Crystallite size strain analysis of nanocrystalline La0.7Sr0.

3MnO3 perovskite by
Williamson-Hall plot method
Dinesh Kumar, Narendra Kumar Verma, Chandra Bhal Singh, and Akhilesh Kumar Singh

Citation: AIP Conference Proceedings 1942, 050024 (2018); doi: 10.1063/1.5028655

View online: https://doi.org/10.1063/1.5028655
View Table of Contents: http://aip.scitation.org/toc/apc/1942/1
Published by the American Institute of Physics
 Crystallite Size and Strain Analysis of Nanocrystalline
La0.7Sr0.3MnO3 Perovskite by Williamson-Hall Plot Method
Dinesh Kumara), Narendra Kumar Vermab), Chandra Bhal Singhc) and Akhilesh
Kumar Singhd)*

School of Materials Science and Technology, Indian Institute of Technology (BHU), Varanasi-221005, India

Corresponding author: a)dineshiitbhu@gmail.com, b) narendraiitbhu@gmail.com, c)cbs.ic81@gmail.com,

d)*
aksingh.mst@iitbhu.ac.in

Abstract. The nanocrystalline Sr-doped LaMnO3 (La0.7Sr0.3MnO3 = LSMO) perovskite manganites having different
crystallite size were synthesized using the nitrate-glycine auto-combustion method. The phase purity of the manganites
was checked by X-ray diffraction (XRD) measurement. The XRD patterns of the sample reveal that La0.7S0.3MnO3
crystallizes into rhombohedral crystal structure with space group R-3c. The size-dependence of structural lattice
parameters have been investigated with the help of Rietveld refinement. The structural parameters increase as a function
of crystallite size. The crystallite-size and internal strain as a function of crystallite-size have been calculated using
Williamson-Hall plot.

Keywords: Perovskite; Manganite; x-ray diffraction; Rietveld analysis; Williamson-Hall plot Method.

INTRODUCTION
In recent years, the size-dependence of structural and physical properties of mixed valence perovskite
manganites have attracted the attention of researchers because the structural and physical properties strongly depend
on crystallite/particle size of the system [1]. The mixed valence La1-xSrxMnO3 perovskite manganites are very
important because it shows colossal magnetoresistance (CMR) along with ferromagnetic ordering [2]. These
manganites can be an essential candidate for hyperthermia diagnostic and treatment applications [3]. The
phenomena of CMR is explained by double exchange interactions between Mn4+ and Mn3+ cations via O2- anion in
the system as suggested by C. Zener in 1951 [4]. The mixed valence perovskite manganites with x = 0.3 show
strongest magnetic properties in which the ratio of Mn4+/Mn3+ is 3/7 [5]. D. H. Manh et al. studied the size
dependent structural properties of La0.7Sr0.3MnO3 manganite with possible application for magnetic hyperthermia
treatment of cancer [3]. Hintze et al. also reported size-induced structural behavior and investigated that
ferromagnetic Curie temperature TC decreases with reducing particle size due to finite size effect and structural
changes resulting in weakening of double exchange interactions [1]. The structural phase transitions in the
perovskite ABO3 can be identified by structural tolerance factor t, (t = dA-O/√2 dB-O) given by Goldschmidt [6]. The
perovskite structure is stable for 0.89 < t < 1.02. Any discrepancy in the value of t from 1 designates to the distortion
in the perovskite structure. According to the ionic radii having structural tolerance factor (t), the crystalline state of
the manganite changes to the rhombohedral structure (0.96 < t < 1) and then to the orthorhombic crystal structure (t
< 0.96), in which the Mn3+-O2--Mn4+ bond angles deform [7]. In the earlier reported papers, the different type of
structures such as cubic, monoclinic, orthorhombic, and rhombohedral have been examined for LSMO compound.
First time R. Bindu in 2004 observed hexagonal structure at room temperature [8]. Crystallite size also affects the
lattice strain in nano samples which in turn affects the properties of nanocrystalline manganites.
In this article, we have studies the size dependent structural behavior of nanocrystalline La0.7Sr0.3MnO3
perovskite manganite synthesized by an auto-combustion method. The structural parameters (unit cell constants, unit

DAE Solid State Physics Symposium 2017

AIP Conf. Proc. 1942, 050024-1–050024-4; https://doi.org/10.1063/1.5028655
Published by AIP Publishing. 978-0-7354-1634-5/$30.00

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cell volume, bond-lengths, bond-angles and tolerance factor) were refined using Rietveld refinement of powder x-
ray diffraction data. Williamson-Hall plot method has been used to estimate the crystallite size and lattice strain.

