M.Sc.

Dissertation Report
Doping induced Dielectric Properties of
Nd1-xSrxCoO3

Date-9th july, 2018

Written and submitted by

Sadddam Hussain

M.Sc. (2nd Year); Batch:2016-18

Class Roll No:-001620702040

Exam Roll No:-MPD1822035

Registration No:-138322 of 2016-17

Department of Physics, Jadavpur University

Guided and Supervised By- Prof.(Dr.) Ruma Ray

Department of Physics, Jadavpur University

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 CERTIFICATE
This is to certify that the project work entitled “Doping Induced
Dielectric Properties of Nd1-xSrxCoO3” is a bonafide work submitted
by Saddam Hussain, M.Sc 2nd yr, bearing Exam-Roll No
:MPD1822035 and Registration No:138322 of 2016-17 of Jadavpur
University, Kolkata, West Bengal as per the requirements specified
by the University for the award of Master of Science (M.Sc) degree
in physics.
This project has been carried out under our supervision during the
academic year of 2017-18.

Prof.Sukhen Das Prof.Debasish Lohar Prof. Ruma Ray

(Project convenor) ( Head ) (Project guide)
Department of physics Department of physics Department of physics
Jadavpur University Jadavpur University Jadavpur University

Kolkata-700032 Kolkata-700032 Kolkata-700032

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3
 contents

TOPICS
1. Introduction
2. Cobaltates
3. Sol-Gel
4. Synthesis of sample
5. Characterization techniques
6. Cluster model for Sr doped cobaltate Nd1-xSrxCoO3
7. Results and discussions
8. Conclusions
9. Acknowledgement
10. References

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 Doping Induced Dielectric Properties of Nd1-xSrxCoO3

1.INTRODUCTION:
The cobaltates with perovskite-type structure have been lately studied
with greater interest because of their specific properties, which make
them promising materials for use in solid oxide fuel cell, chemical
reactors, gas separation membranes and many other applications [1].
Regarding electronic transport properties, the cobaltates, depending on
oxygen content, either belongs to the class of metals with poor
conductivity or semiconductors.

Strontium-doped rare earth cobaltite oxides RE1-xSrx CoO3-δ have been

also studied extensively because of their many potential applications
mentioned above. The crystal structure, electrical and magnetic
properties of these oxides have been studied by many researchers. Sr
doped LaCoO3 in contact with YSZ electrolyte shows high electrical
conductivity [2-5].

Here we choose Nd1-xSrxCoO3 (NSCO) (x=0,0.03,0.06,0.09,0.22) with

NdCoO3 (NCO)as mother sample. These materials exhibit metal
insulator (M-I) transition when Sr content increases [6]. Therefore in
this work we investigate the effect of Sr doping on structural and
dielectric properties of selected materials.

2.Cobaltates:

Cobaltates are the family of materials named after Cobalt which is key
gradient of the compounds. The chemical composition is A1-xRxCoO3
where A= La, Pr, Nd etc (Rare Earth Materials) , R= Ca, Sr, Ba etc (Alkali
Earth Metals).It has a perovskite structure. The ideal case, cubic
perovskite structure is a convenient starting point for the analysis .A
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site = La, Pr, Nd etc B site = Co, Mn, O site = O,A and B site can be
interchangeable for different material and structure.

Fig.1 shows the crystal structure of NdCoO3

3.Sol-Gel:
Sol-Gel is a chemical solution process used to make metal oxides,
ceramics, glass materials in form of thin films or powder. A Sol is a
colloidal ( the dispersed phase is so small that gravitational forces do
not exist , only Van- der waal’s forces and surface charges are present )
or molecular suspension of solid particles of ions in a solvent. A Gel is
semi rigid mass that forms when the solvent from the sol begins to
evaporate and the particles or ions left behind begin to join together in
a continuous network.

