Ceramics International xxx (xxxx) xxx–xxx

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Tunable structural and electrical impedance properties of pyrochlores based

Nd doped lanthanum zirconate nanoparticles for capacitive applications
⁎
Ghulam M. Mustafa, Shahid Atiq , S. Kumail Abbas, Saira Riaz, Shahzad Naseem
Centre of Excellence in Solid State Physics, University of the Punjab, Lahore 54590, Pakistan

A R T I C L E I N F O A B S T R A C T

Keywords: Pyrochlore structure based compounds have shown valuable interest in practical applications because of their
Pyrochlores structure tunability and stability. In this context, the stability of pyrochlore structure in a particular phase is
Structural morphology quite essential for practical optimization of valuable dielectric and impedance characteristics of rare-earth zir-
Impedance spectroscopy conates. Thus, in the present work, a series of Nd substituted lanthanum zirconates were synthesized to in-
Electrically active regions
vestigate its effect on the structural, morphological, electrical and dielectric properties. Structural analysis
confirmed the formation of sustainable pyrochlore phase in all the samples having space group Fd3m. A drastic
reduction in grain size with Nd substitution was visualized by the images obtained using a field-emission
scanning electron microscope. The electrical impedance spectroscopy was performed to check the frequency
response of the dielectric behaviour, giving tenable information about changes in electrical permittivity due to
Nd substitution. Impedance analysis shows a contribution of grains and grain boundaries in these heterogeneous
zirconate samples. These regions are easily distinguishable in the sense of their electrical conductivity and
impedance characteristics. The conductivity values obtained were lying in the range of nano-Farad predicted
these materials to be used as solid oxide fuel cells.

1. Introduction Pyrochlores are ranked among ternary oxides, represented by the

Fast-increasing demand of energy storage requires the development
of high performance materials. Such materials should come up with
some novel characteristics which can be put up with long-term services
even in severe environments [1]. Properties like ionic conductivity,
magnetic and thermal characteristics should be controlled in such a
way that the performance of a material could be enhanced. Huge
structural flexibility makes pyrochlores a potential candidate to meet
such requirements. Various research groups world-wide have used
these oxides for different purposes, for instance, in thermal barrier
coatings in gas turbines and diesel engines [2,3], high temperature
catalysts [4,5], magnetic devices [6], metal transistors, gas sensors and
immobilization hosts of actinides in nuclear wastes [7]. In addition,
extensive theoretical and experimental studies on electronic as well as
ionic conductivities of pyrochlores have also been conducted [8–10].
Recently, the focus of researchers has been shifted towards the di-
electric properties of pyrochlores [11]. Modern electronic devices re-
quire low power consumption and high switching ability [12,13]. Thus,
high dielectric constant, low loss factor and high switching ability make
such pyrochlores a potential candidate in modern-day electronic tech-
nology.
general formula A2B2O6O′. The space group of ideal pyrochlores is
Fd3m with 8 molecules per unit cell. Here A and B are metal cations
which may be either divalent and pentavalent or trivalent and tetra-
valent, respectively [14]. There are five unique positions called
Wyckoff positions, available for constituent elements: 16c for A-site
cations and 16d for B-site cations, 48f for O and 8a for O′ while fifth 8b
site is unoccupied. Oxygen ions at 8a sites are stable, having tetrahedral
coordination with A-site cations. Whereas, oxygen ions at 48f site move
towards neighboring empty 8b sites; thus, are bound with two A-site
and two B-site cations [15,16]. Pyrochlore structure is stable in wide
range of composition, and their stability, in particular depends upon the
radius ratio of cations at A and B-sites [17]. Several attempts have been
made to tune different properties of pyrochlores through suitable sub-
stitution at A and B-sites [18]. Sohn et al. investigated the catalytic
activities of Ln2B2O7 by substituting Sm, Eu, Gd and Tb at Ln-site and
Ti, and Zr at B-site. It was found that Ln2Zr2O7 showed high catalytic
activity due to low bonding energy of Ln species with Zr [19]. Wuensch
et al. found three orders of magnitude increase in conductivity on
substituting Zr at Ti-site in Y2Ti2O7. Wang et al. comprehensively stu-
died the effect of simultaneous partial substitution of Zn2+ at A as well
as at B-site in Bi2Nb2O7, and observed the effect of this doping on

