Chapter 2.

BASICS OF X-RAY DIFFRACTION

A crystal may be defined as a solid composed of atoms arranged in a pattern periodic in three
dimensions. As such, crystals differ in a fundamental way from gases and liquids because the
atomic arrangements in the latter do not possess the essential requirement of periodicity. Not all
solids are crystalline, however; some are amorphous, like glass, and do not have any regular
interior arrangement of atoms. There is, in fact, no essential difference between an amorphous
solid and a liquid, and the former is often referred to as an "undercooled liquid."
Lattice: In thinking about crystals, it is often convenient to
ignore the actual atoms composing the crystal and their
periodic arrangement in Space, and to think instead of a
set of imaginary points which has a fixed relation in space
to the atoms of the crystal and may be regarded as a sort
of framework or skeleton on which the actual crystal is
built up.
This set of points can be formed as follows. Imagine
space to be divided by three sets of planes, the planes in
each set being parallel and equally
spaced. This division of space will produce a set of cells
each identical in size, shape, and orientation to its Since all the cells of the lattice
neighbors. The space-dividing planes will intersect each shown in the figure are identical,
other in a set of lines, and these lines in turn intersect in we may choose any one, for
the set of points referred to above. A set of points so example the heavily outlined one,
formed has an important property: it constitutes a point as a unit cell.
lattice, which is defined as an array of points in space so
arranged that each point has identical surroundings.
 Unit cell and crystal systems: The size and shape of the
unit cell can in turn be described by the three vectors a, b,
and c drawn from one corner of the cell taken as origin.
These vectors define the cell and are called the
crystallographic axes of the cell. They may also be
described in terms of their lengths (a, b, c) and the angles
between them (α, β, and γ). These lengths and angles are
the lattice constants or lattice parameters of the unit cell.

Seven Crystal Systems

 14 Bravais Lattice
Seven different point lattices can be obtained simply
by putting points at the corners of the unit cells of the
seven crystal systems. However, there are other
arrangements of points which fulfill the requirements
of a point lattice, namely, that each point have
identical surroundings. The French crystallographer
Bravais worked on this problem and in 1848
demonstrated that there are fourteen possible point
lattices and no more;this important result is
commemorated by our use of the terms Bravais
lattice and point lattice as synonymous. For example,
if a point is placed at the center of each cell of a cubic
point lattice, the new array of points also forms a
point lattice. Similarly, another point lattice can be
based on a cubic unit cell having lattice points at each
corner and in the center of each face.

A lattice point in the interior of a cell "belongs" to

that cell, while one in a cell face is shared by two
cells and one at a corner is shared by eight. The
number of lattice points per cell is therefore
given by
Nf
N where Ni = number of interior points, Nf = number
N = Ni + + c of points on faces, and Nc = number of points on
2 8
corners.
 Symmetry
Both Bravais lattices and the real crystals which are built up on them exhibit various
kinds of symmetry.
 Crystalline materials are characterized by the
orderly periodic arrangements of atoms.
The (200) The (220)
planes of atoms planes of atoms
in NaCl 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.
 Interplanar Spacing
The various sets of planes in a lattice have various values of interplanar spacing. The
planes of large spacing have low indices and pass through a high density of lattice
points, whereas the reverse is true of planes of small spacing. The interplanar spacing
d is measured at right angles to the planes, is a function both of the plane indices
(hkl) and the lattice constants. The exact relation depends on the crystal system
involved and for the cubic system takes on the relatively simple form

1 h2 + k 2 + l 2
= Cubic system
d2 a 2

1 h2 + k 2 l 2
= + 2 Tetragonal system
d2 a 2
c
1 4 (h 2 + hk + k 2 ) l 2
= + Hexagonal system
d2 3 a2 c2
1 h2 k 2 l 2 Orthorhombic
= + +
d2 a2 b2 c2 system
 Directions of Diffraction
• Random arrangement of atoms in space
gives rise to scattering in all directions:
weak intensities.
• By atoms arranged periodically in space
– In a few specific directions satisfying Bragg’s
law: strong intensities of the scattered
beam :Diffraction
– A diffracted beam may be defined as a beam
composed of a large number of scattered rays
mutually reinforcing each other
Defines the spacing (d) of atomic planes and incident angle (θ)
at which X-rays of a particular wavelength will diffract in phase

Waves add if the path difference AB + BC is equal to nλ.

The incident beam, the normal to the reflection
plane, and the diffracted beam are always co-
planar.
The angle between the diffracted beam and the
transmitted beam is always 2θ (usually
measured).
Sin θ cannot be more than unity; this requires
nλ < 2d, for n=1, λ < 2d
λ should be less than twice the d spacing we wish to study
Soru: Calculate diffraction angle from {110} crystal planes of BCC iron with a lattice
constant of 0.287 nm using Cu Kα radiation (λ = 0.1541 nm).

