Journal of Alloys and Compounds 739 (2018) 1048e1058

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Review

Structural, electric, and dielectric characterizations of

La0.5Pr0.2Sr0.3Mn1
xFexO3 perovskite prepared by self combustion
method
Kh. Abdouli a, b, *, W. Cherif a, b, E. Kadri c, Kh. Dhahri c, P.R. Prezas d, M.P.F. Graça d,
M.A. Valent d, L. Ktari b
a
National Engineering School of Sfax (ENIS), Laboratory of Electromechanical Systems (LASEM), B.P.W. 3038, Sfax, Tunisia
b
Sfax University, Faculty of Sciences, B. P. 1171, 3000, Tunisia
c
Laboratory of Applied Physics, Faculty of Science, University of Sfax, B. P. 1171, 3000 Sfax, Tunisia
d
I3N - University of Aveiro, Aveiro, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: Polycrystalline of La0.5Pr0.2Sr0.3Mn(1
x)FexO3 (x ¼ 0, 0.15 and 0.2) samples have been elaborated by the
Received 25 February 2017 self-combustion reaction method. Single-phase compound formation was confirmed by preliminary
Received in revised form X-ray structural analysis. Detailed studies of the electric and dielectric properties of the compound in the
20 June 2017
frequency range from 100 Hz to 1 MHz and temperatures between 100 and 400K were investigated using
Accepted 23 December 2017
Available online 29 December 2017
the impedance spectroscopy technique. The results show that all samples exhibit dependence of both ac
and dc conductivity on the iron content. Furthermore, the values of dielectric loss, dielectric loss tangent,
real and imaginary parts of the impedance, real and imaginary parts of the electrical modulus, ac and dc
Keywords:
Impedance spectroscopy
electrical conductivity were found considerably sensitive to both temperature and applied frequency.
Electric modulus © 2018 Elsevier B.V. All rights reserved.
Self combustion
AC conductivity
DC conductivity

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1048
2. Experimental procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1049
3. Results and discussions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1050
3.1. Structural analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1050
3.2. Conductivity study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1050
3.2.1. DC conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1050
3.2.2. AC conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1053
3.3. Complex impedance spectroscopy analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1053
3.4. Complex modulus analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1055
3.5. Dielectric analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1058
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1058
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1058

1. Introduction

In recent years the scientists have paid much attention to the

synthesis and characterization of manganese oxides materials due
* Corresponding author. National Engineering School of Sfax (ENIS), Laboratory of
Electromechanical Systems (LASEM), B.P.W. 3038, Sfax, Tunisia. to competing interactions which lead to the coupling of charge,
E-mail address: khaledkhaled88@yahoo.com (Kh. Abdouli). spin, orbital and lattice degrees of freedom [1]. This interplay leads