⁎
Corresponding author.
E-mail address: satiq.cssp@pu.edu.pk (S. Atiq).

http://dx.doi.org/10.1016/j.ceramint.2017.10.172
Received 22 September 2017; Received in revised form 24 October 2017; Accepted 25 October 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Mustafa, G.M., Ceramics International (2017), http://dx.doi.org/10.1016/j.ceramint.2017.10.172
G.M. Mustafa et al.
stability of pyrochlore structure in orthorhombic along with cubic
phase. It was found that when Zn2+ contents at A-site were less than
4 mol%, pyrochlore adopted pure orthorhombic phase. Nevertheless, as
the contents were increased from 4 to 18 mol%, a mixture of orthor-
hombic and cubic pyrochlore was observed. However, on further in-
creasing Zn2+ contents from 18 to 25 mol%, pyrochlore structure
transformed into pure cubic phase. This transformation of pyrochlore
structure from orthorhombic to cubic caused an increase in dielectric
constant by two orders of magnitude [20].
In this paper, our prime focus is to study the variation of internal
structure of La2Zr2O7 with Nd substitution and correlate it with ionic
conductivity and dielectric properties. Nd has three possible oxidation
states 4+, 3+ and 2+, among which the most stable one is 3+. The
ionic radius of Nd3+ is (0.995 Å) while that of La3+ is (1.061 Å). From
literature review, it was observed that the substitution of smaller size
cation at A-site was favorable for ionic conductivity [10]. This sub-
stitution would reduce the cationic radius ratio which in turn induces
the cationic disorder in the crystal structure [21]. This cationic disorder
assists the ionic conduction throughout the crystal structure and makes
these materials a strong candidate to be used as solid electrolyte.
2. Experimental
2.1. Preparation
Nd-doped lanthanum zirconates with nominal composition of
La2−xNdxZr2O7 (x = 0.0, 0.2, 0.4, 0.6 and 2.0) were prepared using
sol–gel auto-combustion technique. In this method, lanthanum nitrate
hexahydrate [La(NO3)3·6H2O, ≥ 99%], neodymium nitrate hexahy-
drate [Nd(NO3)3·6H2O, ≥ 99%] and zirconium nitrate hydrate [Zr
(NO3)4.H2O, ≥ 99%], purchased from Sigma-Aldrich were used as
precursors. Urea [CH4N2O] and glycine [NH2CH2COOH] were used as
fuel agents by adjusting their ratio with metal nitrates as 2:1. Highly
negative combustion heat of urea (−2.98 kcal g−1) and glycine
(−3.24 kcal g−1) made them a better choice as fuel agents as they help
in reducing the combustion temperature [22]. All the reagents were of
analytical grade purity and used without any further purification. In
order to start the synthesis process, stoichiometric amounts of all metal
nitrates were dissolved separately in deionized water to make their
separate solutions. All solutions were then mixed in a beaker to form
100 mL solution which was placed on a hot metal plate with a magnetic
stirrer in it. For the homogeneous mixing of the solution, the speed of
the magnetic stirrer was maintained at 350 rpm with a constant heating
at 95 °C for 2 h. A continuous removal of vapours made the solution
quite thick which led to a xerogel. As the xerogel was formed, the
magnetic stirrer was removed and the temperature was raised up to
200 °C to remove the nitrates. The temperature was further increased to
300 °C gradually, leading to a spontaneous and vigorous exothermic
reaction. After combustion, a white colored ash was obtained which
was then grinded using mortar and pestle to get fine powder. To obtain
a perfect crystal growth and to ensure the phase purity, the powders
were put in ceramic boats and placed in a muffle furnace to calcine the
samples at 1200 °C for 1 h. Subsequently, the powder samples were
pressed into the cylindrical pellets of diameter 10 mm and thickness
