For teaching purposes ONLY (ANU 2007)

X-Ray Diffraction
(XRD)

Ulrike Troitzsch
Department of Earth and Marine Sciences
Australian National University
 What is X-ray diffraction?
• Scattering phenomenon, X-rays passing through
crystal
• A tool for the characterisation of solid materials
based on their crystal structure

• Used by
 Earth Scientists
 Chemists
 Physicists
 Material Scientists
 Archaeologists
 Biologists …

Rosalind E. Franklin 1952

 What is XRD used for?

• Identification of minerals
• Quantification of minerals
• Determination of crystal structure
o Unit-cell dimensions, symmetry, atom positions …
• Determination of grain sizes, strain

Typical samples
• Minerals, rocks, corals, shells
 What is X-ray diffraction?

XRD complements other analytical methods

• Visual (colour, streak, cleavage, symmetry …)

 Need large crystals! cm
• Optical microscopy (colour, birefringence,
pleochroism …)
 Need ‘large’ crystals! µm to mm
• SEM (composition: wt.% SiO2, CaO …)
 What about polymorphs? (Calcite, Aragonite = CaCO3)
 Need ‘large’ crystals! > 3 µm
• XRF (composition: wt.% SiO2, CaO …)
 What about polymorphs? (Calcite, Aragonite = CaCO3)
 History

• Discovery of X-rays by W. C. Röntgen in 1895

o X-ray radiography (relative absorption of X-rays is
function of average atomic number and density of matter)
• Max von Laue in 1912: X-rays have dual character of
particle and wave [Nobel prize 1914 “for his discovery of
the diffraction of X-rays by crystals”]
o X-ray crystallography (interaction of X-rays with crystal structures)
 Single crystal or powder XRD!
• L. Bragg 1913, analysed KCl and NaCl with X-ray
crystallography and developed Bragg’s Law [Nobel Prize
1915]
• Technological improvements (last 40 years)
o Computers (20 atom structure took 1-2 years, now 200 atoms can
be refined in 1-2 days)
o X-ray spectrometry (characteristic X-rays from each element)
SEM, XRF
 What are X-rays?
Interacts
with
• Beams of electromagnetic radiation electrons!
o Short wavelength, high energy

Wave (sinusoidal, oscillating electric field with, at

right angles to it, a magnetic field)
wavelength 
frequency 
Particle (photon)
Photon energy E E = h
(h is Planck’s constant: 6.625 x 10-34 Js)
 Properties of a wave

Wave  = c /  (c=300.000 km/s)

 Electromagnetic
radiation

Å (Ångström) is non-SI unit of length X-rays: 10-8 to 10-11 m

1 Å = 10-10 m = 0.1 to 100 Å
0.1 nm dimension of atoms, bonds, unit-cells …
 How are X-rays
generated?
1.Radioactive materials
undergo decay (too many
nuclear particles or too high
neutron/proton ratio)
1532P -> 1632S + X-ray

– Machines (accelerated
particles hit ‘target’ matter) e-
o X-ray tube (accelerates
electrons which interact with
electrons of target)
o Particle accelerator
 X-ray tube
3. Electrons interact
with target (anode),
producing X-rays
X-rays Target (Co,
Cu)
2. Electrons are
accelerated in
Electron electric field
beam
Tungsten 1. W filament is
Filament heated, electrons
‘boil off’
Typical X-ray spectrum

• Continuous
radiation

• ‘Spikes’
 Two types of X-radiation are produced:

1. Bremsstrahlung (‘braking radiation’, white radiation),

produces a continuous spectrum of X-ray
wavelengths
 Two types of X-radiation are produced:

2. Characteristic Radiation (X-rays of distinct

wavelengths, unique for each element)
1. Incoming electron
knocks inner shell
electron out of its place
 2. Empty site is filled by an

electron from a higher
shell
3. The difference in binding
energy between inner
and outer shell electrons
is released as X-ray of
characteristic wavelength
Typical X-ray spectrum

• Continuous radiation
= Bremsstrahlung
• ‘Spikes’ =
Characteristic radiation

Characteristic radiation
is used in XRD, which
requires monochromatic
radiation
(eg. CuK = 1.5418 Å)
 Interaction of X-rays with crystal structures
Crystal structure:
three-dimensional,
periodic
arrangement
of atoms in space.
Unit-cell of NaCl

Na Cl

Many different layers of atoms exist in a crystal structure.