Solution:

a 0.287
d110 = = = 0.2029 nm
h +k +l
2 2
1 +1 + 0
2 2 2

λ = 2d hkl sin θ Note that n is equal to 1 when Bragg law is used for the calculation.
0.1541 = 2(0.2029)(sin θ )
θ = 22,32o
or
1 (h 2 + k 2 + l 2 )
2
=
d a2
λ = 2d sin θ Bragg Law
λ2
sin θ =
2
(h 2 + k 2 + l 2 )
4a 2
0.15412 2 2
sin θ =
2
2
(1 + 1 + 0 2
)
4(0.287)
θ = 22,32o
 INTENSITIES ( I ) OF DIFFRACTED X-RAYS
1 + cos 2
2θ
I = F P( 2
2
) A(θ )e − 2 M
sin θ cos θ

F= Structure factor

P= Multiplication factor: P=6 for {100} ; (100) ( 1 00) (010) (0 1 0) (001) (00 1 )
P=8 for {111}

1 + cos 2 2θ
= Lorentz-polarization factor.
sin θ cos θ
2

A(θ ) = Absorption factor

e −2 M = Temperature Factor
 Structure Factor
N
Fhkl = ∑ f n e 2π i ( hun + kvn + lwn )
Intensity of the diffracted beam α |F|2
1
− h,k,l : indices of the diffraction plane under consideration
− u,v,w : co-ordinates of the atoms in the lattice
− N : number of atoms
− fn : scattering factor of a particular type of atom

Bravais Lattice Reflections possibly present Reflections necessarily absent

Simple All None

Body Centered (h+k+l): Even (h+k+l): Odd

Face Centered h, k, and l unmixed i.e. all h, k, and l: mixed

odd or all even
eix = cos x + i sin x
i = −1
eπ i = cos π + i sin π = −1 + 0 Some useful equations

eπ i = e3π i = e5π i = −1
e 2π i = e 4π i = e 6π i = +1
e nπ i = (−1) n

a) Simple Bravais lattice

F = fe 2π i ( 0 ) = f
F 2= f 2 F is independent of hkl.
(b) Base centered unit cell : There are two atoms at (0,0,0) ve (1/2,1/2, 0).

h k
2π i ( 0 ) 2π i ( 2 + 2 )
F= f e +f e = f + feπi ( h + k )
= f (1 + eπi ( h + k ) )

There are two cases:

i) h, k unmixed (all even or odd) (h+k=even)

F =2f
F 2= 4 f 2

ii) h, k mixed eπ i (h + k ) = −1
F = 0, F 2 = 0
For example: For (111), (112), (113), (021), (022), (023) diffractions F = 2f;
For (011), (012), (013), (101), (102), (103) , F = 0.
(c) Body centered unit cell: There are two atoms at (0,0,0) and (1/2,1/2,1/2)

 h + k +l 
2π i  
F = f e 2π i ( 0 ) + f e  2 
= f (1 + eπ i (h + k + l ) )

i) (h+k+l) even F =2f, F =4f 2 2

ii) (h+k+l) odd F = 0, F = 0

2

(d) Question: For face centered unit cell, show that diffraction intensities of (hkl)
planes of unmixed indices are not zero, while those of mixed indices are zero.

(e) Question: Calculate structure factors for NaCl.

Hints: In this case there are two different atoms.
Their coordinates are :
Na: (0,0,0) (1/2,1/2,0) (1/2,0,1/2) (0,1/2,1/2)
Cl: (1/2,1/2,1/2) (0, 0,1/2) (0, 1/2, 0) (1/2,0 ,0)
X-ray diffraction pattern of NaCl
Permitted Reflections