1–1.2 mm, using an Apex hydraulic press by applying a force of 30 kN.
2.2. Characterisation
Crystal structure of the calcined samples was determined using a
Bruker D8 Advanced X-ray diffractometer (XRD) employing Cu Kα ra-
diations having wavelength 1.5418 Å. The morphological analysis was
performed using NovaNano SEM-450, field-emission scanning electron
microscope (FESEM) operated at 5 kV. The compositional investigation
was conducted using Oxford Instruments, energy dispersive X-ray
spectroscopic (EDX) analysis. In order to check the response of the
material to external electric field, the dielectric analysis was carried
2
Ceramics International xxx (xxxx) xxx–xxx
(440)
(222)
(400)
(622)
(662)
(511)
(444)
(311)
(842)
(800)
(111)
Intensity (Arb. units)
x = 2.0
x = 0.6
x = 0.4
x = 0.2
x = 0.0
10 20 30 40 50 60 70 80 90
2θ (degree)
Fig. 1. Indexed XRD patterns of La2.0−xNdxZr2.0O7 (x = 0.0, 0.2, 0.4, 0.6 and 2.0)
samples obtained at room temperature.
out. Dielectric analysis of all the compositions La2−xNdxZr2O7 (x = 0.0,
0.2, 0.4, 0.6 and 2.0) was performed using Wayne Kerr Precision
Impedance Analyzer 6500B. For this purpose, the pellets of diameter
10 mm and thickness in the range 1–1.2 mm were made and sintered at
1200 °C for 1 h. All measurements were taken at room temperature in
the frequency range of 20 Hz to 20 M Hz. The sample holder was made
of two copper electrodes and the pellets were sandwiched in between
these electrodes.
3. Results and discussion
3.1. Structural analysis
To confirm the phase formation and crystalline nature of the pre-
pared samples, XRD analysis was carried out. This analysis includes the
indexing of the diffraction patterns, calculation of lattice parameters,
unit cell volume, the crystallite size, X-ray density and the porosity of
the samples. Fig. 1 shows the indexed XRD patterns of La2−xNdxZr2O7
(x = 0.0, 0.2, 0.4, 0.6 and 2.0) ceramics in the 2θ range of 10–85°. The
indexing exhibits that all compositions possess single phase pyrochlore-
type cubic structure. The indexing of the diffracted intensity peaks was
performed using the indexing method of cubic structure as given by
Cullity [23]. The diffraction peaks for x = 0.0 at 2θ values of 28.18°,
32.75°, 35.91°, 47.26°, 56.17°, 58.97°, 69.41°, 76.78° and 79.07° were
indexed corresponding to the planes (222), (400), (311), (440), (622),
(444), (800), (662) and (842), respectively and subsequently matched
with the ICSD card no. 01-071-2363 which confirmed the cubic pyro-
chlore structure with space group Fd3m having lattice constant a =
10.886 Å for parent compound. Attainment of cubic pyrochlore struc-
ture for La2Zr2O7 through sol–gel route with 1 h calcination tempera-
ture shows that it is the most feasible method for synthesis as it has
significantly reduced the calcination time [24]. When Nd was sub-
stituted at La-site, no significant or gradual change in intensity of the
peaks was observed, depicting that the stability of crystalline texture
was prevailing over the whole series of samples. However, a gradual
shift in peak position towards higher angle with Nd-substitution is
observed, as shown in Fig. 2(a). This shift of peak position towards
higher angle indicates a decrease in lattice parameter to 10.834 Å for x
= 0.6, which is attributed to the substitution of smaller sized Nd3+
(0.995 Å) at relatively larger site of La3+ (1.061 Å) [25]. Finally,
Nd2Zr2O7 sample was matched with the ICSD card no. 00-017-0458
having the Fd3m space group for cubic pyrochlore structure with
10.787 Å lattice constant.
The crystallite size of the prepared samples was calculated using
Williamson-Hall (W-H) approach which was given by a simple equation
below [26]:
G.M. Mustafa et al. Ceramics International xxx (xxxx) xxx–xxx

