GG 711: Advanced Techniques in Geophysics and Materials Science

X-Ray Diffraction: Lecture 1

X-ray Diffraction I: Powder Diffraction

Pavel Zinin, Li Chung

HIGP, University of Hawaii, Honolulu, USA

www.soest.hawaii.edu\~zinin
 Why X-Rays

Best possible resolution of :

OM > 0.2 µm.
AFM > 1.0 nm
SEM > 1.0 nm
TEM > 0.2 nm
0.61 0.61 0.61
rAiry   ;
sin  NA nNA

TEM AFM OM eye

1Å 1 nm 1 µm 1 mm 1 cm

Computer Red Blood Hair

Atoms Molecules Viruses Cells
Circuits
 Why X-rays
Definition: X-radiation (composed of X-rays) is a form of electromagnetic radiation. X-rays
have a wavelength in the range of 10 to 0.01 nm, corresponding to frequencies in the range
30 petahertz to 30 exahertz (3 × 1016 Hz to 3 × 1019 Hz) and energies in the range 120 eV to
120 keV (Wikipedia, 2009).

c
E  h f  h 

hc

E
1240
 (nm) 
E (eV )

1 eVt is 1 volt (1 joule divided by 1 coulomb) E is the energy of the photon, h is

multiplied by the electron charge (1.6021×10-19 the Plank’s constant, f is the
coulomb). One electron volt is equal to 1.6021 ×10-19 frequency,  is the wavelength.
joules.
EM Spectrum Lines Produced by Electron Shell Ionization

K X-ray is produced due to removal of K shell electron, with L shell electron taking its place.
K occurs in the case where K shell electron is replaced by electron from the M shell.
L X-ray is produced due to removal of L shell electron, replaced by M shell electron.
M X-ray is produced due to removal of M shell electron, replaced by N shell electron.
 X - Ray
In 1895 at the University of Wurzburg, Wilhelm Roentgen (1845-1923) was studying
electrical discharges in low-pressure gases when he noted that a fluorescent screen
glowed even when placed several meters from the gas discharge tube and even when
black cardboard was placed between the tube and the screen. He concluded that the effect
was caused by a mysterious type of radiation, which he called x-rays because of their
unknown nature.

Nucleus of target atom Copper Tungsten rod target

Typical x-ray wavelengths are about 0.1 nm, which is of the order of the atomic spacing
in a solid. X-rays are produced when high-speed electrons are suddenly decelerated, for
example, when a metal target is struck by electrons that have been accelerated through a
potential difference of several thousand volts.
 X-ray generation

Spectrum of the X-rays emitted by an X-ray tube with a rhodium target, operated at 60
kV. The smooth, continuous curve is due to bremsstrahlung, and the spikes are
characteristic K lines for rhodium atoms.
 Historical Background

He wrote an initial
report "On a new kind
of ray: A preliminary
communication" and on
December 28, 1895
submitted it to the
Wurzburg's Physical-
Medical Society journal.
This was the first paper
http://www.nobel.se/physics/laureates/1901/rontgen-bio.html
written on X-rays.
On November 8, 1895, Roentgen referred to the
German physics professor radiation as "X", to
Wilhelm Conrad Roetgen indicate that it was an Print of Wilhelm Rontgen's first x-
stumbled on X-rays while unknown type of ray, the hand of his wife Anna taken
experimenting with Lenard radiation. on 1895-12-22, presented to
and Crookes tubes and Professor Ludwig Zehnder of the
began studying them (1901 Physik Institut, University of
Freiburg, on 1 January 1896.
Nobel prize in Physics).
 History of X-ray and XRD

•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".
His collaborators Walter Friedrich and Paul
Knipping took the picture on the bottom left in
1912. It shows how a beam of X-rays is scattered
Max von Laue (1897-1960)
into a characteristic pattern by a crystal. In this case
it is copper sulphate.

