Crystal Structures

and X-Ray (c) 2003 B rooks/C ole Publishing / Thom son Learning™
intensidad

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 X-RAY
• X-rays were discovered in
1895 by the German
physicist Wilhelm Conrad
Röntgen and were so
named because their
nature was unknown at
the time.

• He was awarded the

Wilhelm Conrad Röntgen
Nobel prize for physics in (1845-1923)
1901.
 X-RAY PROPERTIES
• X ray, invisible, highly penetrating electromagnetic
radiation of much shorter wavelength (higher frequency)
than visible light. The wavelength range for X rays is
from about 10-8 m to about 10-11 m, the corresponding
frequency range is from about 3 × 1016 Hz to about 3 ×
1019 Hz.
Generation of X-rays
X-rays are commonly produced by
accelerating electrons through a potential
difference (a voltage drop) and directing
them onto a target material, usually
tungsten, molybdenum or copper.

The incoming electrons release x-rays as

they slow down in the target (braking
radiation or bremsstrahlung). The x-ray
photons produced in this manner range in
energy from near zero up to the energy of
the electrons.

An incoming electron may also collide with

an atom in the target, kicking out an electron
and leaving a vacancy in one of the atom’s
electron shells. Another electron may fill the
vacancy and in so doing release an x-ray
photon of a specific energy (a characteristic
x-ray). The x-ray spectrum shown in the
picture is a plot of the number of photons
against the photon energy.
 Diffraction
 Diffraction - The constructive interference, or reinforcement, of a
beam of x-rays or electrons interacting with a material. The
diffracted beam provides useful information concerning the
structure of the material.
 Constructive & Destructive
Interference
• Constructive interference • Destructive İnterference
is the result of . results when two out-of-
synchronized light waves phase light waves cancel
that add together to each other out, resulting in
increase the light darkness.
intensity.
 Crystalline Materials
The atoms in a crystal are a periodic array of coherent scatterers
and thus can diffract light.

The (200) planes The (220) planes

of atoms in NaCl of atoms in NaCl
 X-Ray Diffraction & Bragg Equation
• English physicists Sir W.H.
Bragg and his son Sir W.L.
Bragg developed a relationship
in 1913 to explain why the
cleavage faces of crystals
appear to reflect X-ray beams at
certain angles of incidence
(theta, θ).This observation is an
example of X-ray wave Sir William Henry Bragg (1862-1942),
William Lawrence Bragg (1890-1971)
interference.

o 1915, the father and son were awarded the Nobel prize for
physics "for their services in the analysis of crystal structure by
means of Xrays".
 Bragg’s law is a simplistic model to understand
what conditions are required for diffraction.

n  2d hkl sin   

dhkl dhkl
• For parallel planes of atoms, with a space dhkl between the planes,
constructive interference only occurs when Bragg’s law is satisfied.
– In a diffractometers, the X-ray wavelength  is fixed.
– Consequently, a family of planes produces a diffraction peak only at a specific
angle .
• The space between diffracting planes of atoms
determines peak positions.
• The peak intensity is determined by what atoms
are in the diffracting plane.
Powder Diffractometer

Detector
X-ray
tube

  
 Single crystal specimen
Produce only one family of peaks in the diffraction pattern.

2

At 20.6 °2, Bragg’s law
fulfilled for the (100) planes,
producing a diffraction peak.
The (110) planes would diffract at 29.3
°2; however, they are not properly
aligned to produce a diffraction peak
(the perpendicular to those planes does
not bisect the incident and diffracted
beams). Only background is observed.
The (200) planes are parallel to the (100)
planes. Therefore, they also diffract for this
crystal. Since d200 is ½ d100, they appear at
42 °2.
 Polycrystalline specimen
A polycrystalline sample should contain thousands of crystallites.
Therefore, all possible diffraction peaks should be observed.

2 2 2

• For every set of planes, there will be a small percentage of crystallites that are properly
oriented to diffract (the plane perpendicular bisects the incident and diffracted beams).
• Basic assumptions of powder diffraction are that for every set of planes there is an equal
number of crystallites that will diffract and that there is a statistically relevant number of
crystallites, not just one or two.
 Miller indices
• For a lattice of known
dimensions, the Miller n  2d hkl sin 
indices can be used to
calculate the d-spacing
between hkl planes (a,b,c
Origin at orange dot
= lattice parameters). Miller index, hkl

(-110) (100)
• This d-spacing will
determine where powder
diffraction peaks are
observed.

(150)
(2-10)
Distance between planes (Miller indices)