Fig. 2. (a) Shifting of 222 peak for

(a) 0.005 (b) La2.0−xNdxZr2.0O7 (x = 0.0, 0.2, 0.4, 0.6 and 2.0)
x = 0.0 samples, (b) W-H plot for La2Zr2O7 sample.

0.004
Intensity (Arb. units)

x = 0.0

βhklcosθ
0.003 slope = ε = 0.0013
x = 0.0
0.002 Crystallite Size = D = 55.44 nm
x = 0.0

0.001 kλ /D = 0.00250
x = 0.0

0.000
28.0 28.2 28.4 28.6 28.8 29.0 0.8 1.2 1.6 2.0 2.4
2θ (degree) 4sinθ

kλ
βhkl cos θ = + 4ε sin θ
D (1)
where βhkl is the full width at half maximum (FWHM) corresponding to
the diffraction angles 2θ, k is a structure factor which is 0.9 for sphe-
rical symmetry, λ is the wavelength of Cu Kα i.e. 1.5418 Å, D is the
crystallite size and ε is the lattice strain. W-H approach is an appro-
priate technique which includes the strain induced peaks broadening
arising from the crystal imperfection and distortion. An alternative
approach used to calculate the crystallite size is the Scherrer approach.
One of the fundamental difference between these two approaches is the
dependence of crystallite size on different trigonometric functions of
diffraction angle. In Scherrer approach crystallite size varies as 1/ cos θ
while in W-H approach it varies as tan θ . This distinct θ dependencies of
both effects laid the basis for the separation of size and strain broad-
ening in the analysis of W-H approach [26]. To calculate D, a graph is
plotted between along y-axis with 4sinθ along x-axis. The y-intercept
will give the value of D, while ε is calculated from the slope of the linear
fit. The lattice strain calculated from the slope of linear fit is a measure
of the variation of lattice constants arising from the crystal imperfec-
tions such as crystal dislocation. Other sources of crystal strain may
include the grain boundary, contact or sinter stresses and stacking
faults. W-H plot of the parent compound, La2Zr2O7 is shown in
Fig. 2(b). The lattice parameters, crystallite size, unit cell volume and
crystal strain for all samples are summarized in Table 1.
The data obtained from diffraction was also used to calculate X-ray
density (ρx), bulk density (ρb) and porosity of the samples. ρx was cal-
culated using 8M/VNA, where 8 is the formula unit, M is the molecular
weight, V is the unit cell volume and NA is the Avogadro's number. The
ρb was computed from m/V, where m is the mass of the pellet and V is
its volume (V = πr2h). Using X-ray density and bulk density, porosity
was determined by the relation (1- ρb / ρx). The X-ray density and bulk
density were found to increase from 5.896 to 6.004 g/cm3 and 3.635 to
4.524 g/cm3, respectively. The increase in X-ray density is attributed to
the decrease in lattice constant and thus the unit cell volume. However,
the increase in bulk density may be attributed to the grain growth with
Nd-substitution revealing dense morphology of the prepared samples
suitable for electrical measurements. The porosity on the other hand
shows a decreasing trend from 38.35% to 24.65%. The values of ρx, ρb
and porosity are tabulated in Table 1.
3.2. Morphological analysis
The morphological and compositional analysis of pure La2Zr2O7 and
Nd doped La2Zr2O7 samples was performed using field emission scan-
ning electron microscopy (FESEM). All images were taken at a magni-
fication of 100,000 with operating voltage of 5.0 kV, as shown in Fig. 3.
The images revealed that a nominal amount of Nd doping imparts a
drastic variation in microstructure of La2Zr2O7. Fig. 3(a) corresponding
to pure La2Zr2O7, uncovered the homogeneous, well-dispersed and
quite porous grains with diffused grains boundary. These grains were
interconnected and roughly spherical in shape. From this micrograph,
one can also observe the formation of intergranular pores and coales-
cence of grains in the range of 30–128 nm. Fig. 3(b)-(e) confirm the
densification of samples with Nd doping with respect to microstructure
of La2Zr2O7. It is obvious from the micrographs that grains were gra-
dually grown having sharper grain boundaries with the Nd doping at
the La-site. When the Nd contents were increased to 0.2, 0.4 and 0.6
(Fig. 3(b)-(d)), shape of grains was distorted from spherical symmetry,
and an increased average grain size was noted in the range of
142–506 nm. A complete replacement of La with Nd resulted in further
increase in grain size. This increase in grain size is attributed to the
coalescence of small grains into larger ones with Nd substitution. This
coalescence of grains significantly decreases the effective surface area
of the grains which in turn affects the electrical and dielectric properties
the samples. The EDX spectra of all the samples are shown in Fig. 4. It
can be seen that all the samples consist of La, Nd, Zr and O in the same

Table 1
Variation of lattice constant, crystallite size, unit cell volume, X-ray density, bulk density, and porosity of La2.0−xNdxZr2O7 (x = 0.0, 0.2, 0.4, 0.6 and 2.0) samples.

