Вы находитесь на странице: 1из 8

Ceramics International xxx (xxxx) xxx–xxx

Contents lists available at ScienceDirect

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


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

(440)
(222)
(400)

(622)
stability of pyrochlore structure in orthorhombic along with cubic

(662)
(511)

(444)
(311)

(842)
(800)
(111)
phase. It was found that when Zn2+ contents at A-site were less than

Intensity (Arb. units)


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

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

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

4
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. Ceramics International xxx (xxxx) xxx–xxx

Fig. 7. Variation of (a) real part of impedance (Z'),


5k (a) x = 0.0 25M (b) x = 0.0
(b) imaginary part of impedance (Z") with frequency
x = 0.2 x = 0.2
for all samples with doping contents of Nd in
x = 0.4 x = 0.4
4k x = 0.6
20M x = 0.6
La2−xNdxZr2O7 (x = 0.0, 0.2, 0.4, 0.6 and 2.0).

x = 2.0 x = 2.0
3k 15M

Z" (Ω)
Z' (Ω)

2k 10M

1k 5M

0 0
1 2 3 4 5 6 7 1 2 3 4 5 6 7
Log f Log f

required for hopping of the charge carriers. At the opposite end, the arc confirms the nature of relaxation phenomenon in the material. Each
high frequency region, less resistive grains come into play enabling low semi-circular arc is modeled by a parallel combination RC, where R is
energy for hopping [33]. Furthermore, value of tangent loss depends on the resistance and C is the capacitance. The intercepts of the plot with
the stoichiometry, concentration of defects and structural homogeneity real impedance axis gives the value of grains (Rg) while the value of
of the material [30]. The lowering of intensity peak confirms the re- grains capacitance is calculated from the top most point of the arc
duction in defects and impurity with doping concentration, which in which are tabulated in Table 2. The capacitance values obtained for all
turn is an indication of grain growth, as can be seen by SEM micro- the samples lie in the range of 1.39–7.44 nF which are considered to be
graphs. 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.
3.3.2. Complex impedance spectroscopy
In order for better elucidation of microstructural electroactive re-
gions in the samples, impedance spectroscopy has been used. 3.3.3. Complex modulus spectroscopy
Impedance is actually the total opposition offered by the sample to the Complex Modulus spectroscopy is another powerful approach to
flow of ac current. Fig. 7(a) and (b) show the real and imaginary parts explore the electrical properties of the material and to confirm the re-
of impedance as a function of frequency. The decreasing trend of real laxation process present inside the material. Modulus plots can give
impedance can be explained on the basis of material's conductivity. In dynamical information regarding the electrical stability of the materials
low frequency range, high impedance confirms the grain boundary by analyzing the ion/carrier hopping [38]. These plots are more sen-
dominancy in this regime, which decreases with increase of frequency sitive towards the bulk properties; thus giving a clear idea about the
[34,35]. A further decrease in Z′ with doping contents confirmed grain electrical properties of such materials. The real and imaginary parts of
growth, as established by SEM images, which enhanced the conducting complex modulus can be calculated using the following expressions.
behaviour of samples with concentration. The variation of imaginary M ′ = ε′ / ε′ 2 + ε″ 2 (5)
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 M ″ = ε″ / ε′ 2 + ε″ 2 (6)
indication of presence of relaxation process in the material as well as its
polycrystalline nature [33]. Since peak height is decreased with doping, The variation of real part of electric modulus with frequency is
so conclusively, the overall impedance decreases with increasing shown in Fig. 9(a). This figure shows low values of M′ at low fre-
doping concentration. quencies for all the samples, but as the frequency increases, the mod-
Complex impedance analysis provides us useful information re- ulus shows an increasing trend. Such type of behaviour is categorized
garding electrical (grains and grain boundary) properties [36]. Fig. 8 under the asymmetric behaviour which is caused by short range mo-
shows the plot of imaginary part of impedance (Z′′) against its real part bility of the charge carriers [39]. Fig. 9(b) shows the imaginary mod-
(Z′) also called as Nyquist plot. Complex impedance plot is character- ulus plots showing strong dependence of the M" on concentration as the
ized by semicircular arcs describing the contribution of grains, grain peaks positions are shifted towards the high frequency region. The
boundaries and electrode effects [35]. The shape and diameter of 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
Fig. 8. Nyquist plot of Nd-doped La2−xNdxZr2O7 (x = 0.0, 0.2, 0.4, 0.6 and 2.0).
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. Ceramics International xxx (xxxx) xxx–xxx