EXPERIMENTAL DETAILS
The nanocrystalline LSMO with different particle sizes were synthesized using nitrate-glycine auto-combustion
method followed by the calcination process. The stoichiometric amount of La2O3 (Aldrich), SrCO3 (Aldrich) and
Mn(CH3COO)2.4H2O (Aldrich) were used as starting materials. The La2O3 and SrCO3 were dissolved in dilute nitric
acid (dil. HNO3, Hi-media) to form nitrates of the La and Sr, the chemical reactions in the solution can be
represented by equations (1) and (2), respectively:
La2O3+ 6HNO3 Æ 2La(NO3)3 + 3H2O … (1)
SrCO3 + 2HNO3 Æ Sr(NO3)2 + H2O + CO2 … (2)
While the stoichiometric amount of Mn(CH3COO)2.4H2O and glycine were dissolved in de-ionized water. Then,
all the solutions were poured into a single beaker of capacity 3L and put on a magnetic hot plate with constant
stirring at 250°C inside a fume-hood. After 6-8h of continuous stirring auto-ignition occurs, generate an enormous
amount of gasses resulting into blackish-brown powder, the required product. The chemical reaction occurs
according to the reaction given by equation (3):
0.7La(NO3)3 + 0.3Sr(NO3)2 + (CH3COO)2Mn Æ La0.7Sr0.3MnO3 + CO + 3CO2+ 2NH3 + 0.7NO2 + 0.7/2O2 … (3)
The resultant blackish-brown powder was calcined at various temperatures to get pure polycrystalline LSMO
with different crystallite sizes. The room temperature powder XRD patterns were recorded in the 2θ range 20°-120°
with step size 0.02°. The obtained XRD patterns were used to analyze the crystal structure by Rietveld refinement
using FullProf software package [9].

RESULTS AND DISCUSSION

The room temperature powder XRD patterns of LSMO calcined at different temperatures (S1@900°C,
S2@1000°C, S3@1100°C, S4@1200°C and S5@1300°C) are depicted in Figure 1(a). Analysis of the XRD patterns
reveals that LSMO crystallizes in the rhombohedral crystal structure with space group R-3c. In the XRD patterns, no
secondary/impure phase is detected in sample S5, while a small impurity phase less than 2% is detected for other
samples. The inset of Figure 1(a) represents selected Bragg’s reflections (110)/(104) between 32° and 34° for bulk
and nano systems. The Bragg’s peaks (110)/(104) get broadened with decreasing crystallite size from bulk to nano
and shifted towards higher angle side due to decrease in lattice constants. The structural parameters i.e. lattice
constants, atomic coordinates and thermal coefficients, etc. were refined using Rietveld refinement method. In the
process of Rietveld refinement, we choose hexagonal setting for space group R-3c, in which the La/Sr atoms are
occupied at 6a (0, 0, 3/4) position, Mn atoms at 6b (0, 0, 0) and oxygen atoms at 18e (x, y=x, 1/4) positions.
Variation of lattice parameters and unit cell volume as a function of crystallite size is shown in Figure 1(b). The
Rietveld fit for bulk LSMO and molecular structure are shown in Figure 2(a) and 2(b), respectively. The Mn atom in
the LSMO system is coordinated by six oxygen atoms forming MnO6 octahedra as displayed in the inset of Figure
2(a). The MnO6 octahedra between two layers along c-axis are tilted resulting lattice distortion in the system.

FIGURE 1. (a) Room temperature powder x-ray diffraction patterns for La0.7Sr0.3MnO3 calcined at different temperatures. (b)
Variation of lattice parameters and unit cell volume as a function of crystallite-size.

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 FIGURE 2. (a) Rietveld fit for the XRD pattern of La0.7Sr0.3MnO3 calcined at 1300°C (S5). Dots indicate experimental data,
while the calculated pattern is shown by continuous line. The lower curve shows difference between experimental and calculated
XRD patterns. Vertical bars indicate positions of Bragg’s peaks. Inset shows MnO6 octahedra. (b) Ball and stick model of the
system La0.7Sr0.3MnO3 calcined at 1300°C (S5).