Each set of layers has a distinct interplanar distance (d-
spacing).
Interaction of X-rays with crystal structures
X-rays (electromagnetic wave) interact with the
electrons of the atoms in the crystal
• Coherent Scatter: elastic collision between a
photon (X-ray) and and electron (in crystal)
o outgoing photons (X-ray) have same
wavelength, frequency and energy as
incoming photons [XRD!]
• Incoherent Scatter (= Compton scatter):
inelastic collision between photon and electron
- outgoing photons have lower energy
Interaction of X-rays with a scattering center
Interferenc
+ e

-
+
-
Incoming
wave

Every electron/atom in structure acts as a

scattering center, and is a source of spherical
waves of the same wavelength and frequency as
the incoming wave.
 Positive Negative
Interference Interference

Crests and troughs add up and Crests and troughs are offset
form a wave with twice the and cancel each other out.
amplitude.

This happens to most X-

rays scattered in crystals
due to the large number of
scattering centers ...
X-rays passing through a crystal lattice

X-rays
out of
phase!
 Diffraction
However: … There is an ‘exception’, allowing some
X-rays to experience positive (or constructive)
interference in crystals. This is called diffraction.

“When a periodic array of objects each scatter

radiation coherently, the concerted constructive
interference at specific angles is called
diffraction.”

Diffraction in crystalline materials is best described

with

Bragg’s Law: n  = 2 dhkl sin

 Bragg’s Law
X-rays
in
n  = 2 dhkl phase!
sin


dhk
 l

hkl

For positive interference to occur, the path-difference

must be equal to one wavelength ( or multiple
wavelengths (n.
 The X-ray diffractometer
n=2d
sin




Powder diffractometer with Bragg-Brentano geometry.

Analyst controls  (choice of target in X-ray tube)
 (positions of X-ray tube/sample/detector
 Sample
• We are choosing incoming angle = outgoing angle.  sample 
• Therefore only diffraction from atomic planes in the crystal structure
that are parallel to the flat sample surface are detected

For example, if we analysed this single

muscovite crystal with XRD, lying flat on the
(001) sample holder with its 001 plane, only (001)
planes would diffract.

However, we want ALL crystallographic planes

to contribute to the XRD pattern.
muscovite
All samples need to be ground up very finely
(ideally 1-10 µm grain size), and the grains
oriented randomly in the sample holder.

Powder X-ray Diffraction

 Typical XRD scan

Backgroun
d

• Background
• Peaks (at certain angle and with certain intensity) resulting from
positive interference of X-rays with crystal structure of one or
more minerals
How do we know which minerals caused the peaks?
 Typical XRD scan
9

6
Peak 2 angle Absolute Relative d spacing
No 3 4 Intensity Intensity
2 8
1 1 20.325°7 32 counts 5%
2 20.66 ° 40 counts 7%
3 21.07 ° 173 counts 29 %
4 28.12 ° 192 counts 32 %
… … … …
X-ray wavelength
9 32.88 ° 590 counts 100 %
… … … … used:
CoK= 1.7889 Å
5.07 Å
4.98 Å
4.89 Å  = 2 d sin
3.68 Å
…
3.16 Å
…
sin
 = d
 ICDD (International Centre for Diffraction Data)
publishes the datasets called PDF (Powder Diffraction
File)

Compare with the d-spacings and relative intensities of your sample.

 ICDD (International Centre for Diffraction Data)
publishes the datasets called PDF (Powder Diffraction
File)

Compare with the d-spacings of the strongest peaks in your sample.