Sample Composition Lattice Parameters Crystallite size Unit cell Volume Crystal X-ray density (g/ Bulk density (g/ Porosity %
La2.0−xNdxZr2O7 (Å) (nm) (Å)3 strain cm3) cm3)

x = 0.0 10.886 55.44 1289.863 1.306 × 5.896 3.635 38.35

10−3
x = 0.2 10.873 50.40 1285.491 1.197 × 5.904 4.246 28.08
10−3
x = 0.4 10.844 48.63 1275.021 1.219 × 5.915 4.368 26.15
10−3
x = 0.6 10.834 47.79 1271.761 1.320 × 5.926 4.671 21.12
10−3
x = 2.0 10.787 40.76 1255.168 1.646 × 6.004 4.524 24.65
10−3

3
G.M. Mustafa et al.
stoichiometric ratio as given by their respective empirical formula and
no impurity element is present in the samples [27]. It is evident from
the Fig. 4 that there is no peak of Nd in the parent compound which
confirms the formation of pure La2Zr2O7. However, as the doping
content increased from x = 0.2 to 0.6, number of peaks corresponding
to Nd start increasing. For x = 2.0 the absence of La peaks confirms
successfully replacement of La with Nd.
3.3. Dielectric spectroscopic study
3.3.1. Complex dielectric constant
In order to probe into frequency dependent variation of real and
imaginary parts of dielectric constant, the pellets were placed between
two copper electrodes. By passing an ac signal, values of parallel ca-
pacitance Cp and parallel resistance Rp were obtained which in turn
were used to calculate the real as well as imaginary part of dielectric
constant. The real part of permittivity was calculated using the relation
[28]:
ε′ = Cp d/ ε0 A (2)
where ε' is the real part of dielectric constant, ε0 is the permittivity of
free space, Cp is the parallel capacitance, d and A are thickness and area
of cross section of the pellet, respectively. All the calculated values of ε'
vs frequency and doping concentration have been plotted in Fig. 5(a)
and (b), respectively. It is obvious from the pattern in Fig. 5(a) that
there is a sharp decrease in ε' with increasing frequency in the low
frequency range. This decrease in real part of dielectric constant is
4
Ceramics International xxx (xxxx) xxx–xxx
Fig. 3. SEM micrographs for La2−xNdxZr2O7 for (a) x
= 0.0, (b) x = 0.2, (c) x = 0.4, (d) x = 0.6, (e) x =
2.0.
attributed to the dielectric relaxation phenomenon [29–31]. It is re-
ported that dielectric constant is caused by different polarization me-
chanisms (i.e. atomic, electronic, orientation and space charge) under
the action of external electric field. All these phenomena have their
specific relaxation time. In the low frequency range, all polarization
mechanisms (i.e. atomic, electronic, orientation and space charge), take
part to contribute in the net polarization. That is why, in the low fre-
quency range dielectric constant show a high value. As the frequency
increases, polarization mechanisms like space charge and orientation
polarizations start to die out. As a result, dielectric constant decreases
with the increase in frequency and ultimately becomes almost fre-
quency independent [29]. This type of behaviour can be described in
terms of polarization mechanisms based on the theories given by
Maxwell and Wagner. According to these theories, the polarization
mechanism inside a heterogeneous material depends upon the existence
of grains and corresponding grain boundaries. Due to perfect crystalline
nature of grains, they are referred to as regions having less resistive
properties while the grain boundaries show high resistance due to in-
terfacial defects. Maxwell-Wagner interfacial polarization occurs at the
grain boundaries due to high charge accumulation. This type of po-
larization is highly frequency dependent. As at low frequencies, the
accumulated charges can be easily tuned according to the polarity of
the applied ac signal. As the frequency increases, these charges do not
find time to relax, the reason why the polarization mechanism freezes at
high frequency yielding low dielectric constant values. Fig. 5(b) also
shows that the response of real dielectric constant varies with the
substitution of Nd ions at La-site. This variation can be attributed to the
G.M. Mustafa et al. Ceramics International xxx (xxxx) xxx–xxx

x = 2.0
Nd
Zr
O Nd Nd Nd
x = 0.6
Zr
La
La Nd
O Nd

x = 0.4
La Zr
O La
Nd Nd

x = 0.2
La Zr
O Nd La
Nd

Zr x = 0.0
La
La La
O La La

0 1 2 3 4 5 6 7 8
Energy (keV)
Fig. 4. EDX spectra of all the elements present in La2−xNdxZr2O7 (x = 0.0, 0.2, 0.4, 0.6
and 2.0).

