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Synthesis, characterization and electrical properties of

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 CHAPTER 7
Apple Academic Press
SYNTHESIS, CHARACTERIZATION,
AND ELECTRICAL PROPERTIES OF
CERIUM OXIDE NANOPARTICLES

Author Copy
PRIYANKA K. P.1, BABITHA K. K.1, SHEENA XAVIER2,
MOHAMMED E. M.2, and THOMAS VARGHESE1*
Department of Physics, Nanoscience Research Centre (NSRC),
1

Nirmala College, Muvattupuzha 686661, Kerala, India

2
Department of Physics, Maharajas College, Ernakulam, Kerala, India
*
Corresponding author. E-mail: nanoncm@gmail.com

CONTENTS

Abstract.......................................................................................................62
7.1 Introduction........................................................................................62
7.2 Experimental......................................................................................63
7.3 Results and Discussion......................................................................64
7.4 Conclusions........................................................................................66
Acknowledgment........................................................................................66
Keywords....................................................................................................67
References...................................................................................................67

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 62 Functionalized Engineering Materials and Their Applications

ABSTRACT

Cerium oxide nanoparticles or nanoceria were synthesized by using cerium

nitrate hexahydrate and ammonium carbonate as precursors. Structural char-
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acterizations were performed by using X-ray diffraction and transmission
electron microscopy. The dielectric properties of cerium oxide have been
studied as a function of frequency and temperature. It is found that dielec-
tric constant and dielectric loss for all temperatures have high values at low
frequencies, which decrease rapidly as frequency increases and attain a
constant value at higher frequencies. The same results were observed for AC
conductivity also. These properties make cerium oxide useful for applica-

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tions in microelectronics and optics.

7.1 INTRODUCTION

CeO2 nanoparticles are of great interest due to their novel properties

and variety of potential applications such as fuel cells, gas sensors, NO
removal, counter electrodes in smart window devices, and humidity
sensors.2–4,14 CeO2 has a high refractive index, strong adhesion, mechan-
ical abrasion, and stability toward high temperature. CeO2 has been devel-
oped as a fuel additive to improve the efficiency of combustion.1 It was
reported that cerium oxide-containing coatings significantly improve the
oxidation and spallation resistance of high-alloy steels in oxidizing envi-
ronments.16 It was suggested that the adsorption of Ce4+ ions on the oxide
grain boundaries hinders grain growth under oxidizing circumstances,
resulting in a better adherence to the substrate due to enhanced plasticity
of the oxide.
In the present work, we report a successful synthesis of cerium oxide
nanoparticles at room temperature, adopting careful control of the reaction
kinetics of aqueous precipitation; structural characterizations were done
by using X-ray powder diffraction (XRD) as well as transmission electron
microscopy (TEM), and dielectric properties of the material have been inves-
tigated as a function of frequency and temperature. The dielectric properties
and AC conductivity of the nanomaterials differ from those of bulk materials
due to increased interfacial atoms or ions and sinking of large amount of
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defects at or near the grain boundaries. Each interface acts as a capacitor,
thereby changing the dielectric values of the material.
 Synthesis, Characterization, and Electrical Properties 63

7.2 EXPERIMENTAL

Cerium nitrate, ammonium carbonate, and EDTA (99.9% purity) were

purchased from Sigma Aldrich Chemicals and were used without further
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purification. Nanosized powders of cerium oxide were prepared by reacting
aqueous solutions of cerium nitrate and ammonium carbonate (0.01 M each)
at room temperature. The precipitate formed was centrifuged, filtered, and
washed with distilled water a number of times, and dried in an oven to get
fine powders of cerium oxide. The precursor is annealed in air at 400°C for
3 h. The scheme of preparation of nanocrystalline CeO2 used in this work has
been presented schematically as shown in Figure 7.1.

Author Copy

FIGURE 7.1  The scheme of preparation of nanoceria by chemical precipitation method.