https://doi.org/10.1016/j.jallcom.2017.12.269
0925-8388/© 2018 Elsevier B.V. All rights reserved.
 Kh. Abdouli et al. / Journal of Alloys and Compounds 739 (2018) 1048e1058
Fig. 1. Powder X-ray diffraction pattern of La0.5Pr0.2Sr0.3Mn1
x FexO3 (x ¼ 0.0, 0.15 and 0.2).
to various phenomena like ferroelectricity [2], charge-ordering
[3,4], superconductivity [5], colossal magnetoresistance [6e8], cat-
alytic activity [9] and a multitude of dielectric properties, which are
interesting for basic science as well as for many important potential
applications like microelectronics and telecommunication.
Lanthanum manganite with general formula (LaMnO3) is one of
the most investigated systems [10,11]. The control of the ferro-
magnetic and electric properties of these materials can be achieved
by varying the sintering conditions and by doping with various
cations on both La and Mn sites [12,13]. The doping and substituting
with different types of magnetic ions are a very useful experimental
technique to modify, and enhance the properties of the compound
[14,15]. In this framework, the substitution of manganese in the
Lay(Ca, Sr)1-yMn1-xRxO3 compounds by Ga [16], Ti [16], Cr [17e19]
elements, exhibit rich varieties of electrical properties which were
explained by the double-exchange (DE) mechanism, based on a
strong exchange interaction between Mn3þ and Mn4þ ions [20]. In a
similar way, the substitution of manganese by iron can produce
important modifications in the magnetic and transport properties
of these materials [21,22].
La0.7Sr0.3MnO3 perovskite compound has a relatively high Curie
temperature (TC ¼ 365 K [23]). Potential applications magnetic
refrigeration (MR) and ferroelectric random access memory
(FRAM) [24,25] require having transition temperature TC close to
room temperature. This can be achieved by an appropriate amount
of oxygen stoichiometry [26] or by substitution of La by Pr cation.
1049
The present work summarizes the results of an extensive
study made on the electrical and dielectrical properties
La0.5Pr0.2Sr0.3Mn(1
x)FexO3 using the impedance spectroscopy
technique which is a powerful tool in characterizing the electrical
properties of manganese oxides. Respectively, The variation of sdc
sAC, ε00 , tand, real and imaginary part of the impedance (Z0 and Z00 ),
the equivalent circuit and real and imaginary part of electric
modulus (M0 and M00 ) have been investigated as a function of
frequency and temperature.
2. Experimental procedure
The samples had been prepared by the glycine-nitrate process
(GNP) which is based on the self-combustion of glycine and nitrate
mixture. This process enables the synthesis of perovskite in a very
short time utilizing strong exothermic reactions. It has been
revealed that self-combustion, is a fast, simple, and economical way
of producing nanoscale materials. Stoichiometric amounts of
La(NO3)3,6 H2O, Pr(NO3)3,6 H2O, Sr(NO3)2, Mn(NO3)2,4 H2O,
Fe(NO3)3,9 H2O (~at least 99.995%) in purity and glycine (C2H5NO2),
with a molar ratio of 1 between glycine and nitrate, were used.
Then all nitrates were dissolved in distilled water to form the
precursor solution for La0.5Pr0.2Sr0.3Mn (1
x) FexO3 (x ¼ 0, 0.15 and
0.2) composition. The precursor solution was heating on a hot plate
at about 100  C for 1 h under magnetic stirring. Water was grad-
ually vaporized during heating and formed a transparent viscous
1050 Kh. Abdouli et al. / Journal of Alloys and Compounds 739 (2018) 1048e1058

Table 1 600 and 800  C for 12 h with pressing into pellets form (of about
Refined structural parameters of La0.5Pr0.2Sr0.3Mn1
x FexO3 (x ¼ 0.0, 0.15 and 0.2). 1 mm in thickness) under 4 tonnes/cm2. This preparation was done
Compounds x¼0 x ¼ 0.15 x ¼ 0.2 in the LASEM Laboratory at the University of Sfax.
a (A ) 5.4610 5.4580 5.4734
Phase purity and homogeneity were determined by XRD pattern
b (A ) 7.7476 7.7369 7.7520 which was recorded and refined using a Phillips powder diffracto-
c (A ) 5.5026 5.5015 5.5063 meter PW 1710 with CuKa radiation (l ¼ 1.5405 Å) in a wide range
V (A3) 232.8130 232.3174 232.6312 of Bragg angles (5 2q  105 ) with a step scanning of 0.02 and a
c2 1.69 1.41 1.56
counting time of 5s per step.
For electrical and dielectric measurements the samples were
placed between two parallel plate electrodes. The impedance
gel. When a critical temperature was reached (350  C), the auto- spectroscopy measurements were carried out in the temperature
ignition started, lasting only few seconds combustion and a great range 100e400 K and in the frequency range of 100 Hz-1 MHz
deal of foams produced. The obtained powders were preheated at using an Agilent 4294A Precision Impedance Analyzer in the CpeRp
350  C for about 4 h to remove the remaining organic and configuration During the measurements, the samples were
decompose the nitrates of the gel. These powders were sintered at maintained in a helium atmosphere in order to improve the heat
transfer and eliminate the moisture. The impedance spectroscopy
measurements were performed in Physics Department e I3N,
University of Aveiro (Portugal).