variation of grain size [32] that was observed from the SEM images in
Fig. 3. The highest value of dielectric constant was achieved with the
Nd2Zr2O7 sample having the largest grain size. This behaviour predicts
an enhanced dipolar orientation which is mainly attributed to mobility
of the charge carriers and their local displacements [32].
Fig. 6(a) shows the imaginary part of dielectric constant which was
calculated using:
ε″ = ε′ tan δ (3)

where, ε" is the imaginary part of dielectric constant and tanδ is the
tangent loss factor. The tangent loss in turn is calculated using:
tan δ = 1/2πfRp Cp (4)

where, Cp and Rp are equivalent parallel capacitance and resistance, Fig. 6. Variation of imaginary part of dielectric constant (ε") with (a) frequency, (b)
respectively. It is clear from Fig. 6(a) and (c) that ε'' and tanδ follow a doping contents (x = 0.0, 0.2, 0.4, 0.6 and 2.0) and (c) tangent loss (tan δ) with fre-
behaviour similar to ε', a usual decreasing behaviour with increasing quency for La2−xNdxZr2O7.
frequency. These results are in accordance with the Koop's phenom-
enological theory which states that the energy losses are high at low
frequency and vice versa. The reason behind this trend is the high re-
sistive nature of grain boundaries at low frequency. Thus, high energy is

Fig. 5. Variation of real part of dielectric constant

with (a) frequency and (b) doping contents of Nd in
La2−xNdxZr2O7 (x = 0.0, 0.2, 0.4, 0.6 and 2.0).

