Kuliah-10

X-Ray Diffraction
Objectives:
1. Students are able to explain how X-ray diffraction works and its basic
principles (C3)
2. Students are able to predict the type of crystal structure of a material in
according to its X-ray diffraction pattern (C3).

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 Topik Bahasan

1. Pendahuluan
2. What is X-ray
3. X-ray Production
4. Basic XRD
5. Applications of X-Ray Diffraction
6. Indexing Pattern
7. Crystallite Size
 1. Pendahuluan
• Material characterization is a central activity of materials science.
• The general approach: to probe the material with a beam of radiation or high-
energy particles.
• X-rays are a form of electromagnetic radiation having a short wavelength (λ≈0.1
nm).
• X-ray diffraction (XRD) is used to obtain structural information about crystalline
solids.
• Useful in biochemistry to solve the 3D structures of complex bio-molecules.
• Bridge between physics, chemistry, and biology.

X-ray diffraction is important for

• Solid-state physics
• Biophysics
• Medical physics
• Chemistry and Biochemistry
 2. What is X-ray
• Beams of electromagnetic radiation
• smaller wavelength than visible light,
• higher energy
• more penetrative
3. X-ray Production
4. Basic XRD
4.1. Specimen Preparation
 4.2. What is X-ray Diffraction (XRD)
• Most useful in the characterization of crystalline
materials; Ceramics, metals, intermetallics,
minerals, inorganic compounds
• rapid and non-destructive techniques
• Provide information on unit cell dimension

Components
• X-ray source
• Device for
restricting
wavelength range
“goniometer”
• Sample holder
• Radiation
detector
• Signal processor
and readout
 4.3. How XRD works: Schematic

• A continuous beam of X-rays

is incident on the crystal
• The diffracted radiation is
very intense in certain
directions - These directions
correspond to constructive
interference from waves
reflected from the layers of
the crystal
• The diffraction pattern is
detected by photographic
film
4.4. Detection Of XRD
4.5. Single Crystal X-
ray Diffraction
• Used to determine
• crystal structure
• orientation
• degree of crystalline
perfection/imperfections
• Sample is illuminated with
monochromatic radiation
• Easier to index and solve the
crystal structure because its
diffraction peak is uniquely
resolved
4.6. X-ray Powder Diffraction
• More appropriately called polycrystalline X-ray
diffraction, because it can also be used for
sintered samples, metal foils, coatings and films,
finished parts, etc.
• Used to determine
• phase composition (commonly called phase
ID)- what phases are present?
• quantitative phase analysis- how much of
each phase is present?
• unit cell lattice parameters, crystal structure
• average crystallite size of nanocrystalline
samples
• crystallite microstrain and texture
• residual stress (residual strain)
 4.7. Bragg’s Law
• The beam reflected from the
lower surface travels farther
than the one reflected from the
upper surface Upper plane
• If the path difference equals
some integral multiple of the lower plane
wavelength, constructive
interference occurs
• Bragg’s Law gives the conditions
for constructive interference
5. Applications of X-Ray Diffraction
 6. Powder Diffraction: Indexing
• Indexing is the process of determining the unit cell parameters from the peak positions. To
index a powder diffraction pattern, it is necessary to assign Miller indices, hkl, to each
peak.
• A diffraction pattern cannot be analyzed until it has been indexed. It is always the first step
in the analysis.
• Unfortunately, it is not just the simple reverse of calculating peak positions from the unit
cell dimensions and wavelength.
• We will show how one can manually index diffraction patterns of high-symmetry
structures. For lower symmetry structures (monoclinic, triclinic) it is usually necessary to
use a computer algorithm. This is called Autoindexing.
• The information in an XRD pattern is a direct result of two things:
1. The size and shape of the unit cells, which determine the relative positions of the
diffraction peaks.
2. Atomic positions within the unit cell, which determine the relative intensities of the
diffraction peaks
 INDEXING A DIFFRACTION PATTERN FROM CUBIC MATERIALS
Bragg’s Law
Substitute plane-spacing equation into Bragg’s law:

Obtain interplanar spacing, dhkl, from the plane THUS

spacing equation:
• In cubic systems, the first XRD peak in the diffraction pattern will be due to diffraction from
planes with the lowest Miller indices
• simple cubic (SC), (100), h2+ k2+ l2 = 1
• body-centered cubic (BCC), (110), h2+ k2+ l2 = 2
• face-centered (FCC), (111), h2+ k2+ l2 = 3
• If the lattice is not primitive certain classes of all hkl peaks will be missing. These are called
systematic absences and we can use them to determine the space group (or at least narrow
down the possibilities).
• Conditions for allowed reflection for cubic lattices:
• Primitive:
• All possible h, k, and l values. Hence h2+ k2+ l2 = 1,2,3,4,5,6,8,9,10,11,12,13,14,16…
• Body-centered:
• reflection is allowed when (h+k+l) is even. Hence h2+ k2+ l2 = 2,4,6,8,10,12,14,16…
• reflection is not allowed (missing peaks) when (h+ k+ l) is odd
• Face-centered:
• reflection is allowed when h, k, and l are either all even or all odd. Hence h2+ k2+ l2 =
3,4,8,11,12,16,19,20,24,27,32…
• no reflection (missing peaks) when h, k, and l are mixed i.e., even and odd
Selection Rules for reflection in Cubic Crystals
 Two Methods of Indexing
1. Mathematical
2. Analytical

Example-1
Step 1: Identify the peaks and their proper 2θ values. 8 peaks for this pattern

Step 2: Determine sin2θ

Step 3. Calculate the ratio sin2θ/sin2θmin and multiply by the appropriate integers

Step 4. Select the result from step 3 that yields h2+ k2+ l2 as a series of integers
Step 5. Compare results with the sequences of h2+ k2+ l2 values to identify the
Bravais lattice

Step 6. Calculate lattice parameters

Analytical Methods
Step 1: Identify the peaks and their proper 2θ values. 8 peaks for this pattern

Step 2: Determine sin2θ

Step 3. Calculate the ratio sin2θ/(integers)

Step 4. Identify the lowest commont quotient from step 3 and identify the
integers to which it corresponds. Let the lowest common quotient be K
Step 5: Devide sin2θ by K for each peak.
This will give you a list of integers
corresponding to h2+ k2+ l2
Step 6: Select the appropriate pattern
h2+ k2+ l2 values and identify the
Bravais lattice

Step 7. Calculate lattice parameters

INDEXING A DIFFRACTION PATTERN FROM NON-CUBIC
MATERIALS
Indexing non-cubic crystal

2 variables

4
Tetragonal System
• In this system, the sin2θ values obey the following relation:
• sin2θ = A (h2+ k2) + C l2
• where A(= λ2/4a2) and C (= λ2/4c2) are constants for any pattern.
• First of all, these constants (A and C) are found which will then disclose the cell
parameters a and c and enable the line indices to be calculated. The value of A is obtained
from the hk0 lines. When l= 0 the above equation becomes:
• sin2θ= A (h2+ k2)
• The permissible values of (h2 + k2) are 1, 2, 4, 5, 8, 9, etc. Therefore, the hk0 lines must
have sin2θ values in the ratio of these integers and A will be some number which is 1, 1/2,
1/4, 1/5, 1/8, 1/9, etc., times the sin2θ values of these lines. C is obtained from the other
lines on the pattern and by the use of the following equation.
• Sin2θ − A (h2+ k2) = C l2
• Differences represented by the left-hand side of the equation are set up, for various
assumed values of h and k, in an attempt to find a consistent set of C l2 values, which must
be in the ratio of 1, 4, 9, 16, etc. Once these values are found, C can be calculated.
Autoindexing

• Manual indexing of cubic unit cells is a reasonably straightforward process.