3. Results and discussions

3.1. Structural analysis

Fig. 1 shows the room temperature x-ray diffraction (XRD)

patterns of the La0.5Pr0.2Sr0.3Mn (1
x) FexO3 (x ¼ 0, 0.15 and 0.2)
samples. One can see that the pure perovskite structure has been
successfully formed, and there are no anomalous peaks related to
the precursors. The refinement was carried out using the “pattern
matching” option of Fullprof program. At the end of each refine-
ment, based on reasonably good agreement between observed
(obs) and calculated (cal) inter planar spacing (d), an orthorhombic
crystal system with Pnma space group, was finally selected for each
sample. The refined lattice parameters are also summarized in
Table 1.

3.2. Conductivity study

3.2.1. DC conductivity
Fig. 2-a shows the temperature dependence of electrical con-
ductivity for La0.5Pr0.2Sr0.3Mn1
x FexO3 (x ¼ 0.0, 0.15 and 0.2)
compounds. It is evident from the electrical conductivity plots that

Fig. 2. a: Temperature dependence of dc conductivity (sdc) of La0.5Pr0.2Sr0.3Mn1
x

FexO3 (x ¼ 0.0, 0.15 and 0.2). b: The temperature dependence of the electrical Fig. 3. Dependence of Log (sdc T) on temperature for La0.5Pr0.2Sr0.3Mn1
x FexO3
resistivity r (T) of La0.5Pr0.2Sr0.3Mn1-x FexO3 (x ¼ 0.0, 0.15 and 0.2). (x ¼ 0.0, 0.15 and 0.2).
 Kh. Abdouli et al. / Journal of Alloys and Compounds 739 (2018) 1048e1058 1051

Fig. 4. Frequency dependence of ac conductivity (sac) at various temperatures of La0.5Pr0.2Sr0.3Mn1
x FexO3 (x ¼ 0.0, 0.15 and 0.2).

Fig. 5. Variation of real part of impedance (Z0 ) as a function of frequency (u) of La0.5Pr0.2Sr0.3Mn1
x FexO3 (x ¼ 0.0, 0.15 and 0.2).
1052 Kh. Abdouli et al. / Journal of Alloys and Compounds 739 (2018) 1048e1058
the sample with x ¼ 0.0 exhibit an insulator behavior. When
introducing 15% and 20% of Fe in La0.5Pr0.2Sr0.3Mn1
x FexO3 system,
an insulator-metal (IM) transition is observed.
The decrease of the conductivity with increasing the value of x is
commonly encountered when iron is introduced [27]. This is due to
the fact that when Fe replaces Mn, the electron hopping from Mn3þ
to Fe3þ is prohibited [28e30].
In order to confirm our dc results, the variation of the dc-electrical
resistivity with temperature for the La0.5Pr0.2Sr0.3Mn1
xFexO3
(x ¼ 0.00, 0.15 and 0.20) samples is shown in Fig. 2-b. It is found that
resistivity decreases when increasing temperature. The Sample
x ¼ 0.00 behaves as insulator material.
At low temperature the compounds x ¼ 0.15 and x ¼ 0.20
present an insulating behavior (i.e. dr/dT < 0). With increasing
temperature, the insulator-metal (IM) transition is clearly observed
at temperature Tr, where (dr/dT > 0) for a metallic behavior.
The Value of the electrical transition temperature Tr decreases
from 102 K for x ¼ 0.15e108K for x ¼ 0.20. The decrease in Tr with
Fe doping in our samples should be refer to the decrease of the ratio
Mn3þ/Mn4þ and hence to high probability of encountering anti-
ferromagnetic interactions, which greatly weakens the influence of
double-exchange (DE) interactions [31]. This behavior can be
explained by localization and delocalization of carriers. In fact, at
high temperatures, carriers are thermally activated to their nearest
neighbour site with high mobility. But when temperature
Fig. 6. Variation of imaginary part of impedance (-Z00 ) as a function of frequency (u) of La0.5Pr0.2Sr0.3Mn1
x FexO3 (x ¼ 0.0, 0.15 and 0.2).
decreases, thermally activated behavior decreases and hopping
process dominates, and conduction takes place by hopping of
Charge carriers between the localized states distributed unevenly.
Normally carrier localization changes the conductivity to insulating
and carrier delocalization leads to metal like behavior.
In the hopping process, the carrier mobility is temperature
dependent, which is usually characterized by activation energy. The
activation energies Ea of the dc conduction are obtained from the
slope of ln(s.Τ) vs 1000/T using the Arrhenius equation:



Ea
sdc T ¼ A exp (1)
KB T
where A is the pre-exponential factor, Ea the activation energy, T
the absolute temperature and KB the Boltzmann constant.
The plots of Log(sdc) vs. 1000/T shown in Fig. 3 are linear over a
wide temperature range, confirming a thermally activated polaron
hopping. The activation energy values, increases from 143 to 173
and 198 meV for x ¼ 0.0, 0.15 and 0.2, respectively. The increase of
Ea value with the increase in x is in good agreement with that found
in the work of Rahmouni et al. in which Mn was substituted by Fe
[27] in La0.66Ba0.33MnO3 compound. In fact, when replacing Mn3þ
by Fe3þ in La0.5Pr0.2Sr0.3MnO3 manganites, the Mn3þ-O-Mn4þ
network is perturbed. Then, the available sites for hopping are
reduced.
 Kh. Abdouli et al. / Journal of Alloys and Compounds 739 (2018) 1048e1058 1053

3.2.2. AC conductivity increase of concentration decreases the concentration of intrinsic

The study of frequency dependent conductivity is a well donors. Thus hopping between Mn3þ and Fe3þ is not so ease at
established method for characterizing the hopping dynamics of the higher concentration of Fe. In other words Fe doping ceases
charge carrier/ions. Fig. 4 shows the Log s versus Log u plots at hopping mechanism and hence results in a decrease in the AC
different temperatures. The plots are characterized by two distinct electrical conductivity with increase of Fe concentration.
regimes, exhibiting the typical behavior of ionic material, the low
frequency plateau region and the high frequency dispersion region.
The observed behavior is in agreement with the prediction of the 3.3. Complex impedance spectroscopy analysis
jump relaxation model [32].
The plateau region corresponds to frequency independent The complex impedance spectroscopy (CIS) is used to charac-
conductivity s0. At dispersion region, the dependence of the elec- terize the electrical properties and conduction mechanism of
trical conductivity with the frequency can be analyzed by Jonsch- different materials [34]. This technique is based on analyzing the
er's Universal power law equation [33]: response of a system to an alternating field, and study the evalu-
ation of impedance and related parameters as a function of
frequency and temperature [35].
sac ðuÞ ¼ sdc þ AðTÞusðTÞ (2)
The impedance is a complex quantity, having both magnitude jZj
and phase angle q expressed are:
where is the dc conductivity due to band conduction, A is the
temperature dependent constant and S is an exponent, generally pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Z 02 þ Z 2
00
less than or equal to unity. jZj ¼ (3)
It is clear that the AC electrical conductivity increases with the

00 
increase in frequency. As frequency increases, hopping between Z
q ¼ tan
1 (4)
charge carriers increases which results an increase in AC con- Z0
ductivity value of all samples. At any frequency, conductivity is
found to decrease with the increase in Fe concentration. The where Z0 and Z00 can be written as:

Fig. 7. Complex impedance plots for La0.5Pr0.2Sr0.3Mn1
x FexO3 (x ¼ 0.0, 0.15 and 0.2) at various temperatures.
1054 Kh. Abdouli et al. / Journal of Alloys and Compounds 739 (2018) 1048e1058

Fig. 8. Equivalent circuit of the Cole Cole plot for La0.5Pr0.2Sr0.3Mn1
x FexO3 (x ¼ 0.0, 0.15and 0.2).

  indicates the presence of space charge polarization [36]. Z0

ap
R2g Qg u cos 2g þ Rg decreases at low frequencies due to the increase in the mobility of
0
Z ¼
  2
  2 charges carriers and a decrease in the density of trapped charges
ap ap
Rg Qg uag cos 2g þ 1 þ Rg Qg uag sin 2g [37]. This plot provides an indication of increasing conduction with
  frequency. The same phenomena of Z0 at lower frequencies was
R
1
a p
þ Qgb uagb cos gb2 observed by Costa et al. [38]. Moreover, Z0 increase when Fe is
gb
þ
! introduced in the system, this result confirms the decreases of
    
agb p 2 agb p 2 conductivity observed in Fig. 4.
Rgb þ Qgb u cos 2

1 a gb þ C u þ Qgb u sin 2
ag b
The variation of imaginary part of the impedance Z00 for x ¼ 0.
x ¼ 0.15 and x ¼ 0.2 as a function of frequency for several
(5)
temperatures of measurement is shown in Fig. 6. The strength and
a p position of the relaxation peak are the most important parameters
00 R2g Qg u sin 2g þ Rg witches characterize this type of spectra. In all the samples, an only

Z ¼  a p 2   2
ap
Rg Qg uag cos 2g þ 1 þ Rg Qg uag sin 2g
 
a p
C u þ Qgb uagb sin gb2
þ ! Table 2
 2
 2  The extract parameters for the circuit elements.
a p a p
Rgb Qgb u gb cos 2

1 a gb
þ C u þ Qgb u gb sin 2
a gb

Compounds x¼0 x ¼ 0.15 x ¼ 0.2

(6) Rg (KU) 20.636 13.655 21.125 E2

C (10
12F) 4.245 90.42 25.68
Fig. 5 depicts the real part of impedance Z0 versus frequency at Rgb (KU) 96.694 44.630 E2 432.380
different temperatures. As seen in this figure Z0 magnitude CPE Q (10
10F) 1.271 0.3365 2.462
abg 0.90 0.91 0.84
decreases with increasing frequency as well as temperature, which
 Kh. Abdouli et al. / Journal of Alloys and Compounds 739 (2018) 1048e1058
one peak Z00 is observed for each temperature. This peak decreases
with frequency and shifts to higher frequency with increasing the
temperature. The centers of such peak [Z00 max] are not in the same
frequency reflecting the non-Debye type of relaxation. Also, we can
note that with increasing the temperature the Z00 peaks broaden,
which suggests a thermal relaxation processes in the system. This
relaxation can be due to the presence of electrons/immobile species
at low temperatures and defects in the higher temperature region
[39]. Similar behavior has been reported for other manganites and
different perovskite systems [40e42].
In order to avoid the ambiguity arising out of the presence of
grain/grain boundary effect at different temperatures typical
impedance plots (imaginary part of complex impedance Z00 versus
real one of complex impedance Z0 ) are plotted for
La0.5Pr0.2Sr0.3Mn1
x FexO3 (x ¼ 0.0, 0.15 and 0.2) compounds at
selected temperatures and over a wide range of frequency As
shown in Fig. 7. All the Nyquist plots are not centered on the real
axis which indicating the departure from the ideal Debye behavior
[34]. All curves represent the grain boundaries corresponding to
low frequencies and the grains corresponding to high frequencies.
The evolution of Z00 ¼ f (Z0 ) curves for different temperature reflect
the thermal resistance of the material. Indeed, the increase of
temperature is accompanied by an increase in conductivity. In
Fig. 9. Variation of real part of modulus (M0 ) as a function of frequency (u) at different temperatures for La0.5Pr0.2Sr0.3Mn1
x FexO3 (x ¼ 0.0, 0.15 and 0.2).
1055
order to analyze the impedance spectrum, it is useful to have an
equivalent circuit model that provides a realistic representation of
the electrical properties of the respective regions. Fig. 8 shows the
Simulate Nyquist plots with the equivalents circuits elements for
La0.5Pr0.2Sr0.3Mn (1
x) FexO3 (x ¼ 0, 0.15 and 0.2) samples at 120 K.
This circuit is modeled by a combination series of two parallel R-C,
R-CPE circuits, with R the polarization resistance (bulk resistance)
C is the capacitance and CPE the complex element; constant phase
element (capacity of the fractal interface). With (Rg, Rgb) and
(C, CPEgb) are resistance and capacitance of grain and grain
boundaries respectively. The values of the equivalent circuit
element have been listed in Table 2.
3.4. Complex modulus analysis
Pioneered by Macedo et al. [43], the modulus formalism is a
powerful convenient visual monitor to gain an information about
the contribution of the grains, grain boundaries and film/electrodes
effects on the charge transport phenomenon in the polycrystalline
materials such as mechanism of electrical transport, conductivity
relaxation, and ion dynamics as a function of frequency and
temperature in ion conductors. The dielectric modulus is defined as
the inverse of the complex dielectric permittivity ε*.
1056 Kh. Abdouli et al. / Journal of Alloys and Compounds 739 (2018) 1048e1058