5
G.M. Mustafa et al.
5k (a) x = 0.0 25M
x = 0.2
x = 0.4
4k x = 0.6
20M
x = 2.0
3k 15M
Z" (Ω)
Z' (Ω)
2k 10M
1k 5M
0 0
1 2 3 4 5 6 7 1
Log f
required for hopping of the charge carriers. At the opposite end, the
high frequency region, less resistive grains come into play enabling low
energy for hopping [33]. Furthermore, value of tangent loss depends on
the stoichiometry, concentration of defects and structural homogeneity
of the material [30]. The lowering of intensity peak confirms the re-
duction in defects and impurity with doping concentration, which in
turn is an indication of grain growth, as can be seen by SEM micro-
graphs.
3.3.2. Complex impedance spectroscopy
In order for better elucidation of microstructural electroactive re-
gions in the samples, impedance spectroscopy has been used.
Impedance is actually the total opposition offered by the sample to the
flow of ac current. Fig. 7(a) and (b) show the real and imaginary parts
of impedance as a function of frequency. The decreasing trend of real
impedance can be explained on the basis of material's conductivity. In
low frequency range, high impedance confirms the grain boundary
dominancy in this regime, which decreases with increase of frequency
[34,35]. A further decrease in Z′ with doping contents confirmed grain
growth, as established by SEM images, which enhanced the conducting
behaviour of samples with concentration. The variation of imaginary
part of impedance (Z′′) with log of frequency is plotted in Fig. 7(b). The
spread peak in the low frequency range called the relaxation peak is an
indication of presence of relaxation process in the material as well as its
polycrystalline nature [33]. Since peak height is decreased with doping,
so conclusively, the overall impedance decreases with increasing
doping concentration.
Complex impedance analysis provides us useful information re-
garding electrical (grains and grain boundary) properties [36]. Fig. 8
shows the plot of imaginary part of impedance (Z′′) against its real part
(Z′) also called as Nyquist plot. Complex impedance plot is character-
ized by semicircular arcs describing the contribution of grains, grain
boundaries and electrode effects [35]. The shape and diameter of the
Fig. 8. Nyquist plot of Nd-doped La2−xNdxZr2O7 (x = 0.0, 0.2, 0.4, 0.6 and 2.0).
Ceramics International xxx (xxxx) xxx–xxx
Fig. 7. Variation of (a) real part of impedance (Z'),
(b) x = 0.0
(b) imaginary part of impedance (Z") with frequency
x = 0.2
for all samples with doping contents of Nd in
x = 0.4
x = 0.6
La2−xNdxZr2O7 (x = 0.0, 0.2, 0.4, 0.6 and 2.0).
x = 2.0
2 3 4 5 6 7
Log f
arc confirms the nature of relaxation phenomenon in the material. Each
semi-circular arc is modeled by a parallel combination RC, where R is
the resistance and C is the capacitance. The intercepts of the plot with
real impedance axis gives the value of grains (Rg) while the value of
grains capacitance is calculated from the top most point of the arc
which are tabulated in Table 2. The capacitance values obtained for all
the samples lie in the range of 1.39–7.44 nF which are considered to be
typical values for solid electrolytes [37]. In order to better understand
the electrolytic process for the Nd doped La2Zr2O7, complex modulus
and conductivity studies are also performed.
3.3.3. Complex modulus spectroscopy
Complex Modulus spectroscopy is another powerful approach to
explore the electrical properties of the material and to confirm the re-
laxation process present inside the material. Modulus plots can give
dynamical information regarding the electrical stability of the materials
by analyzing the ion/carrier hopping [38]. These plots are more sen-
sitive towards the bulk properties; thus giving a clear idea about the
electrical properties of such materials. The real and imaginary parts of
complex modulus can be calculated using the following expressions.
M ′ = ε′ / ε′ 2 + ε″ 2 (5)
M ″ = ε″ / ε′ 2 + ε″ 2 (6)
The variation of real part of electric modulus with frequency is
shown in Fig. 9(a). This figure shows low values of M′ at low fre-
quencies for all the samples, but as the frequency increases, the mod-
ulus shows an increasing trend. Such type of behaviour is categorized
under the asymmetric behaviour which is caused by short range mo-
bility of the charge carriers [39]. Fig. 9(b) shows the imaginary mod-
ulus plots showing strong dependence of the M" on concentration as the
peaks positions are shifted towards the high frequency region. The
strong peaks divide the frequency region in two parts i.e. the lower
frequency part and the higher frequency part. The region below the
peak maximum (which is the lower frequency region), shows the mo-
bility of charge carriers at long distances while the other higher fre-
quency region shows the carrier mobility at confined distances [40].
The complex modulus plot of M" vs M' for all compositions is shown
in Fig. 10. The appearance of multiple peaks suggests that impedance
data can be understood in a better way by replotting it in modulus form
[41]. As peak height in complex impedance spectra is proportional to R,
similarly the peak height in complex modulus spectra corresponds to
the reciprocal of capacitance C−1 [42]. The M′′ vs M′ plot shown in
Fig. 10, clearly suggests two overlapping semicircles which indicates
the existence of both grains and grain boundaries in the material. It is
obvious from the graph that height and radius of first semicircle (cor-
responding to grain boundaries) goes on decreasing while that of
second semicircle (corresponding to grains) goes on increasing with the
increase of Nd substitution at the place of La. Since the intercept of the
first semicircle on the M′ axis gives the value of grain boundary
6
G.M. Mustafa et al. Ceramics International xxx (xxxx) xxx–xxx

Table 2
Grain resistance (Rg) and grains capacitance (Cg) of La2.0−xNdxZr2O7 (x = 0.0, 0.2, 0.4, 0.6 and 2.0) samples.

La2.0Zr2O7 La1.8Nd0.2Zr2.0O7 La1.6Nd0.4Zr2.0O7 La1.4Nd0.6Zr2.0O7 Nd2.0Zr2.0O7

Rg (MΩ) 1.2 0.4 4.7 1.6 0.13

Cg (nF) 1.39 1.54 1.86 4.33 7.44

resistance Rgb, thus, the suppression of radii of first semicircle confirms

that grain boundary resistance decreases with substitution. Conse- 0.020
quently, it is inferred that the substitution of smaller radii Nd ions at the
A-site of zirconate family (La2−xNdxZr2O7) pushes them toward con- 0.015
ducting regime [42].
0.010