•The X-ray diffraction pattern of a pure substance is

like a fingerprint of the substance. The powder
diffraction method is thus ideally suited for
characterization and identification of polycrystalline
phases.
X-ray generation

X-ray spectrograph of
lysozyme, the second
protein to have its
molecular structure
determined by x-ray (From
L. Bragg’s Nobel Prise
lecture..
 X-ray generation

Ionizing spectrometer was the instrument used by W.H. Bragg to

conduct x-ray spectra collection
 Wave interference

Wave diffraction can cause complex

patterns of destructive and
constructive interference.
 X-ray generation

Diffraction of the parallel rays from two parallel surfaces.

 Historical Background

He wrote an initial
report "On a new kind
of ray: A preliminary
communication" and on
December 28, 1895
submitted it to the
Wurzburg's Physical-
Medical Society journal.
This was the first paper
http://www.nobel.se/physics/laureates/1901/rontgen-bio.html
written on X-rays.
On November 8, 1895, Roentgen referred to the
German physics professor radiation as "X", to
Wilhelm Conrad Roetgen indicate that it was an Print of Wilhelm Rontgen's first x-
stumbled on X-rays while unknown type of ray, the hand of his wife Anna taken
experimenting with Lenard radiation. on 1895-12-22, presented to
and Crookes tubes and Professor Ludwig Zehnder of the
began studying them (1901 Physik Institut, University of
Freiburg, on 1 January 1896.
Nobel prize in Physics).
 History of X-ray and XRD

•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".
His collaborators Walter Friedrich and Paul
Knipping took the picture on the bottom left in
1912. It shows how a beam of X-rays is scattered
Max von Laue (1897-1960)
into a characteristic pattern by a crystal. In this case
it is copper sulphate.

•The X-ray diffraction pattern of a pure substance is

like a fingerprint of the substance. The powder
diffraction method is thus ideally suited for
characterization and identification of polycrystalline
phases.
 Analysis of crystal structure by means of X-rays

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
Sir William Henry William Lawrence techniques and plays a major role in fields
Bragg (1862-1942) Bragg (1890-1971)
as diverse as structural biology and
materials science.
The father and son team of Sir
William Henry and William
Lawrence Bragg were awarded Wikipedia. 2009

the Nobel prize for physics

"for their services in the
analysis of crystal structure by
means of Xrays“ in 1915.
 X-ray Diffraction

In physics, Bragg's law states that

when X-rays hit an atom, they make
the electronic cloud move as does
any electromagnetic wave. The
movement of these charges re-
radiates waves with the same (or
elastic scattering).
These re-emitted wave fields interfere with each other either constructively or destructively
(overlapping waves either add together to produce stronger peaks or subtract from each
other to some degree), producing a diffraction pattern on a detector or film. The resulting
wave interference pattern is the basis of diffraction analysis. X-ray wavelength is
comparable with inter-atomic distances (~1.5 Å) and thus are an excellent probe for this
length scale (Wikipedia, 2009).

n  2d sin 
 X-ray Diffraction

Plane wave
Plane and spherical waves
 X-ray Diffraction

In physics, Bragg's law states that

when X-rays hit an atom, they make
the electronic cloud move as does
any electromagnetic wave. The
movement of these charges re-
radiates waves with the same (or
elastic scattering).
These re-emitted wave fields interfere with each other either constructively or destructively
(overlapping waves either add together to produce stronger peaks or subtract from each
other to some degree), producing a diffraction pattern on a detector or film. The resulting
wave interference pattern is the basis of diffraction analysis. X-ray wavelength is
comparable with inter-atomic distances (~1.5 Å) and thus are an excellent probe for this
length scale (Wikipedia, 2009).

n  2d sin 
 Inter-Planar Spacing, dhkl, and Miller Indices

The (200) planes The (220) planes

of atoms in NaCl of atoms in NaCl

• The unit cell is the basic repeating unit that defines a crystal.
• Parallel planes of atoms intersecting the unit cell are used to define
directions and distances in the crystal.
– These crystallographic planes are identified by Miller indices.
X-ray Diffraction

Adding up phases at the detector of the wavelets

scattered from all the scattering centers in the
sample:
 The crystallographer’s world view

