The correction of the line profiles for x-ray

diffraction peaks by using three analysis

methods
Cite as: AIP Conference Proceedings 2123, 020044 (2019); https://doi.org/10.1063/1.5116971
Published Online: 17 July 2019

Rasha Munir Chellab, and Khalid Hellal Harbbi

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AIP Conference Proceedings 2123, 020044 (2019); https://doi.org/10.1063/1.5116971 2123, 020044

© 2019 Author(s).
 The Correction of the Line Profiles for X- Ray Diffraction
Peaks by Using Three Analysis Methods
Rasha Munir Chellaba) and Khalid Hellal Harbbi

Department of Physics, College of Education for Pure Science, Ibn Al-Haitham, University of Baghdad, IRAQ
a)
Corresponding author: rashamuner2@gmail.com

Abstract. In this study used three methods such as Williamson- hall, size-strain Plot, and Halder-Wagner to analysis x-
ray diffraction lines to determine the crystallite size and the lattice strain of the nickel oxide nanoparticles and then
compare the results of these methods with two other methods. The results were calculated for each of these methods to
the crystallite size are (0.42554) nm, (1.04462) nm, and (3.60880) nm, and lattice strain are (0.56603), (1.11978), and
(0.64606) respectively were compared with the result of Scherrer method (0.29598) nm,(0.34245),and the Modified
Scherrer (0.97497) . The difference in calculated results Observed for each of these methods in this study.

Keywords: X-ray diffraction, Three analysis methodhs, Williamson- hall , size-strain Plot, and Halder-Wagner .

INTRODUCTION
X-ray diffraction is a convenient method for determining the mean size of nano crystallites in nano crystalline
bulk materials. The first scientist, Paul Scherrer, published his results in a paper that included what became known
as the Scherrer equation in 1918 [1].
It is assumed that if there are N different peaks of a specific nano crystal in the range of 0-180° (2θ) or 0 - 90°
(θ), then all of these N peaks must present identical D values for the crystal size.. Modified Scherrer formula is
based on the face that we must decrease the errors and obtain the average value of D though all the peaks (or any
number of selected peaks) by using least squares method to mathematically decrease the source of errors. If we plot
lnβ against ln(1 /cosθ ), then a straight line with a slope of around one and an intercept of a bout ln K/D must be
obtained. Theoretically this straight line must be with a slope of 45° since tan45°= 1. But, since errors are
associated with experimental data, the least squares method gives the best slope and most accurate ln K/D. After
getting the intercept, then the exponential of the intercept is obtained.[2]
Scherrer-equation follows a 1/cosθ dependency but not tanθ as W-H method. This basic difference was that both
microstructural causes small crystallite size and microstrain occur together from the reflection broadening.
Depending on different θ positions the separation of size and strain broadening analysis is done using Williamson
and Hall. The following results are the addition of the Scherrer equation and ε ≈ βhkl/tanθ [3].
Williamson-Hall plot has illustrated that line broadening was basically isotropic. Due to microstrain contribution
the diffracting domains were isotropic. Size-strain parameters can be obtained from the size-strain plot (SSP). This
has a benefit that less importance is given to data from reflections at high angles. In this estimation, it is assumed
that profile is illustrated by strain profile by a Gaussian function and the crystallite size‖ by Lorentzian function [4].
For the determination of D and ε, Halder and Wagner [5,6] proposed an alternative equation containing the
integral breadth, β*, of the reciprocal lattice point and the latticeplane spacing, d*, for the reciprocal cell.
In the Halder–Wagner (HW) plot, y = (β/tanθ)2 is plotted against x = β/(tanθsinθ). Then, the slope and y
intercept of the resulting straight line afford Kλ/D and 16ε2, respectively. As described in the previous section, the
value of K = 4/3 [7] is believed to be valid on the definition of the crystallite size as the volume-weighted average
one for spherical crystallites.
When used all these methods we can notes the difference values of the obtain crystallite size (D) and the lattice
strain.