6
 Precursors

Hydrolysis

Sol

Heating with water

Gel

Heating

Precursor Powder

Final Heating

Sample

4.Synthesis of Sample:
The polycrystalline Nd1-xSrxCoO3(x=0.03,0.06,0.09,0.22) has been
synthesized by sol-gel method. Neodymium-oxide(Nd2O3), Co-powder,
Strontium-oxide (SrO) and citric acid were taken as a precursors
.Stoichiometric proportions of Nd2O3, SrO and Co powders were
dissolved in an aqueous solution of nitric acid and mixed thoroughly.
Citric acid was then added to the solution to achieve a homogeneous
mixture of metal citrates. The metal citrates were dried and
decomposed at 873 K for 6 h. Finally, the powdered samples were
pressed into pellets and heated at 1073 for 12 h followed by final
annealing at 1273 K for 12 hrs with slow cooling at a rate of 0.7 Kmin−1
[7].
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Nd(NO3)3 Co(NO3)2

Aqueous Solution

Add Sr(NO3)2

Precursor Solution

Add citric acid solution

Final Solution

Dried Sample

Decomposed at 873 K

Pressed into pellet

Heating at 1073 K

Final Annealing At 1273K

Sample Nd1-xSrxCoO3

8
5.Characterization Techniques:
The nano powders were characterized for crystal phase identification
by X-ray diffraction (XRD) .The powder x-ray diffraction was performed
using automated x-ray diffractometer (Burker D8 Advance) with Cu Kα
radiation of wavelength 1.5425Å, operating at voltage 40 Kv and
current 100Ma.The sample were scanned in the angular range from 10
to 70 with scanning the rate 0.0198o/s and step size 0.03o.

To measure the electrical properties, samples were pressed into pellet

of thickness 1-2 mm and of diameter 10 mm under uniaxial pressure.
Silver electrodes were made on both sides of the pellet by using silver
paste and then the pellet was dried for 15 min to get thermal stability.

The frequency dependence of the capacitance, conductance, loss and

impedance of the sample was measured using impedance spectrometer
at the room temperature and in the frequency range 40 to2 MHz, the
oscillation voltage of 500 mv.

6.Cluster model for Sr-doped cobaltateNd1-xSrxCoO3:

The ferroelectric properties are mostly controlled by the relative sizes
of the ions A and B in ABO3 type oxide . The electrical and magnetic
properties are mainly dependent on the electronic con-figuration of
the ions. Dopants and substituents have a profound influence on the
properties of the ABO3 oxides.

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 Primarily due to the fact that in addition to the charge, spin, orbital
and lattice degrees of freedom that interplay in the manganites to
produce effects such as colossal magnetoresistance (CMR), The
cobaltites possess an additional degree of freedom; the Co ion spin-
state. The flexibility in the spin-state adopted by the Co ions is a
consequence of the comparable sizes of the Hund’s rule exchange
energy (Eex) and the crystal field splitting (∆CF) meaning that the low-
spin, intermediate-spin, and high-spin states are accessible to Co3+
ions in undoped cobaltites and Co4+ ions in doped cobaltites . In
addition to this extra spin-state degree of freedom the doped
cobaltites have also received considerable attention because of the
unusual phase competition between long-range ordered
ferromagnetism (F) and spin-glass (SG) or cluster-glass (CG) ground
states. There is a smooth evolution from a SG or CG phase at low
doping to a phase dominated by long range F order at higher doping.
The glassy phase displays a number of unusual features including a
large field cooled magnetization, whereas the parts of the phase space
dominated by F order have been suggested to exhibit anomalous
features more consistent with glassy behavior. This unconventional
magnetic behavior has been interpreted by numerous authors in
terms of an inhomogeneous ground state where hole-rich F ordered
short-range clusters form in a hole-poor insulating matrix.

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 Fig.2
Fig.2 shows schematic representation of the random spin structure of a spin –
glass(top) and the ordered one of a ferromagnet (bottom).

With increasing doping the clusters are supposed to increase in size and
eventually coalesce, resulting in the existence of a long-range ordered
metallic ground state. Recently this “cluster model” has been verified
experimentally by transmission electron microscopy (TEM), Co- nuclear
magnetic resonance (NMR) and small angle neutron scattering (SANS),
providing unequivocal evidence that magnetic phase separation occurs
in these compounds. These various investigations have proven that F
clusters form in the SG/CG phase and are responsible for the large
magnetizations observed. Even in the “F phase” at high doping the
system still possesses a significant phase fraction of low spin and SG/CG
phases, with the various phases competing over the whole doping
range. The crossover at the critical dopant concentration of x=0.18 in
the La1−xSrxCoO3 system is simply the point at which the F ordered
phase begins to dominate over the non-F phases,i.e., the point where F
clusters coalesce and percolation occurs. Partial substitution for A or B
ions may also influence the electrical properties significantly. For
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example in NdCoO3 progressive substitution by strontium (Sr) for
Neodymium gradually imparts a metallic character. This is due to the
creation of Co4+ions at the B site for charge compensation. Because of
its higher charge Co4+ enhances the covalent nature of the B-O
interactions and hence due to profoundly overlapping of electron
orbital between B and O enhances the metallic nature. The B-O
interaction depends on the electronic configuration of A and B ions
which can be controlled by the different doping concentration.