Diamond Atomic structure of diamond

Definition: A crystal consists of atoms arranged in a pattern that repeats periodically in

three dimensions.
There are two aspects to this pattern: Periodicity; Symmetry

Ideal Crystal:
• An ideal crystal is a periodic array of structural units, such as atoms or molecules.
• It can be constructed by the infinite repetition of these identical structural units in space.
• Structure can be described in terms of a lattice, with a group of atoms attached to each lattice point.
The group of atoms is the basis.
 Periodicity and a Crystal Lattice
A Primitive Cubic Lattice
of Diamond

To describe the periodicity, we

superimpose (mentally) on the crystal
structure a lattice. A lattice is a regular
array of geometrical points, each of which
has the same environment (they are all
equivalent).
 Atomic Structure of Solids

A crystal consists of atoms arranged in a pattern that repeats periodically in three dimensions
(D. E. Sands, “ Introduction to Crystallography”, 1975). A crystalline solid possesses rigid and long-
range order. In a crystalline solid, atoms, molecules or ions occupy specific (predictable)
positions.
An amorphous solid does not possess a well-defined arrangement and long-range molecular
order.
A unit cell is the basic repeating structural unit of a crystalline solid.

lattice At lattice points:

point • Atoms
• Molecules
• Ions

Unit Cell Unit cells in 3 dimensions

Professor Dr. Supot Hannongbua Lecture: General Chemistr
 Descriptions of the Unit Cell

A unit cell of a lattice (or crystal) is a

volume which can describe the lattice
using only translations. In 3 dimensions
(for crystallographers), this volume is a
parallelepiped. Such a volume can be
defined by six numbers – the lengths of
the three sides, and the angles between
them – or three basis vectors.

vectors: a, b, c
Angles: , , 

position of the point in unit cell:

A three dimensional Bravais lattice x1a + x2b + x3c, 0  xn < 1
consists of all points with position
vectors R that can be written as a lattice points R = ha + kb + lc,
linear combination of primitive h,k,l – integers.
vectors. The expansion coefficients
must be integers.
Choice of a Unit Cell
In the 2-dimensional lattice shown here there
are 6 possible choices to define the unit cell,
labeled a through f.

In defining a unit cell for a crystal the choice

is somewhat arbitrary. But, the best choice is
one where: (a) The edges of the unit cell
should coincide with the symmetry of the
lattice; (b) the edges of the unit cell should be
related by the symmetry of the lattice; (c) the
smallest possible cell that contains all
elements should be chosen.

Definition of the Unit Cell: smallest

repetitive volume which contains the
complete lattice pattern of a crystal.

A unit cell is always a parallepiped.

3-D Unit Cell
 Two-dimensional lattices
Two dimensional repeating patterns These are known mathematically as two-dimensional
lattices or nets, and they provide a nice stepping-stone to the three-dimensional lattices of
crystals. Given the almost-infinite variety of designs of these kinds, it may be surprising
that they can be constructed from only one of five basic unit cells:

Square Lattice: Parallelogram Rectangular Rhombic or Hexagonal

x = y, 90° angles lattice lattice centered- lattice
x ≠ y, angles < x ≠ y, angles = rectangle (but unit cell is a
90° 90° lattice: x = y, rhombus with x
angles neither = y and angles
60° or 90°; 60°)

The work of the Dutch artist Maurits Escher (1888-1972).

Seven Crystal Systems

If we go to the three-
dimensional world of
crystals, there are just seven
possible basic lattice types,
known as crystal systems,
that can produce an infinite
lattice by successive
translations in three-
dimensional space so that
each lattice point has an
identical environment.
 Lattices

Auguste Bravais
(1811-1863)

•In 1848, Auguste Bravais demonstrated that

in a 3-dimensional system there are fourteen
possible lattices
•A Bravais lattice is an infinite array of
discrete points with identical environment An infinite array of discrete
•seven crystal systems + four lattice centering points with an arrangement
types = 14 Bravais lattices and orientation that appears
•Lattices are characterized by translation exactly the same, from any of
symmetry the points the array is viewed
http://www.tsl.uu.se/uhdsg/Personal/Mikael/Fysikmusik.html from.
Fourteen Bravais Lattices in Three Dimensions
Types of Cubic Cells
 SIMPLE CUBIC STRUCTURE (SC)

• Cubic unit cell is 3D repeat unit

• Rare (only Po has this structure)
• Close-packed directions (directions along which atoms touch each other)
are cube edges.
• Coordination # = 6
(# nearest neighbors)
 Body Centered Cubic Structure (BCC)

• Atoms touch each other along cube diagonals.