Fig. 10. Variation of imaginary part of modulus (M00 ) as a function of frequency (u) at different temperatures for La0.5Pr0.2Sr0.3Mn1
x FexO3 (x ¼ 0.0, 0.15 and 0.2).

Fig. 11. Imaginary part of dielectric constant (ε00 ) versus Logarithm of (u) at different temperatures for La0.5Pr0.2Sr0.3Mn1
x FexO3 (x ¼ 0.0, 0.15 and 0.2).
 Kh. Abdouli et al. / Journal of Alloys and Compounds 739 (2018) 1048e1058 1057

of M0 (approximately zero) in the low frequency region. This

00
0 observation confirms that the electrode polarization makes an
1 ε ð uÞ ε ð uÞ
M * ¼ juC0 Z * ¼ ¼
i * almost negligible contribution towards M0 [48]. M0 shows a
ε* ε* ðuÞ 2 ε ðuÞ 2
continuous dispersion with increasing frequency. This may be due
00
¼ M 0 ðuÞ þ iM ðuÞ to the short-range mobility of charge carriers [49]. In these figures,
(7)
2 3 M0 reaches a constant value (M∞) at high frequencies for all the
Z∞ temperatures. For x ¼ 0 and 0.15 M0 shows relaxation process,
df
¼ M∞ 41
expð
iutÞ $dt 5 which occurs in the materials.
dt
0 Fig. 10 shows the semi-log plot of M00 versus frequency for the
different compositions at different temperatures. The variation of
where C0 is the vacuum capacitance of the cell and ε* is the complex M00 as a function of frequency is characterized by:
permittivity, M∞ ¼ 1/ε∞ is the high frequency asymptotic value of
the real part of the dielectric permittivity and f(t) is the relaxation  The maxima M00 max shifts toward higher frequencies side with
function 0  f(t)  1 [44]. rising temperature, this suggests that the dielectric relaxation is
The relaxation function, in the present case, is taken as the a thermally activated process. This type of effect has been
Kohlraushe WilliamseWatts (KWW) function [45,46] or stretched reported in the modulus spectrum of some ionic conductors
exponential function and it is given by: [50].
 For x ¼ 0, the broadening of the asymmetric peak indicates the
h i
4ðtÞ ¼ exp
ðt=tÞb (8) spread of relaxation times with different time constants, and
hence, relaxation is of non-Debye type
 Clearly resolved two peaks in M00 are observed for x ¼ 0.15 and
where b measures the extent of the non-exponential behavior and t
x ¼ 0.2 indicating the occurrence of two relaxation processes.
is the mean relaxation time. b is a fractional number, and generally
These two peaks are related to the relaxation of ionic conduction
falls in the range, 0.3 < b < 0.7 [47].
of mobile ions and there orientation of dipoles. These two
In these samples, the dependence of the real part of the
relaxation peaks were overlapped gradually at high frequency
dielectric modulus (M0 ) as a function of frequency over a range of
with increasing temperature.
temperature is given in Fig. 9. It is characterized by very low value