Fig. 11. Variation in ac conductivity with (a) fre-


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

References [22] A.B. Salunkhe, V.M. Khot, M.R. Phadatare, S.H. Pawar, Combustion synthesis of
cobalt ferrite nanoparticles influence of fuel to oxidizer ratio, J. Alloy. Compd. 514
(2012) 91–96.
[1] M.K. Elizabeth, T.K. Susan, Bismuth pyrochlore thin films for dielectric energy [23] B.D. Cullity, J.W. Weymouth, Elements of X-ray diffraction, Am. J. Phys. 25 (1957)
storage, J. Appl. Phys. 118 (2015) 054101. 394–395.
[2] G. Rekhila, R. Brahimi, Y. Bessekhouad, M. Trari, Physical and photo electro- [24] X. Cheng, Z. Qi, T. Li, G. Zhang, C. Li, H. Zhou, Y. Wang, M. Yin, Infrared phonon
chemical characterizations of the pyrochlore La1.9Ba0.1Sn2O7, Application to chro- modes and dielectric properties of La2Zr2O7 Comparing thin film to bulk material,
mate reduction under solar light, J. Photochem. Photobiol. A 332 (2017) 345–350. Phys. Status Solidi b 249 (2012) 854–857.
[3] G. Giampaoli, Jun Li, A.P. Ramirez, A.W. Sleight, M.A. Subramanian, [25] R.D. Shannon, Revised effective ionic radii and systematic studies of interatomic
Bi2–xCaxIr2O6+y pyrochlore phases: structure and properties with varied Ir oxida- distances in halides and chalcogenides, Acta Crystallogr. 32 (1976) 751–767.
tion state from 3.9+ to 4.3+, Inorg. Chem. 56 (2017) 4706–4715. [26] A.K. Zak, W.H.A. Majid, M.E. Abrishami, R. Yousefi, X-ray analysis of ZnO nano-
[4] Y. Ma, X. Wang, X. You, J. Liu, J. Tian, X. Xu, H. Peng, W. Lui, C. Li, W. Zhou, particles by Williamson–Hall and size–strain plot methods, Solid State Sci. 13
P. Yuan, X. Chen, Nickel‐supported on La2Sn2O7 and La2Zr2O7 pyrochlores for (2011) 251–256.
methane steam reforming: insight into the difference between tin and zirconium in [27] L. Kong, I. Karatchevtseva, D.J. Gregg, M.G. Blackford, R. Holmes, G. Triani, A
the B-site of the compound, Chem. Cat. Chem. 12 (2014) 3366–3376. novel chemical route to prepare La2Zr2O7 pyrochlore, J. Am. Ceram. Soc. 96 (2013)
[5] T. Yuping, X. Qian, W. Zhao, L. Lu, Synthesis and catalytic properties of TiO2/ 935–941.
Nd2Zr2O7 nanocomposites, J. Chin. Ceram. Soc. 41 (2013) 34–37. [28] M. George, S.S. Nair, K.A. Malini, P.A. Joy, M.R. Anantharaman, Finite size effects
[6] H. Zhang, K. Haule, D. Vanderbilt, Metal-insulator transition and topological on the electrical properties of sol–gel synthesized CoFe2O4 powders: deviation from
properties of pyrochlore iridates, Phys. Rev. Lett. 118 (2017) 026404. Maxwell–Wagner theory and evidence of surface polarization effects, J. Phys. D.
[7] J. Zhang, J. Lian, A.F. Fuentes, F. Zhang, M. Lang, F. Lu, R.C. Ewing, Enhanced Appl. Phys. 40 (2007) 1593–1602.
radiation resistance of nanocrystalline pyrochlore Gd2(Ti0.65Zr0.35)2O7, Appl. Phys. [29] S.K. Abbas, S. Atiq, S. Riaz, S. Naseem, Thermally activated variations in con-