--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

examples: Cr, W, Fe (), Tantalum, Molybdenum

• Coordination Number = 8

Adapted from Fig. 3.2,

Callister 7e.

2 atoms/unit cell: 1 center + 8 corners x 1/8

 Face Centered Cubic Structure (FCC)
• Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.
exanples: Al, Cu, Au, Pb, Ni, Pt, Ag

• Coordination Number = 12

Adapted from Fig. 3.1, Callister 7e.

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

 Shared by 2 unit cells

Shared by 8 unit cells

Professor Dr. Supot Hannongbua Lecture: General Chemistry
1 atom/unit cell 2 atoms/unit cell 4 atoms/unit cell
(8 x 1/8 = 1) (8 x 1/8 + 1 = 2) (8 x 1/8 + 6 x 1/2 = 4)
 Close packed crystals

A plane
B plane

C plane

A plane

…ABCABCABC… packing …ABABAB… packing

[Face Centered Cubic (FCC)] [Hexagonal Close Packing (HCP)]
 FCC Stacking

A
B
C

A
B
C
• FCC Unit Cell

From D.D. Johnson, 2004, MSE, Illinois

 Hexagonal Close-Packed Structure (HCP)

• ABAB...
A Stacking Sequence
B

Layer A
• 3D Projection

Layer B
A sites
• Coordination Number = 12
c B sites
6 atoms/unit cell. ex: Cd, Mg, Ti, Zn
• APF = 0.74
A sites
• c/a = 1.633
a
 Types of Crystals and General Properties

Type of Forces Holding the General Properties Examples

Crystal units Together
Ionic Electrostatic attraction Hard, brittle, high melting LiF, MgO, NaCl,
point, poor conductor of CaCO3
heat and electricity
Covalent Covalent bond Hard, high melting point, C (diamond),
poor conductor of heat and SiO2(quartz)
electricity
Molecular Dispersion forces, Soft, low melting point, Ar, CO2, I2, H2O
hydrogen bonds, poor conductor of heat and
dipole-dipole forces electricity
Metallic Metallic Bond Soft to hard, low melting All metallic
point, poor conductor of elements, for
heat and electricity example, Na, Mg,
Fe, Cu
 Ionic Crystals
• Lattice points occupied by cations and anions
• Held together by electrostatic attraction
• Hard, brittle, high melting point
• Poor conductor of heat and electricity

CsCl ZnS CaF2

 Covalent Crystals
• Lattice points occupied by atoms
• Held together by covalent bonds
• Hard, high melting point
• Poor conductor of heat and electricity

carbon
atoms

diamond graphite
 Molecular Crystals Metallic Crystals
• Lattice points occupied by molecules • Lattice points occupied by metal atoms
• Held together by intermolecular • Held together by metallic bonds
forces • Soft to hard, low to high melting point
• Soft, low melting point • Good conductors of heat and electricity
• Poor conductor of heat and electricity

Cross Section of a Metallic Crystal

nucleus &
inner shell e-

mobile “sea”
of e-
 The Diffraction Pattern

• Crystals provide two things:

1. Amplification: A single molecule will emit a very weak signal. 1010 molecules
amplify the signal by 1010
2. Periodicity: The Diffraction pattern is related to the Fourier Transform of the
electron density of the molecule
• Fourier Transform assumes that the signal is periodic; the crystal lattice
provides the periodicity

• In XRD, the detector records the position and

intensity of each reflection
• The crystal is rotated several times to get a full
sampling of the 3D reciprocal space
– The reciprocal lattice
• By convention, each reflection is labeled by 3
integers, h,k,l, (called Miller Indices)
representing the position of the reflection in the
3D reciprocal lattice
 Data Collection