 Mineral Identification
The XRD pattern of a mineral is like its fingerprint
Baddeleyite ZrO2
Hematite Fe2O3
Pseudobrookite Fe2TiO5
Rutile TiO2
 Mineral Quantification
Sample A
Baddeleyite 40 wt.%
Hematite 30 wt.%
Pseudobrookite 25 wt.%
Rutile 5 wt.%

Sample B
Baddeleyite 20 wt.%
Hematite 2 wt.%
Pseudobrookite 18 wt.%
Rutile 60 wt.%

Important: The intensity of XRD reflections depends not only on the

abundance of a mineral in the sample, but on elemental composition
(atomic scattering factors), hkl, grain size, crystal structure strain …
The lower the symmetry, the more complex the diffraction pattern

Triclinic: a≠b≠c,
≠≠

Cubic: a=b=c,
==
 Order of reflection
n  = 2 dhkl sin
n : Order of Reflection
Multiply n with hkl, for example:
hkl
Plane
100
100 produces reflections 100 (1st order, n=1)
200 (2nd
200 order, n=2)
300
300 (3rd order,
2theta
n=3)
400

… etc.
• = 2 d/n sin
Reflections are produced by plane dhkl and
‘fictitious planes’ dhkl/2, dhkl/3, etc
 Systematic absences or extinctions
Recap:
1. Every plane with its characteristic d-spacing can diffract at
a specific angle (Bragg’s Law)
– A single plane can cause several reflections (n=1, 2, 3,
…)
• However, not all reflections of one plane are necessarily
present due to systematic absences caused by
 Centering of the lattice (I, F, A …)
 Screw axes
 Glide planes

n  = 2 dhkl sin
changes to
n  = 2 (dhkl/2)
sin or
2n 
Only =order
even 2 dhkl sin
reflections are present! Eg. Plane 100: reflections 200, 400, …
Relationship between d spacing and unit cell
dimensions
cubic system
tetragonal
orthorhombic
(after that it gets reasonably complicated …)

n  = 2 dhkl
sin
peak positions << >> d-spacing << >> unit cell
dimensions
(provided hkl is known)
 Effect of solid solution: eg. Calcite

Calcite Mg-rich Calcite

CaCO Mg0.064Ca0.93
3 6CO3 Ionic radii:
(6-fold coordination)

Ca2+ 1.00 Å
Mg2+ 0.72 Å

Same crystal structure, different cation sizes change in d-spacing

Effect of strain on peak shape
For example: annealed
brass
High
strain

Low
strain
 Effect of grain size on peak shape
Sample: 3 For grain sizes less than ~100 µm:
minerals
• The larger the grain size, the sharper the
peak
o eg. clay minerals are typically very fine
grained, their peaks small and broad
• Grains << 1 µm have very broad peaks,
eventually flattening out and creating a
‘hump’ in the background (‘amorphous’
materials)
1 µm
 eg. Minerals precipitated during
surface weathering processes (iron
oxides and oxyhydroxides) are often
‘amorphous’, ie. so fine grained that
they do not diffract X-rays.
 Amorphous material can be
quantified, but mineral phases can not
be distinguished
 What determines intensity of a peak Ihkl ?
(Among other things …)
• Atomic scattering factor f: the ability of an
atom (or ion) to scatter X-rays
o Depends on number of electrons, ie atomic
number
Light elements scatter little, heavy elements scatter a lot.
o Depends on angle 
o Look up in tables
• Atom positions in unit cell (x,y,z coord.)
• hkl
All combined in Structure factor F (sum over all atoms)

If enough reflections are available, one can use the intensities of the peaks
to determine the position of every atom in the unit cell, their thermal motion
etc. (Rietfeld refinement)
 Information in a diffraction pattern

• Peak positions give unit cell size and

shape
• Systematic absences give type of unit
cell and space group information
• Peak intensities tell you about
o the electron density inside the unit cell, i.e.
where the atoms are located
o the abundance of a mineral in a mineral
mixture
• Peak shapes and widths tell you
about any deviation from a perfect
crystal; crystallite size (<200 nm),