The refined lattice constant “a” increases with increasing crystallite size from a = 5.4843(2) Å for 48 nm to a =
5.4927(3) Å for 81nm, while lattice constant “c” enlarges from c = 13.3306(5) Å for 48nm to c = 13.3376(6) Å for
81nm on growth of crystallite size. The unit cell volume increases as a function of crystallite size from 347.23(3) Å3
to 348.49(2) Å3 for crystallite size 48 nm and 81nm, respectively. The unit cell parameters for bulk system are found
to be consistent with the result reported by the earlier authors i.e. a = 5.50742(6) Å, c = 13.3656(2) Å and V =
351.089(7) Å3 [1,3,8]. The average bond length <dLa-O> increases from 2.7402 Å to 2.7433 Å, while <dMn-O>
changes from 1.9455 Å to 1.9470 Å for change in crystallite size 48nm to 81nm, respectively. The calculated value
of structural tolerance factor increases as a function of crystallite size from 0.9959 to 0.9963. The details of the
structural parameters for the synthesized samples are listed in Table 1.

TABLE 1. Structural parameters for La0.7Sr0.3MnO3 system obtained after Rietveld analysis of the XRD patterns

Sample d (nm) a (Å) c (Å) V (Å3) ε χ2 t

-3
S1 48 5.4843(2) 13.3306(5) 347.23(3) 2.45x10 1.73 0.9959
S2 63 5.4870(3) 13.3319(9) 347.61(3) 2.53x10-3 1.74 0.9961
S3 77 5.4896(7) 13.3309(6) 347.93(2) 2.14x10-3 1.75 0.9958
S4 81 5.4927(3) 13.3376(6) 348.49(2) 1.98x10-3 1.91 0.9963
S5 Bulk 5.50742(6) 13.3656(2) 351.089(7) NA 1.51 0.9955

The crystallite sizes of the synthesized samples were calculated using the Williamson-Hall plot method [10]
using the relation (4):
β cosθ = 0.89 λ/d + 4ε sinθ …(4)
where, λ is the wavelength of the X-ray radiation (λ = 1.5406Å), d is crystallite size, θ is Bragg's angle, β is the full
width at half-maximum (FWHM) of the Bragg’s peak, and ε is the internal strain. The crystallite sizes were found to
be 48, 63, 77 and 81 nm for samples S1, S2, S3 and S4, respectively. A representative Williamson-Hall plot for the
sample with crystallite size 48nm is shown in Figure 3(a). The value of internal strain calculated using Williamson-
Hall plot method decreases with increasing crystallite size as shown in Figure 3(b). Figure 4(a-b) shows the
Scanning Electron Microscope (SEM) micrographs for nanocrystalline samples S1 and S4, respectively. The
average particle sizes measured from the micrographs are found to be 120 nm and 450 nm for the samples S1 and
S4, respectively. These results indicate that the particle sizes in each sample are several times larger than the
crystallite size observed by SEM.

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 FIGURE 3. (a) Williamson Hall plot for the sample S1of crystallite size 48 nm, (b) Variation of internal strain as a function of
crystallite size.

FIGURE 4: The SEM micrographs of the samples (a) S1@900°C and (b) S4@1200°C.

CONCLUSIONS
Phase pure nanocrystalline La0.7Sr0.3MnO3 has been synthesized successfully using nitrate-glycine auto-
combustion method followed by calcination process to get different crystallite sizes. Rietveld analysis of the XRD
patterns reveals that LSMO crystallizes in the rhombohedral crystal structure with space group R-3c. The value of
lattice constants increases with increasing crystallite size. The lattice constant “a” varies from a = 5.4843(2) Å for
crystallite size 48 nm to a = 5.4927(3) Å for crystallite size 81 nm, while “c” varies from c = 13.3306(5) Å for
crystallite size 48 nm to c = 13.3376(6) Å for crystallite size 81 nm. The value of internal strain and structural
tolerance factor show strong dependence on crystallite size. The value of internal strain varies from 2.45×10-3 for
crystallite size 48nm to 1.98×10-3 for crystallite size 81nm, while tolerance factor changes from 0.9959 to 0.9963.

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