The angles at which x-rays are diffracted depends on the distance between adjacent layers of atoms
or ions. X-rays that hit adjacent layers can add their energies constructively when they are “in
phase”. This produces dark dots on a detector plate.
Generation of X-rays

But it isn’t quite this simple.

http://hyperphysics.phy-astr.gsu.edu/hbase/quantum/xtube.html#c1
 X-ray Data Collection at Synchrotron
A synchrotron is a particular type of cyclic particle
accelerator in which the magnetic field (to turn the
particles so they circulate) and the electric field (to
accelerate the particles) are carefully synchronised
with the travelling particle beam. The proton
synchrotron was originally conceived by Sir Marcus
Oliphant. The honor of being the first to publish the
idea went to Vladimir Veksler, and the first electron
synchrotron was constructed by Edwin McMillan.

1240
 (nm) 
E (eV )

A very powerful X-ray source

• Thousands or millions of times more powerful
than laboratory sources
• Higher Resolution
• Sometimes proton positions can be resolved
• Works with smaller crystals
• Argonne National Laboratory:  ~ 0.5 Å
X-ray Data Collection at Synchrotron
 X-ray as a plane wave
The most convenient wave to write down introduce equation describing a plane wave is
to use complex exponent ei

expi  cos   i sin  :   Aei kxt    A cos  kx  t     iA sin  kx  t    ;

 Bragg’s Law

Reflections only occur where the waves emitted by each atom interfere constructively

All other positions have destructive interference, and sum to zero

n  2d sin 
where n is an integer determined by the order given,  is the wavelength of the X-rays (and
moving electrons, protons and neutrons), d is the spacing between the planes in the atomic
lattice, and is the angle between the incident ray and the scattering planes.
 Deriving Bragg’s equation

• The angle of incidence of the x-rays

is 
• The angle at which the x-rays are
 C diffracted is equal to
  • the angle of incidence, 
D F • The angle of diffraction is the sum
d of these two angles, 2
E

The two x-ray beams travel at different distances. This difference is related to the
distance between parallel planes. We connect the two beams with perpendicular lines
(CD and CF) and obtain two equivalent right triangles. CE = d (interplanar distance)
DE m
sin   ; d sin   DE  EF 2d sin   EF  DE  difference in path length   m
d k
Reflection (signal) only occurs when conditions for constructive interference between
the beams are met. These conditions are met when the difference in path length equals an
integral number of wavelengths, m. The final equation is the BRAGG’S LAW
m
2d sin   EF  DE    m
k
 Powder Diffraction
Definition: Powder diffraction is a scientific technique
using X-ray, neutron, or electron diffraction on powder or
microcrystalline samples for structural characterization of
materials.
Ideally, every possible crystalline orientation is
represented equally in a powdered sample. The resulting
orientational averaging causes the three dimensional
reciprocal space that is studied in single crystal diffraction
to be projected onto a single dimension.

Single set of planes

• Bragg planes act like mirrors

Powder sample • Each reflection corresponds to a set of Bragg
planes
• These planes are given indices (h,k,l) called
Miller indeces.
• Recall that each reflection was also given an
index
 Powder Diffraction
• Powder Diffraction is more aptly named polycrystalline diffraction
– Samples can be powder, sintered pellets, coatings on substrates, engine blocks, …
• If the crystallites are randomly oriented, and there are enough of them, then they will produce a
continuous Debye cone.
• In a linear diffraction pattern, the detector scans through an arc that intersects each Debye cone at a
single point; thus giving the appearance of a discrete diffraction peak.