Here in this experiment strontium (Sr) has been doped in NdCoO3 we

get ferrimagnetic doped cobaltite Nd1-xSrxCoO3.we have to analyze and
compare the electrical properties of doped cobaltite Nd1-xSrxCoO3with
undoped cobaltate NdCoO3.

7.Results and Discussions:

a) Structural Properties: XRD studies

The X-ray diffraction patterns of Nd1-xSrxCoO3 are shown in Fig. 3. Each

peaks indicate different (h k l) planes of pure NdCoO3 having single-
phase Orthorhombic structure following JCPDS file (space group pnma).
The dimension (D) of different NSCO samples is estimated by using
Scherrer’s formula [8] given by
𝟎.𝟖𝟗𝝀
𝜷 𝐜𝐨𝐬 𝜽 = + 𝜺 𝐬𝐢𝐧 𝜽…..(1)
𝑫
Where ε is the microstrain, β is full width half maxima (FWHM), λ is the
wavelength of the CuKα radiation.

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 (112)

(024)
(220)
Intensity (a.u.)

(022)
(002)
NdCoO3

Nd0.97Sr0.03CoO3

10 20 30 40 50 60 70
deg 

Fig.3 shows XRD plots for x=0.0 and for x=0.03

From XRD plots , we have fitted each peaks using Lorentz function and
got the FWHM (β) and θ position of each peak. Then we have plotted
βCosθ vs Sinθ and fitted linearly. From this linear fitting we get
𝟎.𝟖𝟗𝛌
intercept (I) which can be equated to . Finally we get the D values
𝐃
i.e particle size for each sample in nm usingλ = 0.15406 nm. Fig.4a and
4b show the βcosθ vs sinθ plots with linear fitting for NCO and NSCO
samples respectively.

b)Doping effect on particle size:

The particle size for x=0.0 is 85.163 nm and for x=0.03 is 129.35 nm
shown in Table 1. It is clear that the particle size increases due to
doping.

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 Table 1:particle size for different doping concentration

Sample Doping Average

concentration(%) ParticleSize(nm)

NdCoO3

0.00 85.163

Nd0.97Sr0.03CoO3

3.00 129.35

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 0.0044
NdCoO3
0.0040

Cos 0.0036

0.0032

Cos
0.0028
Linear fit of Cos

0.20 0.25 0.30 0.35 0.40 0.45 0.50

Sin

Fig.4a shows the Sinθ VS βCosθ plot for NCO

0.0045
Nd0.97Sr0.03CoO3
0.0040
Cos

0.0035

0.0030

0.0025
Cos
Linear fit of Cos
0.0020
0.20 0.25 0.30 0.35 0.40 0.45 0.50

Sin

Fig.4b shows the Sinθ VS βCosθ plot for NSCO

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c) Effect of doping and frequency on dielectric constant:

ε’ is the real part of dielectric constant εR .The working formula for ε’ is

given by
−𝐙" 𝛆𝐑
𝛆′ =
(ꙍ𝐂𝐩 (𝐙′ 𝟐 + 𝐙"𝟐 )
Where Z’ and Z” are the real and imaginary part of the impedance
respectively and εR is the dielectric constant of the sample, ω is angular
frequency, Cp is capacitance (CPE).εR is estimated from the equation
εR= (lCp)/(A ε0) where land Aare thickness and cross-sectional area of
pellet, respectively, ε0 is dielectric constant in vacuum.