Lett. 94 (2009) 243110. ductivity and activation energy in SrMnO3, J. Mater. Sci.-Mater. Electron. 28 (2017)
[8] T. Hagiwara, Y. Hiroshi, H. Nishino, Relationship between oxide-ion conductivity 7171–7176.
and ordering of oxygen vacancy in the Ln2Zr2O7 (Ln = La, Nd, Eu) system having a [30] Z. Ullah, S. Atiq, S. Naseem, Influence of Pb doping on structural, electrical and
pyrochlore composition, Mater. Sci. Eng. 18 (2011) 132003. magnetic properties of Sr-hexaferrites, J. Alloy. Compd. 555 (2013) 263–267.
[9] S. Solomon, A. George, J.K. Thomas, A. John, Preparation, characterization, and [31] T. Hussain, S.A. Siddiqi, S. Atiq, M.S. Awan, Induced modifications in the properties
ionic transport properties of nanoscale Ln2Zr2O7 (Ln = Ce, Pr, Nd, Sm, Gd, Dy, Er, of Sr doped BiFeO3 multiferroics, Prog. Nat. Sci. 23 (2013) 487–492.
and Yb) energy materials, J. Electron. Mater. 44 (2015) 28–37. [32] M.J. Verkerk, B.J. Middelhuis, A.J. Burggraaf, Effect of grain boundaries on the
[10] L. Minervini, R.W. Grimes, K.E. Sickafus, Disorder in pyrochlore oxides, J. Am. conductivity of high purity ZrO2-Y2O3 ceramics, Solid State Ion. 6 (1982) 159–170.
Ceram. Soc. 83 (2000) 1873–1878. [33] A. Khalid, M. Ali, G.M. Mustafa, S. Atiq, S.M. Ramay, A. Mahmood, S. Naseem,
[11] K.N. Woods, T.H. Chiang, P.N. Plassmeyer, M.G. Kast, A.C. Lygo, A.K. Grealish, Structural and dielectric properties of sol–gel synthesized (Mn, Cu) co-doped
S.W. Boettcher, C.J. Page, High-κ lanthanum zirconium oxide thin film dielectrics BiFeO3 ceramics, J. Sol-Gel Sci. Technol. 80 (2016) 814–820.
from aqueous solution precursors, Appl. Mater. Interfaces 9 (2017) 10897–10903. [34] A. Khalid, S. Atiq, S.M. Ramay, A. Mahmood, G.M. Mustafa, S. Riaz, S. Naseem,
[12] M.A. Farid, M.Y. Rafique, M. Irfan, A. Firdous, M. Hasan, Structural, electrical and Magneto-electric characteristics in (Mn, Cu) co-doped BiFeO3 multiferroic nano-
dielectric properties of pyrochlore LaCrZr2-xGexO7 nanospheres, J. Nanosci. particles, J. Mater. Sci.-Mater. Electron. 27 (2016) 8966–8972.
Nanotechnol. 17 (2017) 5740–5744. [35] A. Kaushal, S.M. Olhero, B. Singh, D.P. Fagg, I. Bdikin, J.M.F. Ferreira, Impedance
[13] J. Zhuang, Q.J. Sun, Y. Zhou, S.T. Han, L. Zhou, Y. Yan, H. Peng, S. Venkatesh, analysis of 0.5Ba (Zr0.2Ti0.8)O3–0.5(Ba0.7Ca0.3)TiO3 ceramics consolidated from
W. Wu, R.K.Y. Li, V.A.L. Roy, Solution-processed rare-earth oxide thin films for micro-granules, Ceram. Int. 40 (2014) 10593–10600.
alternative gate dielectric application, Appl. Mater. Interfaces 8 (2016) [36] S. Thakur, R. Rai, I. Bdikin, M.A. Valente, Impedance and modulus spectroscopy
31128–31135. characterization of Tb modified Bi0.8A0.1PbFe0.9Ti0.1O3 ceramics, Mater. Res. 19
