X-RAY DIFFRACTION: DETERMINATION

OF CRYSTAL STRUCTURES
Subject: Material Science - Lecture #9
‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬
Kirkuk University - College of Science
Physics Department – 3rd grade
Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬
X-RAY DIFFRACTION: DETERMINATION OF
CRYSTAL STRUCTURES
• Theatomic and molecular arrangements in solids has resulted
from x-ray diffraction investigations.
• X-rays are still very important in developing new materials.
• Understand a brief overview of the diffraction phenomenon and
how, using x-rays, atomic interplanar distances and crystal
structures are deduced.

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

The Diffraction Phenomenon

• Electromagneticradiations (such as visible light) can interact
among themselves and with matter, giving rise to a multitude of
phenomena such as reflection, refraction, diffraction,
scattering, polarization...

reflection refraction diffraction polarization

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• Diffraction
occurs when a wave encounters a series of regularly
spaced obstacles that:
(1) are capable of scattering the wave, and (2) have spacing that
are comparable in magnitude to the wavelength.
• diffraction
is a consequence of specific phase relationships
established between two or more waves that have been
scattered by the obstacles.

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

waves 1 and 2 in Figure a, which have the same

• Consider
wavelength (λ) and are in phase at point 𝑂 − 𝑂′ .
• Now let us suppose that both waves are scattered in such a
way that they traverse (travel across or through) different paths.
• The
path length difference is an integral number of
wavelengths.

constructively
interfere

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• Other
phase relationships are possible between scattered
waves
• The
path length difference after scattering is some integral
number of half-wavelengths.

destructively interfere

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

For example Diffraction of light wave

For electromagnetic radiation to be diffracted the spacing in the
grating should be of the same order as the wavelength

Diffraction of a Diffraction of a plane

Diffraction of a
plane wave when wave at a slit whose
plane wave with
the slit width equals width is several times
two slit
the wavelength the wavelength
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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

X-Ray Diffraction and Bragg’s Law

• X-rays are a form of electromagnetic radiation that have high
energies and short wavelengths from (0.01-10 nm) ( 0.1 -100
Å) -wavelengths on the order of the atomic spacing for solids
(In crystals the typical interatomic spacing ~ 2-3 Å).

• When a beam of x-rays

impinges on a solid material,
a portion of this beam is
scattered in all directions by
the electrons associated with
each atom or ion that lies
within the beam’s path.
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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• Letus now examine the necessary conditions for diffraction of

x-rays by a periodic arrangement of atoms.

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• Considerthe two parallel planes of atoms 𝐴 − 𝐴′ and 𝐵 − 𝐵′ in

Figure below which have the same ℎ, 𝑘, and 𝑙 Miller indices and
are separated by the interplanar spacing 𝑑ℎ𝑘𝑙

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• assume that a parallel, monochromatic, and coherent (in-

phase) beam of x-rays of wavelength λ is incident on these two
planes at an angle 𝜃.

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• Two rays in this beam, labeled 1 and 2, are scattered by atoms

𝑃 and 𝑄. Constructive interference of the scattered rays 1′ and
2′ occurs also at an angle 𝜃 to the planes

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• ifthe path length difference between 1– 𝑃– 1′ and 2– 𝑄– 2′ (i.e.,

𝑆𝑄 + 𝑄𝑇) is equal to a whole number, 𝑛, of wavelengths that is,
the condition for diffraction is:
𝑛λ = 𝑆𝑄 + 𝑄𝑇 … … … (3.20)

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

𝑛λ = 𝑑ℎ𝑘𝑙 sin 𝜃 + 𝑑ℎ𝑘𝑙 sin 𝜃

𝑛λ = 2𝑑ℎ𝑘𝑙 sin 𝜃 … … … (3.21)

Equation 3.21 is known as

Bragg’s law
𝑛 is the order of reflection, which
may be any integer (1, 2, 3, . . .)
consistent with sin 𝜃 not
exceeding unity.

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• Bragg’slaw expression relating the x-ray wavelength and

interatomic spacing to the angle of the diffracted beam.
𝑛λ = 2𝑑ℎ𝑘𝑙 sin 𝜃 … … … (3.21)
Bragg’s law is not satisfied, then the interference will be
• If
nonconstructive so as to yield a very low-intensity diffracted
beam.