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 4
6.0x10
NdCoO3
Nd0.97Sr0.03CoO3

4
4.0x10
R
4
2.0x10

0.0

10 100 1000 10000 100000 1000000

Frequency(Hz)

Fig.5a

4
4x10 NdCoO3
Nd0.97Sr0.03CoO3
4
3x10
'

4
2x10

4
1x10

0
1 2 3 4 5 6
10 10 10 10 10 10

Frequency (Hz)

Fig.5b

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The fig.5a and 5b show the variation of εR and ε’ with frequency for
both x=0.00 and x=0.03. The εR of the NSCO is higher at lower
frequency than that of the NCO .When frequency is increased at first εR
for both decreases rapidly after that it decreases slowly and finally it is
seen that they almost become parallel to each other and also almost
become frequency independent. Dielectric dispersion behavior depicts
that εR decreases rapidly with increasing frequency in the low frequency
region (~ 40Hz) and becomes almost frequency independent beyond
~105Hz. This can be explained by Maxwell-Weigner model [9].
According to this model, dielectric medium consists of a conducting
grains separated by resistive grain boundaries. At low frequency, space
charge polarization and low conductivity of grain boundary are the
main reasons of high εR. In the high frequency range εR decreases as the
dipoles cannot follow the high frequency field and thus lag behind it
[10]. The enhancement in εR with Sr doping may be due to the fact that
Sr2+ ion induces free charge carriers in the system, hence the high
polarisability of conductive particles can be responsible for the increase
in dielectric constant. This enhancement of dielectric constant is
consistent with the increase of both ac and dc conductivity as discussed
later.

ε”is the imaginary part of dielectric constant εR .The working formula

for ε” is given by
𝐙’ 𝛆𝐑
𝛆" =
(ꙍ𝐂𝐩 (𝐙′𝟐 + 𝐙"𝟐 )
Where Z’ and Z” are the real and imaginary part of the impedance
respectively and εR is the dielectric constant of the sample, ω is angular
frequency, Cp is capacitance (CPE).

Fig.6 shows the variation of ε” of Nd1-xSrxCoO3 (x=0.0, 0.03) at room

temperature with frequency in the range 40 Hz – 2 MHz. Here the value
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of ε” for x=0.03 is higher at lower frequency than x=0.0. In addition, ε”
shows the same behaviour as ε’ with frequency.

7
6.0x10

NdCoO3
7 Nd0.97Sr0.03CoO3
4.0x10
"

7
2.0x10

0.0
1 2 3 4 5 6
10 10 10 10 10 10
Frequency (Hz)

Fig.6

d) Effect of doping and frequency on loss :

The figure-7 shows the variation of loss with frequency in the range 40
Hz – 2 MHz for both NCO and NSCO. The loss of NSCO is higher at
lower frequency than the NCO. Loss decreases rapidly with increasing
frequency in lower frequency range. In higher frequency range it
becomes independent of frequency.

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 1400
NdCoO3
Nd0.97Sr0.03CoO3

700
Loss

1 2 3 4 5 6
10 10 10 10 10 10
Frequency (Hz)

Fig.7

e)Effect doping and frequency on conductivity::

The working formula for ac conductivity is given by:

σac =ωεoεRtanδ

where ω is frequency, ε0 is dielectric constant at vacuum, tan δ is

dielectric loss.
The frequency dependence of the conductivity spectra show the two
distinct regimes, within the measured frequency window, 1) plateau
and 2) dispersive regions. The plateau region corresponds to frequency
independent conductivity or known as dc conductivity (σdc). The σdc is
20
obtained on extrapolation to lower frequencies and found to be in good
agreement with the dc conductivity obtained from the impedance
analysis.

The frequency dependence of electrical conductivity is explained by a

simple expression given by Jonscher's power law. The power law relates
the frequency dependent conductivity with dc conductivity as below

σac=σdc+Aωs

where A is a pre-exponential constant, ω is angular frequency and s is

the power law exponent where 0 < s < 1.

The variation of conductivity in the low frequency region may be

attributed to the polarization effects at the grain boundaries. At very
low frequency, more charge accumulation occurs and hence, drop in
conductivity. In the intermediate frequency region, conductivity is
almost found to be frequency independent and equal to dc conductivity
and at the high frequency region, the conductivity increases with
frequency.

σac variation with frequency in the range 40Hz - 2MHz is shown in Fig.8
for NCO and NSCO. For each, σac shows plateau and dispersive regions
clearly. Also, it is seen that σac increases with Sr doping. Inclusion of
Sr2+ions into Nd3+ site leads to increase of charge carriers which
improve in conductivity for NSCO than NCO. In order to that, σdc
increases with doping due to incorporation of Sr2+ into NCO lattice
shown in Table 2.