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AIP Conf. Proc. 2123, 020044-1–020044-8; https://doi.org/10.1063/1.5116971
Published by AIP Publishing. 978-0-7354-1863-9/$30.00

020044-1
 THEORY

The Scherrer method

Scherrer derived his equation for the ideal condition of a perfectly parallel, infinitely narrow and monochromatic
X-ray beam incident on a monodisperse powder of cube-shaped crystallites [1]. The equation is:

𝛽 (1)
Where:
 D is the mean size of the ordered (crystalline) domains, which may be smaller or equal to the grain size;
 K is a dimensionless shape factor, with a value close to unity. The shape factor has a typical value of about
0.9, but varies with the actual shape of the crystallite;
 λ is the X-ray wavelength ;
 𝛽 is the line broadening at half the maximum intensity (FWHM), after subtracting the instrumental line
broadening, in radians . This quantity is also sometimes denoted as Δ(2θ);
 θ is the Bragg angle
It is important to note that Scherrer’s equation can only be applied for average sizes up to about 100–200 nm
(depending on the instrument, sample and signal-to-noise ratio), because diffraction-peak broadening decreases with
increasing crystallite size and it becomes difficult to separate the peak broadening due to crystallite size from the
broadening due to other factors[8]. The equation (1) used to determine the crystallite size. The lattice strain
determine from the equation (2).
𝜀 (2)

The modified Scherrer method

Scherrer's modified equation can provide the advantage of reducing the sum of absolute values of errors, ∑(±∆
lnβ)2, and producing one line through the points to give one value of the lnKλ/D intersection[9]. By take the
logarithm to the two sides in equation (1), get on equation (3). If we plot the results of lnβ against ln (1/ cos θ).The
straight line with a slope of around one and the intercept of a bout ln K/D must be obtained by equation (4). After
getting the intercept, then the exponential of the intercept is obtained [2].The crystallite size determine by the
equation (5).
𝑙𝑛𝛽 𝑙𝑛 𝑙𝑛 (3)
𝑠𝑙𝑜𝑝𝑒 𝑙𝑛 (4)
𝑒 (5)

The Williamson- Hall method

The Williamson-Hall method is defined as follows (β=4εtanθ). Rewrite the equation as follow equation [10]:
𝛽 𝑐𝑜𝑠𝜃 4𝜀 𝑠𝑖𝑛𝜃 (6)
In this method the crystallite size can be determine by the equation (7). The lattice strain can be determine by the
equation (8).
𝐷 (7)
_
𝜀 = slope (8)

The Size-Strain plot method

According to the Size-Strain plot method, the relation between lattice strain and crystallite size is given by[10]:
𝑑 𝛽 𝑐𝑜𝑠𝜃 𝑑 𝛽 𝑐𝑜𝑠𝜃 (9)

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 In this method used equation (9) to determine the crystallite size and the lattice strain .when the crystallite size is
determine from the slope by the equation (10), and the lattice strain determine from the y-intercept by the equation
(11).
𝐷 = (10)
𝜀 2 𝑦_𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 (11)

The Halder-Wagner method

In Halder-Wagner method, the crystallite size and strain profiles are described by the Lorentzian and the
Gaussian function, respectively. Consequently, we have [10]:
∗ ∗
∗ ∗
(12)
( In this method used equation (12) to determine the crystallite size, and the lattice strain. The crystallite size is
determine from the slope by the equation (13), and the lattice strain determine from the y-intercept by the equation
(14).
∗ ∗
𝐷 ∗ ∗ (13)
𝜀 2 𝑦_𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 (14)
Were 𝛽 ∗ 𝛽 𝑐𝑜𝑠𝜃 ⁄𝜆 , and 𝑑 ∗ 2𝑠𝑖𝑛𝜃 ⁄𝜆

RESULTS AND DISCUSSION

Determination of the full- width at half-maximum (FWHM) and the integral Breadth
( 𝜷𝒉𝒌𝒍

X-ray diffraction lines were analyzed by using analytical program such as (Origin) in this method obtained of the
area under the curve for all the curves to the x-ray diffraction pattern of NiO powder [11] which is shown in figure
(1).

FIGURE 1. X-ray diffraction pattern of NiO powder

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 By using diagram we can determine (FWHM) for the line (111) as shown by the figure (2), then calculate the
integral Breadth. This way used for all the six line (111),(200),(220),(221),(222),and(311),then listed all the results
in table(1).

FIGURE 2. Determined (FWHM)for the line(111)

 
TABLE 1.The values of 2θ and 𝛽 of fitted six Diffraction lines for NiO
hkl 2θ 𝛽
111
36.9921112 0.645745028
200
43.25960275 0.896907591
220
44.92028375 0.41225161
221
62.8813394 0.709581489
222
75.3532463 0.839165831
311
65.42556755 0.229798037

Determination of crystallite size and the lattice strain

Used three method to determine the crystallite size and lattice strain. All these results have been compared with
the Debye Scherrer method and modified Scherrer method.
These all method are:

The Scherrer method

In this method used equation (1) to determine the crystallite size for the six line (111), (200), (220), (221), (222),
and (311). The values was(0.23648 nm),(0.17369 nm),(0.38012 nm),(0.23921 nm), (0.21804 nm) ,and (0.74899 nm)
respectively .The lattice strain determine from the equation (2).Where, the values are
(0.50391),(0.57856),(0.27554),(0.30081),(0.27884), and (0.11707) respectively and the results are listed in table (2).