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• Themagnitude of the distance between two adjacent and

parallel planes of atoms (i.e., the interplanar spacing 𝑑ℎ𝑘𝑙 ) is a
function of the Miller indices (ℎ, 𝑘, and 𝑙) as well as the lattice
parameter(s).

For example, for crystal structures that have cubic symmetry,

𝑎
𝑑ℎ𝑘𝑙 = … … … (3.22)
2
ℎ +𝑘 +𝑙2 2

𝑎 is the lattice parameter (unit cell edge length).

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Kirkuk University - College of Science - Physics Department - 3rd grade
Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• Relationships similar to Equation 3.22, but more complex, exist

for the other six crystal systems

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• Bragg’s law, 𝑛λ = 2𝑑ℎ𝑘𝑙 sin 𝜃 … … … (3.21)

is a necessary but not sufficient condition for diffraction by real
crystals.
• It
specifies when diffraction will occur for unit cells having atoms
positioned only at cell corners.
• However, atoms situated at other sites (e.g., face and interior
unit cell positions as with FCC and BCC) act as extra scattering
centers, which can produce out-of-phase scattering at certain
Bragg angles.
• Thenet result is the absence of some diffracted beams that,
according to Equation 3.21, should be present.

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Kirkuk University - College of Science - Physics Department - 3rd grade
Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• For the BCC crystal structure, ℎ + 𝑘 + 𝑙 must be even if

diffraction is to occur

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• for FCC, ℎ, 𝑘, and 𝑙 must all be either odd or even

Aluminum powder pattern

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• reflection rules, are summarized in Table below

• Zero is considered to be an even integer

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

Diffraction Techniques
• One common diffraction technique employs a powdered or
polycrystalline specimen consisting of many fine and randomly
oriented particles that are exposed to monochromatic x-
radiation.
• Each powder particle (or grain) is a crystal, and having a large
number of them with random orientations ensures that some
particles are properly oriented such that every possible set of
crystallographic planes will be available for diffraction.

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• The diffractometer is an instrument used to determine the

angles at which diffraction occurs for powdered specimens; its
features are represented schematically in Figure below:

T is the monochromatic x-ray source

S is the sample
C is the detector (the intensities of
diffracted beams are detected with a
counter labeled C)
O is the axis around which the sample
and detector rotate (this axis is
perpendicular to the plane of the page).
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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• The counter is mounted on a movable carriage that may also be

rotated about the O axis; its angular position in terms of 2𝜃 is
marked on a graduated scale.

• Carriage and specimen are

mechanically coupled such that
a rotation of the specimen
through 𝜃 is accompanied by a
2𝜃 rotation of the counter; this
ensures that the incident and
reflection angles are maintained
equal to one another
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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• Collimators(a device for producing a parallel beam of rays or

radiation)are incorporated within the beam path to produce a
well-defined and focused beam.
• Utilization of a filter provides a near-monochromatic beam.

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• Asthe counter moves at constant angular velocity, a recorder

automatically plots the diffracted beam intensity (monitored by
the counter) as a function of 2𝜃
• 2𝜃is termed the diffraction angle, which is measured
experimentally.

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

One of the primary uses of x-ray diffractometry is for the

• determination of crystal structure.
• The unit cell size and geometry
• thearrangement of atoms within the unit cell is associated with
the relative intensities of these peaks.
• qualitative and quantitative chemical identifications
• determination of residual stresses and crystal size.

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• X-rays,as well as electron and neutron beams, are also used in

other types of material investigations.
For example, crystallographic orientations of single crystals are
possible using x-ray diffraction (or Laue) photographs.

(a) X-ray diffraction photograph [or Laue photograph for a single crystal of magnesium.
(b) Schematic diagram illustrating how the spots (i.e., the diffraction pattern) in (a) are 29
produced.
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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

EXAMPLE PROBLEM
Interplanar Spacing and Diffraction Angle Computations
For BCC iron, compute (a) the interplanar spacing and (b) the
diffraction angle for the (220) set of planes. The lattice parameter for Fe
is 0.2866 nm. Assume that monochromatic radiation having a
wavelength of 0.1790 nm is used, and the order of reflection is 1.
Solution
(a)
𝑎
𝑑ℎ𝑘𝑙 = … … … (3.22)
ℎ2 + 𝑘2 + 𝑙2