~3000
K

Intensity, a.u.
before
melting

Fe at 50 GPa

10 20 30

2, degree

Shen, Prakapenka, Rivers, Sutton, PRL, 92. 185701, (2004)

 Inter-Planar Spacing, dhkl, and Miller Indices

Inter-planar spacings can be The inter-planar spacing (dhkl) between

measured by x-ray diffraction crystallographic planes belonging to the same
(Bragg’s Law) family (hkl) is denoted (dhkl)
We can use Bragg’s Law to interpret Distances between planes defined by the same
the diffraction in terms of the distance set of Miller indices are unique for each
between lattice planes in the crystal material
based on the incident and diffraction
angle of the reflection.
 Inter-Planar Spacing, dhkl, and Miller Indices

The (200) planes The (220) planes

of atoms in NaCl of atoms in NaCl

• The unit cell is the basic repeating unit that defines a crystal.
• Parallel planes of atoms intersecting the unit cell are used to define
directions and distances in the crystal.
– These crystallographic planes are identified by Miller indices.
 Planes in Lattices and Miller Indices

An essential concept required to understand the diffraction of X-rays by crystal lattices (at
least using the Bragg treatment) is the presence of planes and families of planes in the
crystal lattice. Each plane is constructed by connecting at least three different lattice
points together and, because of the periodicity of the lattice, there will a family (series) of
planes parallel passing through every lattice point. A convenient way to describe the
orientation of any of these families of plane is with a Miller Index of the form (hkl) in
which the plane makes the intercepts with a unit cell of a/h, b/k and c/l. Thus the Miller
index indicates the reciprocal of the intercepts.

The meaning of the Miller

indices can be better
understood after considering an
example shown in the Figure.
In Fig. both sets of planes are
parallel to b and c. Hence, in
both cases k = l = 0. The set of
planes shown on the left divides
a into one part, while the

d(100) = a d(200)=a/2
Planes in Lattices and Miller Indices

1 1 1
2
 2 2
d (110) a b

1 4 1 1
2
 2 2 2
d (213) a b c
Planes in Lattices and Miller Indices

Pictures from: http://www.gly.uga.edu/schroeder/geol6550/millerindices.html

 Powder Diffraction – Angular dispersive Method

Bragg Equation

n  2d sin  • Bragg planes act like mirrors

• Each reflection corresponds to a set of Bragg
planes
• These planes are given indices (h,k,l) called
Miller indices.

 • In three dimension, each reflection is

d hkl  represented by a cone with a 2θ angle with

2sin  hkl
respect to the incident beam.

Powder sample

Single set of planes

 Powder Diffraction Pattern of -iron (BCC)

z
(110)
c

y
a b z z
x c c

y y
(211) a a b
b
x
(200) x
 Powder Diffraction Pattern pattern of Diamond

UNIT CELL DATA: a = 3.5597 Å; b = 3.5597 Å; c = 3.5597 Å;

 = 90o;  = 90o;  = 90 °
cell volume: 45.107 Å3; calculated density: 3537.10 kg / m3

RECIPROCAL UNIT CELL DATA

a* = 0.2809; b* = 0.2809; c* = 0.2809 1/Å
 = 90o;  = 90o;  = 90 °
Space Group Symbol: F 41/d -3 2/m
 Powder Diffraction Pattern of Diamond

a=d * √(h2+k2+l2)
ref no. h k l d(hkl) I/Imax
√(h2+k2+l2) a
1 1 1 1 2.05519 100. 1.7321 3.5598
2 0 2 2 1.25854 38.8 2.8284 3.5595
3 1 1 3 1.07329 24.3 3.3166 3.5597
 The lattice parameters a, b, c and dhkl

The relationship between d and the lattice parameters can be determined geometrically
and depends on the crystal system. When the unit cell axes are mutually perpendicular,
the interplanar spacing can be easily derived.
Crystal system dhkl, lattice parameters and Miller indices

Cubic
1 h2  k 2  l 2
2

d hkl a2

Tetragonal 1 h2  k 2 l2
2
 2
 2
d hkl a c

Orthorhombic
1 h2 k 2 l2
2
 2  2  2
d hkl a b c

1 4 h2  k 2 +hk l2
Hexagonal 2
 2
 2
d hkl 3 a c

The expressions for the remaining crystal systems are more complex
 Home Work

1. Definition of the crystal and unit cell (SO).

2. Derive Bagg’s law (KK).

3. Describe three types of cubic unit cell (SO).

4. Definition of Miller indices (KK).

5. Describe Seven Crystal Systems (KK).