M''
3.3.4. Conductivity Analysis
The total conductivity of solids is generally calculated using x = 0.0
0.005 x = 0.2
Jonsher's power law
x = 0.4
σtotal = σd . c + AωS (7) x = 0.6
0.000 x = 2.0
where, σd.c is the dc conductivity due to excess electrons. A is the pre-
exponential factor and s is the exponent. The term Aωs is the ac con- 0.00 0.02 0.04 0.06
M'
ductivity. The frequency dependent ac conductivity is calculated using:
Fig. 10. Complex modulus plot for La2−xNdxZr2O7 (x = 0.0, 0.2, 0.4, 0.6 and 2.0).
σa . c = ωε0 ε′ tan δ (8)
where, εₒ is the permittivity of free space, ε' is the real part of dielectric
behaviour in prepared samples and affirmed the cubic pyrochlore
constant, tan δ is the tangent loss and ω is the angular frequency. The
structure of the Nd3+ substituted La2Zr2O7. The analysis of diffraction
variation of ac conductivity with frequency is shown in Fig. 11(a) for all
data proved that lattice parameters and thus the unit cell volume were
compositions. The plot shows that in low frequency range up to 10 kHz,
contracted with Nd3+ substitution. This contraction of lattice constant
the ac conductivity is almost frequency independent, but increases
from 10.886 to 10.787 Å is attributed to the substitution of smaller sized
slowly in frequency range of 10–100 kHz, and this increase becomes
Nd3+ ion at the La3+-site. X-rays density increases from 5.896 for
exponential on further increase in frequency. An additional increase in
La2Zr2O7 to 6.004 g/cm3 for Nd2Zr2O7. Similarly, bulk density is also
conductivity is also observed with substitution which is also observed
found to increase from 3.635 to 4.524 g/cm3. This increase in densities
by Yamamura et al. [43]. They suggest that substitution of smaller size
result in decrement of porosity from 38.35% to 24.65%, which can also
cation at A-site generates the oxygen vacancies in the lattice, at 48f
be seen from SEM micrographs. Morphological analysis confirmed a
positions accompanying the cation disorder and hence increase the
dispersion in grain size from 30 to 506 nm with the densification of the
conductivity, which is consistent with the results in this work. Clearly
synthesized samples. Frequency dependent dielectric properties of pure
from Fig. 11(b), as the doping concentration of Nd increases, the con-
and Nd doped La2Zr2O7 were interpreted with the help of Maxwell-
ductivity of the samples increases. Low values for conductivity for
Wagner interfacial polarization. The enhancement of ac conductivity
La2Zr2O7 is obtained because of the possible complete occupation of the
with frequency and substitution is also confirmed. This enhancement of
48f site by the oxygen atoms. With decreasing the ionic radius at A-site
ac conductivity was correlated with oxygen vacancies generated at 48f
of the pyrochlore structure, some vacancies at 48f site occur and 8b site
Wykoff position and defect associated. The shift of relaxation peaks in tan
is partially filled [43]. This will generate cation disordering while in-
δ plot is also associated with evolution of oxygen vacancies. Modulus
creasing the oxide ion conductivity.
analysis established that hopping mechanism is responsible for electrical
transport process in the system.
4. Conclusion

A series of Nd doped La2Zr2O7 was synthesized using sol–gel auto- Acknowledgement

combustion route to investigate the effect of Nd substitution at La-site on
its structural characteristics and its consequent effects on morphological, The authors are thankful to Higher Education Commission (HEC) of
dielectric, electrical and impedance spectroscopic properties. Distinct and Pakistan for partially financing this research under HEC project NRPU-
sharp peaks in the X-ray diffraction patterns confirm the crystalline 2471.

Fig. 9. Variation of (a) real part of modulus (M′),

70m x = 0.0 (a) x = 0.0 (b) and (b) imaginary part modulus (M") with fre-
x = 0.2 20m x = 0.2 quency, for all Nd-doped La2−xNdxZr2O7 (x = 0.0,
60m x = 0.4 x = 0.4 0.2, 0.4, 0.6 and 2.0).
x = 0.6 x = 0.6
50m x = 2.0
15m
x = 2.0
40m
10m
M ''
M'

30m
20m 5m
10m
0 0
1 2 3 4 5 6 7 1 2 3 4 5 6 7
Log f Log f

7
G.M. Mustafa et al.
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