0.2866 𝑛𝑚
𝑑ℎ𝑘𝑙 = = 0.1013 𝑚
22 + 22 + 02

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

(b)
𝑛λ = 2𝑑ℎ𝑘𝑙 sin 𝜃 … … … (3.21)

𝑛λ 1 × 0.1790 nm
sin 𝜃 = = = 0.884
2𝑑ℎ𝑘𝑙 2 × 0.1013 nm

𝜃 = sin−1 0.884 = 62.13°

The diffraction angle is 2𝜃, or
2𝜃 = 2 × 62.13° = 124.26 °

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

EXAMPLE PROBLEM
Interplanar Spacing and Lattice Parameter Computations for Lead
Figure 3.24 shows an x-ray diffraction pattern for lead taken
using a diffractometer and monochromatic x-radiation having a
wavelength of 0.1542 nm; each diffraction peak on the pattern
has been indexed. Compute the interplanar spacing for each set
of planes indexed; also, determine the lattice parameter of Pb for
each of the peaks. For all peaks, assume the order of diffraction
is 1

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

RECIPROCAL SPACE
• Reciprocal Lattice: Reciprocal vectors are defined to be
perpendicular to two of the three lattice vectors and with length
equal to 1/length of the third vector.
We construct the axis vectors 𝑎∗ , 𝑏 ∗ , 𝑐 ∗ of the reciprocal lattice:

b×𝑐 c×𝑎 𝑎×𝑏

𝑎∗ = 2𝜋 ; 𝑏 ∗ = 2π ; 𝑐 ∗ = 2π … … (3.23)
a∙𝑏×𝑐 a∙𝑏×𝑐 a∙𝑏×𝑐

• The factors 2𝜋 are not used by crystallographers but are

convenient in solid state physics.
• The reciprocal lattice is a lattice in the Fourier space associated
with the crystal 35
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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

Points in the reciprocal lattice are mapped by the set of vectors

𝐆 = 𝑣1 𝑎∗ + 𝑣2 𝑏 ∗ + 𝑣3 𝑐 ∗ … …(15)
where 𝑣1 , 𝑣2 , 𝑣3 are integers.
A vector 𝐆 of this form is a reciprocal lattice vector.

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• A diffraction
pattern of a crystal is a map of the reciprocal lattice
of the crystal.
• A microscope image, if it could be resolved on a fine enough
scale, is a map of the crystal structure in real space.

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

Brillouin zone
A Brillouin zone is defined as a Wigner-Seitz primitive cell in the
reciprocal lattice.

• primitive cell is a
minimum volume cell
(a unit cell)
corresponding to a
single lattice point of
a structure

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

We now work in reciprocal space, the space of the k’s and G’s.
Select a vector G from the origin to a reciprocal lattice point.

• Reciprocal lattice points near the point O

at the origin of the reciprocal lattice.
• The reciprocal lattice vector 𝐆C connects
points OC; and 𝐆D connects OD.
• Two planes 1 and 2 are drawn which are
the perpendicular bisectors of 𝐆C and
𝐆D , respectively.

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• These planes divide the Fourier space of the crystal into

fragments, as shown in Figure below for a square lattice. The
central square is a primitive cell of the reciprocal lattice. It is a
Wigner-Seitz cell of the reciprocal lattice it call the first
Brillouin zone.

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

The first Brillouin zone is the smallest volume entirely enclosed

by planes that are the perpendicular bisectors of the reciprocal
lattice vectors drawn from the origin.

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

NONCRYSTALLINE SOLIDS
•A noncrystalline solids lack a systematic and regular
arrangement of atoms over relatively large atomic distances.
Sometimes such materials are also called amorphous (meaning
literally “without form”).

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Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

Two-dimensional schemes of the structure of

(a) crystalline silicon dioxide and
(b) (b) noncrystalline silicon dioxide. 43
Kirkuk University - College of Science - Physics Department - 3rd grade
Subject: Material Science Lecture # 9 ‫ الدكتورة روژه برهان الدين عبدالرحمن‬: ‫مدرسة المادة‬

• Metals normally form crystalline solids.

• Some ceramic materials are crystalline, whereas others (the
inorganic glasses) are amorphous.
• Polymers may be completely noncrystalline or semicrystalline
consisting of varying degrees of crystallinity.

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 Thank you for your attention

?
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