[14] A. Chartier, C. Meis, J.P. Crocombette, L.R. Corrales, W.J. Weber, Atomistic mod- (2016) 1–8.
eling of displacement cascades in La2Zr2O7 pyrochlore, Phys. Rev. B 67 (2003) [37] Z.G. Liu, J.H. Ouyang, K.N. Sun, Improvement of electrical conductivity of trivalent
174102. rare-earth cation-doped neodymium zirconate by co-doping gadolinium and ytter-
[15] H. Yamamura, H. Nishino, K. Kakinuma, Relationship between oxide-ion con- bium, Fuel Cells 10 (2010) 1050–1056.
ductivity and dielectric relaxation in the La2Zr2O7 system having pyrochore-type [38] H. Bakkali, M. Dominguez, X. Batlle, A. Labarta, Universality of the electrical
compositions (Ln = Yb, Y, Gd, Eu, Sm, Nd, La), J. Phys. Chem. Solids 69 (2008) transport in granular metals, Sci. Rep. 6 (2016) 29676.
1711–1717. [39] D.A. Vinnik, D.A. Zherebtsov, S.A. Gudkova, R. Niewa, N.S. Zabeivorota,
[16] N. Li, H.Y. Xiao, X.T. Zu, L.M. Wang, R.C. Ewing, J. Lian, F. Gao, First-principles F.V. Podgornov, Broadband impedance spectroscopic characterization of PbTiO3
study of electronic properties of La2Hf2O7 and Gd2Hf2O7, J. Appl. Phys. 102 (2007) crystal grown by spontaneous crystallization from molten oxides, Ceram. Int. 42
063704. (2016) 10787–10792.
[17] F. Lu, M. Nyman, Y. Shen, Z. Dong, G. Wang, F. Zhang, R. Ewing, J. Lian, Ion beam [40] V. Thakur, A. Singh, A.M. Awasthi, L. Singh, Temperature dependent electrical
irradiation-induced amorphization in nano-sized KxLnyTa2O7-v tantalate pyro- transport characteristics of BaTiO3 modified lithium borate glasses, AIP Adv. 5
chlore, MRS Online Proc. Libr. Arch. (2011) 1298. (2015) 087110.
[18] J.M. Pruneda, E. Artacho, First-principles study of structural, elastic, and bonding [41] Sk Anirban, A. Dutta, Dielectric relaxation and charge carrier mechanism in na-
properties of pyrochlores, Phys. Rev. B 72 (2005) 085107. nocrystalline Ce–Dy ionic conductors, RSC Adv. 6 (2016) 49852–49861.
[19] J.M. Sohn, M.R. Kim, S.I. Woo, The catalytic activity and surface characterization of [42] L.S. Lobo, S. Kalainathan, A.R. Kumar, Investigation of electrical studies of spinel
Ln2B2O7 (Ln = Sm, Eu, Gd and Tb; B = Ti or Zr) with pyrochlore structure as novel FeCo2O4 synthesized by sol–gel method, Superlattices Microstruct. 88 (2015)
CH4 combustion catalyst, Catal. Today 83 (2003) 289–297. 116–126.
[20] X. Wang, H. Wang, X. Yao, Structures, phase transformations, and dielectric prop- [43] H. Yamamura, H. Nishino, K. Kakinuma, K. Nomura, Electrical conductivity
erties of pyrochlores containing bismuth, J. Am. Ceram. Soc. 80 (1997) 2745–2748. anomaly around fluorite–pyrochlore phase boundary, Solid State Ion. 158 (2003)
[21] P.J. Wilde, C.R.A. Catlow, Defects and diffusion in pyrochlore structured oxides, 359–365.
Solid State Ion. 112 (1998) 173–183.