Fig. 12. Dielectric loss tangent (Tand) versus Logarithm of (u) at different temperatures for La0.5Pr0.2Sr0.3Mn1
x FexO3 (x ¼ 0.0, 0.15 and 0.2).
1058 Kh. Abdouli et al. / Journal of Alloys and Compounds 739 (2018) 1048e1058
3.5. Dielectric analysis
The complex permittivity formalism has been employed to
reveal significant information about the chemical and physical
behavior of the electrical and dielectric properties, it is expressed
as [51,52]: ε* ¼ ε0 ejε00 , where ε0 and ε00 are the real and imaginary
parts of the dielectric constant, respectively. Usually, the dielectric
permittivity of a material is due to the four types of polarizations
[53]: interfacial, dipolar, atomic and electronic. The contribution
of each type depends either on the frequency and the
temperature.
Fig. 11 shows the frequency dependence, of the imaginary part
of dielectric constant ε00 spectra for x ¼ 0, 0.15 and 0.2 at various
temperatures. The observed increase in ε00 with temperature at
lower frequencies may be due to the dipolar polarization which
facilitates the increase in permittivity [54]. In fact, the dipoles
cannot orient themselves at low temperatures. When the temper-
ature increased, and following thermal movements, the orientation
of dipoles is facilitated which tends to an increase of dielectric
constant value. In the whole explored temperature range and for
different compositions, the dielectric constant decreases with
increasing frequency. The low value of dielectric constant at higher
frequencies is important for extending the material applications
towards photonic and electro-optic [55].
The factor which means the phase difference due to the loss of
energy within the sample at different frequencies is the loss factor
tangent given by Ref. [56]:
. 00 . 00
TanðdÞ ¼ Z0 Z = ¼ ε0 ε
The variation of Tan d with frequency can be seen from Fig. 12.
The dielectric loss increases by increasing temperature at constant
frequency. This behavior can be attributed to the fact that at low
temperatures, the conduction loss is minimal, when the tempera-
ture increases the conduction loss increases due to the increase in
conductivity [57,58]. Furthermore, we can see that, the dielectric
loss found to decrease with increasing frequency. This behavior
may be due, in the high frequency, the charge carriers cannot follow
the electric field.
4. Conclusion
In the present study, we have elaborated La0.5Pr0.2Sr0.3Mn (1
x)
FexO3 (x ¼ 0, 0.15 and 0.2) samples using the self-combustion re-
action which is between the most facile, fast and inexpensive
methods for preparing nanomaterials. Frequency and tempera-
ture dependence of structural, electric, and dielectric properties
have been investigated. Experimental results demonstrated that
introducing iron in La0.5Pr0.2Sr0.3MnO3 system decreases the
electrical conductance since it reduces the population of the
hopping electrons and the number of available hopping sites. In
addition, we can conclude that the activation energy values rise
from Ea ¼ 143 to 173 and 198 meV for x ¼ 0.0, 0.15 and 0.2,
respectively, with the increase of Fe concentration due to the
decrease of the charge carriers. Nyquist plots confirmed the
contributions of grain and grain boundary effect to the conduc-
tivity of the material.
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