
for determining dimensions in crystal structures. Since the
distances between atoms or ions in a crystal is on the order of
10-10m=10-8cm (=1Å), diffraction methods require radiation in the
X-ray region of the electromagnetic spectrum, or beams of
electrons or neutrons with a similar wavelength.
Electrons and neutrons are commonly thought of as particles,
but they have wave properties with the wavelength depending on
the energy of the particles as described by the de Broglie
equation.
The three diffraction methods (X-rays, electrons and
neutrons) have different properties that we will not described
here. Retain only that the penetration depths of the three types of
beams are quite different (neutrons > X-rays > electrons).

X-Ray Diffraction (XRD)

The wavelengths of x-rays are of the same order of
magnitude as distances between atoms in a molecule or crystal
(10-10m=1Å). A crystal diffracts an x-ray beam passing
through it to produce beams at specific angles depending on
the x-ray wavelength, the crystal orientation, and the
structure of the crystal.
X-rays are predominantly diffracted by electron density.
Analysis of the diffraction angles produces an (electron density
map) of the crystal. Since hydrogen atoms have very little electron
density, determining their positions requires extensive refinement
of the diffraction pattern. Electron diffraction and neutron
diffraction are sensitive to nuclei and are often used to
accurately determine hydrogen positions.

Instrumentation - How x-ray is generated?

117
 X-ray diffractometers consist of an x-ray generator, a
goniometer and sample holder, and an x-ray detector such as
photographic film or a movable proportional counter.
X-ray tubes generate x-rays by bombarding a metal
target with high-energy (10-100 k eV) electrons that knock out
core electrons. An electron in an outer shell fills the hole in the
inner shell and emits an x-ray photon.
Two common targets are Mo and Cu, which have strong
K(alpha) x-ray emission at 0.71073 and 1.5418Å, respectively.
The x-rays can also be generated by decelerating electrons in a
target, or a synchrotron ring. These sources produce a continuous
spectrum of x-rays and require a crystal monochromator to
select a single wavelength.

Powder X-ray Diffraction

Powders of crystalline materials diffract x-rays. The beam of
x-rays passing through a sample of randomly oriented micro-
crystals produces a pattern of rings on a distant screen. Powder
x-ray diffraction provides less information than single-crystal
diffraction. However, it is much simpler and faster. Powder x-ray
diffraction is useful for confirming the identity of a solid
material and determining crystallinity and phase purity.

Instrumentation
Modern powder x-ray diffractometers consist of an x-ray
source, a movable sample platform, an x-ray detector, and
associated computer-controlled electronics. The sample is
either packed into a shallow cup-shaped holder or deposited as a
slurry onto a quatz substrate, and the sample holder spins
slowly during the experiment to reduce sample heating. The x-
ray source is usually the same as used in single-crystal Mo or Cu
diffractometer. The x-ray beam is fixed and the sample
platform rotates with respect to the beam by an angle theta
(). The detector rotates at twice the rate of the sample and is
at an angle of 2 with respect to the incoming x-ray beam.
118
 X-RAY DIFFRACTOMWETER

This is a schematic of an x-ray diffraction system. The sample is mounted

(normally on a glass slide) and placed on the axis of the diffractometer. The collector
rotates about that axis and collects data on the scattering intensity. This diagram
shows a Cu anode. In this system, the radiation is associated along the primary K line
(wavelength of 1.54184 Å). The collector then registers the intensity at 2 angles
to the sample plane. The data collected is sent to a personal computer to be
analyzed.
X-ray diffraction works on the principle that x-rays form predictable diffraction
patterns when interacting with a crystalline matrix of atoms. Today, with the help of
computers to do the mathematical calculations involved, the diffraction patterns can
easily be converted into information about the location of atoms within the
matrix. From those positions, the exact crystalline structure can be determined.

119
 Bragg's Law and Diffraction:
How waves reveal the atomic structure of crystals
Applet created by Konstantin Lukin

What is Bragg's Law and Why is it Important?

Bragg's Law refers to the simple equation:

n = 2d sin 
derived by the English physicists Sir W.H. Bragg and his son Sir W.L. Bragg in 1913
to explain why the cleavage faces of crystals appear to reflect X-ray beams at
certain angles of incidence (theta, ). The variable d is the distance between atomic
layers in a crystal, and the variable lambda  is the wavelength of the incident X-ray
beam (see applet); n is an integer.
This observation is an example of X-ray wave interference, commonly known
as X-ray diffraction (XRD), and was direct evidence for the periodic atomic structure
of crystals postulated for several centuries. The Braggs were awarded the Nobel
Prize in physics in 1915 for their work in determining crystal structures
beginning with NaCl, ZnS and diamond. Although Bragg's law was used to explain
the interference pattern of X-rays scattered by crystals, diffraction has been
developed to study the structure of all states of matter with any beam, e.g., ions,
electrons, neutrons, and protons, with a wavelength similar to the distance between
the atomic or molecular structures of interest.

Deriving Bragg's Law

Bragg's Law can easily be derived by considering the conditions necessary to
make the phases of the beams coincide when the incident angle equals the reflecting
angle. The rays of the incident beams are always in phase and parallel up to the
point at which the top beam strikes the top layer at atom z (Fig. 1). The second beam
continues to the next layer where it is scattered by atom B. The second beam must
travel the extra distance AB + BC if the two beams are to continue traveling
adjacent and parallel. This extra distance must be an integral (n) multiple of the
wavelength () for the phases of the two beams to be the same:
n = AB +BC (2).
In deriving Bragg's Law using the reflection geometry and applying
trigonometry, the lower beam must travel the extra distance (AB + BC) to continue
traveling parallel and adjacent to the top beam.
Recognizing d as the hypotenuse of the right triangle Abz, we can use
trigonometry to relate d and  to the distance (AB + BC). The distance AB is
opposite  so,
A B = d sin  (3).
Because A B = B C
eq. (2) becomes,
n  = 2 AB (4)
120
Substituting eq. (3) in eq. (4) we have,
n  = 2 d sin  (1)
Thus, Bragg's Law has been derived. The location of the surface does not change the
derivation of Bragg's Law.

Experimental Diffraction Patterns

The following figure is showing experimental x-ray diffraction pattern of cubic
Silicon Carbide (SiC) using synchrotron radiation.

Text written by Paul J. Schields

Center for High Pressure Research
Department of Earth & Space Sciences
State University of New York at Stony Brook
Stony Brook, NY 11794-2100.

121