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 Table2: DC conductivity for different doping concentration:

Sample Doping concentration(%) D.C Conductivity(mho)

NdCoO3

0.00 0.02104

Nd0.97Sr0.03CoO3
3.00 0.136

0.20

Frequency independent
nt
ity de

0.15 conductivity
tiv en
uc dep
co ncy
ac (Sm-1)

ue
nd

NdCoO3
eq

0.10
Fr

Nd0.97Sr0.03CoO3
nt
ity nde
e
uc dep

0.05
nd y
tiv
co enc

Frequency independent
u

conductivity
eq
Fr

2 3 4 5 6
10 10 10 10 10
Frequency (Hz)

Fig.8

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f) Doping effect on impedance:

The complex impedance Z* is defined as ratio of voltage V(t) to current

l(t) in the time domain on applying a sinusoidal signal of low amplitude
across a solid electrolyte. The complex plane is used to represent the
electrical quantities of real (Z’) and imaginary parts(Z”) of complex
impedance (Z*) . The complex impedance for parallel combination of Cg
and Rg is given by

1/Z* = 1/Rg +jωCp

Z*=Z’- jZ”

Z’ = Rg/(1+(ωRgCg)2)

Z” = ωRg2 Cg/ (1+(ωRgCg)2)

The complex impedance for a parallel combination of Rg & Cg represents

a semicircle intersecting the real axis at origin and at a point R g. The
difference between the two intercepts gives the bulk resistance R g of
the material.
The complex impedance of the real solid electrolyte is represented as
[11]

Z*=K(jω)-α
where 0 ≤ α ≤ 1. When α = 0, Z is frequency independent and K is the
resistance R, whereas when α = 1, Z = - jK/ω, the CPE corresponds to

23
capacitance C. The fractional power law dependence on frequency is
referred to as a constant-phase-angle element or non-Debye capacitor.

1200 120
NdCoO3 Nd0.97Sr0.03CoO3
900 90
-Z" ()

-Z" ()
600 60

300 30

0 0
0 500 1000 1500 2000 2500 3000 0 50 100 150 200 250
Z' () Z' ()

Fig.9

Rg

CPE

Fig.10

Fig.9 shows the impedance spectrum for a polycrystalline sample NCO

and NSCO. These semicircles due to the resistance within the grains of
the materials (bulk resistance) and it may also due to the partial or
complete blocking of charge carriers at grains boundaries. From Fig.9, it

24
is seen that -Z” vs Z’ plot of experimental data shows semicircular plot.
Thus we can conclude that the equivalent circuit for NSCO is given by
the parallel combination of CPE (capacitance of grain) and bulk
resistance (Rg) of the interface shown in Fig.10. The grain boundaries
may act as a hindrance to the ionic transport or may also contribute to
the high conduction path due to the presence of large defect density in
the interfacial region. Here we neglect the grain boundaries
contribution to conduction. A typical representation of grain and grain
boundaries are shown in Fig.11.

Fig.11

25
We get from Fig.9, bulk resistance for NCO is 3.002KΩ and NSCO is
2.333 KΩ. Comparing this two value of bulk resistance,wecan say that
due to the Sr dopping the resistance of NSCO decreases and becomes
more conductingthan NCO.

8.Conclusions:

NdCoO3 and Nd0.97Sr0.03CoO3 have been synthesized by sol-gel method.

X-ray diffraction studies of NCO and NSCO confirm orthorhombic
structure without any secondary phase formation. Dielectric studies at
room temperature in the frequency range of 40Hz to 2MHz reveal the
change of dielectric constant with incorporation of Sr2+into NCO lattice.
It is found that the ac conductivity, dielectric constant and loss increase
due to doping. The obtained σdc is in good agreement with the σac .

9.Acknowledgement:
Firstly I would like to express my deepest gratitude to my guide and
supervisor Prof.(Dr.) Ruma Ray. The completion of this project would
not have been possible without her unrestrained guidance and support.
I am very much obliged to Neepamala Giri, Archita Mondal and
Sanchari sarkar,my trainer scholar and my friends palas Mallik, Ashoke
Murmu, Hrak Koley ,who have inspired and helped me in every step of
this project with great patience. And at last, I thank to my parents for
being supportive.

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