• Tetragonal, trigonal and hexagonal cells can also be indexed manually with some
experience, but it is not a trivial exercise.
• Generally indexing is done using a computer program. This process is called
autoindexing.
• The input for an autoindexing program is typically:
• The peak positions (ideally 20-30 lines)
• The wavelength
• The uncertainty in the peak positions
• The maximum allowable unit cell volume
Example-2
Step 1 calculate the d spacing Step 2: calculate 1/d2
Step 3
Assume the first peak is (100), so all 1/d2 will
be divided by 0.045

No integers that satisfy cubic crystals

Notes for cubic crystal:
SC : 1,2,3,4,5,6,7,8 ……………….
BCC: 2,4,6,8,10, …………………….
FCC : 3,4,8,11,12,16, ……………..
Step 4 assume the first peak is (100)

If tetragonal:
Now, we assume the 2nd peak is (001) The next step find the common factor
so all 1/d2 will be divided by 0.069 that separates the 2 different peaks.
Assume the first peak is the c axis and
the 2nd peak is a axis

Peak 1

If tetragonal : 1, 2, 4, 5, 8, 9, …… Peak 2
Peak 3

Peak 4
Peak 5
Example-3 for hexagonal
Lattice parameter c X2
 7. Crystallite Size
• Sometimes, crystallite and grain sizes are
considered to be the same.
• It is important to note that a grain consists of
a single material but may be crystalline, or
polycrystalline.
• An individual crystallite consists of a single
phase.
• Crystallite and grain are both single crystals.
• A crystallite is a single crystal in powder
form.
• A grain is a single crystal within a bulk form.
• A particle is also thought of as an
agglomerate; small enough in size to not
consider it as a bulk or thin film but Diffraction pattern based on crystallite size
composed of 2 or more individual
crystallites.
• The size of the crystallite will affect the peak
of X-ray diffraction as illustrate in the
following schematic figure.
 Pengaruh ukuran partikel

Figure 2. Simulated powder X-ray diffraction patterns

Figure 5. Simulated wurtzite CdS powder X-ray diffraction
for wurtzite CdS spherical particles of different sizes
patterns of (bottom) 5 nm particles, (middle) 25 nm
that range from 1 μm to 1 nm. The inset shows the
particles, and (top) a mixture that contains 75% 5 nm
1, 2, and 5 nm XRD patterns on an expanded y-axis
particles and 25% 25 nm particles.
scale for clarity.
Analysis Quantitative in Determination of Crystallite Size
with XRD
• XRD can be used to determine the size of crystal (crystallite size) with phase certain.
• The determination refers to the main peaks of the pattern diffractogram through
approach Debye Scherrer's equation formulated as.

• where D is the crystallite size (nm), K is the Scherrer constant (0.9), 𝜆 is the wavelength
of the X-rays used (Cu: 0.15406 𝑛𝑚), 𝛽 is the Full Width at Half Maximum (𝐹𝑊𝐻𝑀,
radians), and 𝜃 is the peak position (radians).

• The steps for identifying crystal size using XRD are as follows:
1) Step 1: Identify the K value
2) Step 2: Identify the 𝜆 value
3) Step 3: Identify FWHM (β)
 Fig 4. Illustration of half
Fig 3. The peak at the the maximum peak
maximum intensity with intensity.
certain 2θ.

• To determine the value of FWHM (β):

a) Identify the sharpest peak or crystalline area in the
diffraction pattern generated by XRD
b) Determine the value of 2θ at the peak with the max
intensity of the XRD diffraction pattern. Fig 3 shows a
peak at the max intensity with certain 2θ
c) Determine the value of half of the max peak intensity. Fig
4 illustrate half of the max peak intensity
d) Determine the min 2θ value and the max 2θ value at half
the maximum intensity of the peak. Fig 5 illustrates the
min 2θ value and the max 2θ value at half the maximum
intensity.
e) Determine the FWHM (β) value using Equation
Fig 5. Illustration of min 2θ value and the
maximum 2θ value at half the max intensity.
4) Determine the value of 𝑐𝑜𝑠 𝜃 from the value of 2𝜃 value
The steps to determine the value of cos from the value of 2θ are as follows:
a) Divide the value of 2θ by the number 2 thus θ is known
b) Change θ value to 𝑐𝑜𝑠 𝜃
5) After all the values from 1) to 4) are known, the last step is to put these values in Equation
so that the crystal size is obtained.

In short, by performing a curve selection of the diffraction peaks of each plane crystal at
position 2θ, we can see half-peak curve widening value diffraction (FWHM), then with a value
of is put into the equation Scherrer to determine the size crystal.
Crystallinity Index