Simple Cubic (100), (110), (111), (200), (210), (211),

(220), (300), (221) ………
BCC (110), (200), (211), (220), (310), (222)….
FCC (111), (200), (220), (311)…..
 Qualitative Analysis-Identification of peaks
Diffraction patterns are best reported using dhkl and relative
intensity rather than 2θ and absolute intensity.
• The peak position 2θ depends on instrumental characteristics such
as wavelength.
• The interplanar spacing dhkl is an intrinsic, instrument-independent, material
property.
• Bragg’s Law is used to convert observed 2θ positions to dhkl.
• The absolute intensity, i.e. the number of X rays observed in a given
peak, can vary due to instrumental and experimental parameters.
– The relative intensities of the diffraction peaks should be instrument
independent.
• To calculate relative intensity, divide the absolute intensity of every peak by
the absolute intensity of the most intense peak, and then convert to a
percentage. The most intense peak of a phase is therefore always called the
“100% peak”.
– Peak areas are much more reliable than peak heights as a measure of
intensity.
 Databases such as the Powder Diffraction File (PDF)
contain d-I lists for thousands of crystalline phases.
• The PDF contains over 200,000 diffraction patterns.
• Modern computer programs can help you determine what phases are
present in your sample by quickly comparing your diffraction data to
all of the patterns in the database.
• The PDF card for an entry contains a lot of useful information,
including literature references.
Name and formula
Reference code: 00-001-1260
PDF index name: Nickel
Empirical formula: Ni
Chemical formula: Ni
Crystallographic parameters
Crystal system: Cubic
Space group: Fm-3m
Space group number: 225
a (Å): 3.5175
b (Å): 3.5175
c (Å): 3.5175
Alpha (°): 90.0000
Beta (°): 90.0000
Gamma (°): 90.0000
Measured density (g/cm^3): 8.90
Volume of cell (10^6 pm^3): 43.52
Z: 4.00
RIR: -
Status, subfiles and quality
Status: Marked as deleted by ICDD
Subfiles: Inorganic
Quality: Blank (B)
References
Primary reference: Hanawalt et al., Anal. Chem., 10, 475, (1938)
Optical data: Data on Chem. for Cer. Use, Natl. Res. Council Bull. 107
Unit cell: The Structure of Crystals, 1st Ed.
Stick pattern from JCPDS

http://ww1.iucr.org/cww-top/crystal.index.html
Actual Pattern

Bulk electrodeposited nanocrystalline nickel

 Analysis of Single Phase
2θ(˚) d (Å) (I/I1)*100
27.42 3.25 10
31.70 2.82 100
45.54 1.99 60
53.55 1.71 5
56.40 1.63 30
Intensity (a.u.)

65.70 1.42 20
76.08 1.25 30
84.11 1.15 30
89.94 1.09 5
I1: Intensity of the strongest peak
 Procedure
• Note first three strongest peaks at d1, d2, and d3
• In the present case: d1: 2.82; d2: 1.99 and d3: 1.63 Å
• Search JCPDS manual to find the d group belonging to the
strongest line: between 2.84-2.80 Å
• There are 17 substances with approximately similar d2 but only 4
have d1: 2.82 Å
• Out of these, only NaCl has d3: 1.63 Å
• It is NaCl……………Hurrah
Specimen and Intensities Substance File Number
2.829 1.999 2.26x 1.619 1.519 1.499 3.578 2.668 (ErSe)2Q 19-443
2.82x 1.996 1.632 3.261 1.261 1.151 1.411 0.891 NaCl 5-628
2.824 1.994 1.54x 1.204 1.194 2.443 5.622 4.892 (NH4)2WO2Cl4 22-65
2.82x 1.998 1.263 1.632 1.152 0.941 0.891 1.411 (BePd)2C 18-225
Caution: It could be much more tricky if the sample is oriented or textured or your goniometer is not
calibrated
 Presence of Multiple phases
• More Complex
• Several permutations combinations possible
• e.g. d1; d2; and d3, the first three strongest lines
show several alternatives
• Then take any of the two lines together and match
• It turns out that 1st and 3rd strongest lies belong to
Cu and then all other peaks for Cu can be
separated out
• Now separate the remaining lines and normalize
the intensities
• Look for first three lines and it turns out that the
phase is Cu2O

• If more phases, more pain to solve 

Analysis of Multiphase sample
Instrumentation-
Diffractometer
Powder Diffraction Method
• Often requires random
orientation of very fine
crystals
• Incident beam of a certain
X-ray wavelength will
diffract from atomic planes
oriented at the appropriate
θ angles for the
characteristic d spacing
• Random orientation of
crystals will produce more
intense diffraction peaks
for particular angles that
correspond to
characteristic atomic
planes
 Slits To limit the size of beam (Divergence slits)

To alter beam profile

(Soller slit angular divergence )

 Narrow slits Lower intensity

+
Narrow peak
 A single crystal specimen in a Bragg-Brentano
diffractometer would produce only one family of peaks in
the diffraction pattern.

2θ

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

2θ 2θ 2θ

• 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.
 Reality
Ideal

Crystallite size can be

calculated using
Scherrer Formula

0.9λ
t=
B cos θ B

Instrumental broadening must be subtracted

(From “Elements of X-ray Diffraction”, B.D. Cullity, Addison Wesley)
Diffraction from a variety of materials

(From “Elements of X-ray

Diffraction”, B.D. Cullity,
Addison Wesley)