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 TABLE 2.The values of crystallite size determine by the Scherrer method
hkl D nm ε
111 0.23648 0.50391
200 0.17369 0.57856
220 0.38012 0.27554
221 0.23921 0.30081
222 0.21804 0.27884
311 0.74899 0.11707

The modified Scherrer method

In this method used equation (3) to determine the crystallite size .The Figure (3) used to calculate the slope and
the intercept, when the crystallite size is extracted from the y-intercept by the equation (5).The value was 0.97497
nm.

FIGURE 3. Plot of modified Scherrer method

The Williamson- hall method

In this method used equation (6) to determine the crystallite size and the lattice strain. Figure (4) used to
calculate the slope and the intercept, when the crystallite size is(0.62197 nm) extracted from the y-intercept by the
equation (7) ,and the lattice strain (0.56603) extracted from the slope by the equation (8).

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 FIGURE 4. Plot of Williamson-Hall method

The size-strain plot method

In this method used equation (9) to determine the crystallite size, and the lattice strain. Figure (5) used to
calculate the slope and the intercept, when the crystallite size is(1.04462 nm) extracted from the slope by the
equation (10), and the lattice strain is(1.11978) extracted from the y-intercept by the equation (11).

FIGURE 5. Plot of Size-Strain plot method

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 The Halder -Wagner method

In this method used equation (12) to determine the crystallite size, and the lattice strain .Figure (6) was used to
calculate the slope and the intercept, when the crystallite size is (3.60880 nm) extracted from the slope by the
equation (13), and the lattice strain (0.64606) extracted from the y-intercept by the equation (14).

FIGURE 6. Plot of Halder-Wagner method

All the values of the crystallite size and lattice to the Scherrer, Williamson-Hall, and Size-Strain Plot and Halder-
Wagner methods listed in the table (3).

TABLE 3. The values of crystallite size and lattice strain for the Scherrer method, and the three methods
Scherrer method Williamson-Hall Size-Strain plot method Halder-Wagner method
method
hkl D nm ε D nm ε D nm ε D nm ε
111 0.23648 0.50391 0.62197 0.56603 1.04462 1.11978 3.60880 0.64606
200 0.17369 0.57856
220 0.38012 0.27554
221 0.23921 0.30081
222 0.21804 0.27884
311 0.74899 0.11707

CONCLUSION
Through the results that have been reached to conclude the following:
1- The Debye - Sherrer method is a simple method to calculate particle size and strain but it is a fast method and
used here to compare with other methods and these formula is not expected to be valid for very small crystallite
sizes (<10 nm).

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 2- In the Williamson-Hall method the larger the intercept result the smaller the crystallite size, and the larger the
slope result the larger the microstrain. Intercept with origin means D is infinity or broadening is only due to
microstrain broadening and zero slope means horizontal line with no microstrain or broadening is only due to
crystallite size broadening
3-And the size-strain plot method is the information on microstrain (ε) and the crystallite size (D) of NiO have
been obtained from βhkl and planar spacing dhkl (the distance between adjacent planes in the set (h k l)) by using
size-strain plot (SSP) method. The SSP method is more accurate, especially at higher diffraction angles. Therefore,
the crystallite size and lattice strain of the sample was calculated using the size-strain plot (SSP) method .
4-The Halder-Wagner method the information on microstrain (εH-W) and the crystallite size (DH-W)
of NiO have been obtained from βhkl and planar spacing dhkl (the distance between adjacent planes in the
set (h k l)) by using H-W method. Halder and Wagner have given an approximation to the integral breadth
of a Voigt function and the crystallite size is determined from the slope inverse of the linearly fitted data
and the root of the y-intercept gives the microstrain, respectively. However, we can observe that the H-W
method is more accurate, with most of data points touching the fitting line compete with other methods.
Therefore, one method is more accurate data points of x-y are more touching the fitting line.

ACKNOWLEDGMENTS
I would like to gratefully acknowledge the support of the Department of Physics – College of Education (Ibn Al-
Haitham) – University of Baghdad; it is their efforts and noble contributions which have made this volume a
valuable addition. I wish to express my special gratitude to Supervisor Professor Dr. Khalid Hellal Harbbi and
Assistant Professor Dr. Akram Raheem Jabur Department of Materials Engineering University of Technology, who
originally continuing support, cooperation, and encouragement this would not have become a reality.

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