The structural characteristics of the synthesized CeO2 nanoparticles have

been studied by XRD using Bruker D8 advance X-ray diffractometer (λ =
1.5406 Å) and TEM using TECNAI F30 FEG model instrument operated at
an accelerating voltage of 300 kV. XRD analyses were carried out for the
identification of the crystal phase and the estimation of the average crystal-
lite size. The crystallite size was estimated from the Debye–Scherrer equa-
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tion: t = 0.9 λ/β cos θ; where, λ is the X-ray wavelength, β is the full width at
half maximum of the peak, and θ is the Bragg’s angle.15
 64 Functionalized Engineering Materials and Their Applications

For TEM studies, the CeO2 powder was dispersed in ethanol using an
ultrasonic bath. A drop of suspension was placed on a copper grid coated
with carbon film. After drying, the copper grid containing nanoparticles was
placed on the holder for the imaging process. The powder was then consoli-
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dated in the form of cylindrical pellets of diameter 11 mm and thickness d =
1.2 mm at a pressure of ~7 GPa using a hydraulic press for dielectric studies.
Both the faces of the pellets were coated with air-drying silver paste. Dielec-
tric measurements as a function of frequency in the range from 100 Hz to
10 MHz are measured at various selected temperatures from 303 to 423 K
using a four-probe LCR meter (Wayne Kerr H-6500B model) in conjunction
with a portable furnace and temperature controller (±1 K). The dielectric

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constant was calculated by using the formula έ = Cd/ε0 A, where A is the
surface area and C, the measured capacitance of the pellet. AC conductivity
(σac) is obtained from the data of dielectric constant (έ) and loss (tanδ) using
the relation σac = έε0 ωtanδ, where ε0 is the permittivity of vacuum and ω the
angular frequency.15

7.3  RESULTS AND DISCUSSION

Figure 7.2(a) displays the XRD pattern of the cubic CeO2 samples annealed
at 400°C for 3 h. From XRD patterns, the average size of the particles
corresponding to annealing temperature estimated using Scherrer equation
was 9 nm. The principal d values taken from the JCPDS file No. 75-0076
for CeO2 are in close agreement with the observed d values. Figure 7.2(b)
shows the TEM image of the synthesized CeO2 particles. The particle size
obtained from TEM images is about 10 nm, which is in agreement with the
XRD analyzed value. The TEM image reveals that particles are not exactly
spherical in shape. Selected area electron diffraction is shown in the inset of
Figure 7.2(b), which clearly indicates that the CeO2 nanoparticles are highly
crystalline in nature.
Figure 7.3(a) shows the variation of dielectric constant with frequency
for temperatures from 303 K to 423 K. It can be seen that the real part of
dielectric constant έ for all temperatures has high values at low frequen-
cies which decrease rapidly as frequency increases and attains a constant
value at higher frequencies. In dielectric nanostructured materials, inter-
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faces with large volume fractions contain a large number of defects, such as
dangling bonds, vacancies, vacancy clusters, and microporosities, which can
cause a change of positive and negative space charge distribution in inter-
faces. When subjected to an electric field, these space charges move. When
 Synthesis, Characterization, and Electrical Properties 65

they are trapped by defects, a lot of dipole moments are formed. At low-
frequency region, these dipole moments easily follow the variation of elec-
tric field11 (Rao et al., 1997). So the dielectric loss and hence the dielectric
constant show large values at low frequency. As temperature is increased,
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more and more dipoles are oriented, resulting in an increase in the value of
dielectric constant for a given value of frequency9. At very high-frequency
(MHz) region, the charge carriers would have started to move before the
field reversal occurs and έ falls to a small value at higher frequencies. Space
charge polarization and reversal of the direction of polarization contribute
much to the έ.6

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FIGURE 7.2  (a) XRD pattern and (b) TEM image of CeO2 nanoparticles.

The variation of tanδ with frequency of sample is shown in Figure 7.3(b).

The variation of tanδ is similar to that of έ. In nanomaterials, the inhomogene-
ities present in the interface layers produce an absorption current resulting in
dielectric loss. This absorption current decreases with increase in frequency
of the applied field. The hopping probability per unit time increases with
increase in temperature. Correspondingly, the loss tangent also increases
with increase in temperature.8,10,13 The loss in CeO2 can be explained by
electronic hopping model, which considers the frequency dependence of the
localized charge carriers hopping in a random array of centers. This model
is applicable for materials in which the polarization responds sufficiently
rapidly to the appearance of an electron on any one site so that the transaction
may be said to occur effectively into the final state.7,9 In the high-frequency
region, tanδ becomes almost constant because the electron exchange interac-
tion (hopping) between Ce3+ and Ce4+ cannot follow the alternatives of the
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applied AC electric field beyond a critical frequency.5 Nanoceria with low
values of dielectric constant and loss tangent at higher frequencies is impor-
tant for the fabrication of materials for ferroelectric, photonic, and electro-
optical devices.
 66 Functionalized Engineering Materials and Their Applications

The variation of AC electrical conductivity as a function of frequency of

sample is shown in Figure 7.3(c). At low frequencies, σac has a small value
which increases at higher frequencies. The values are shifted upwards as
the temperature is raised. It is clear from the figure that the conductivity
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increases as frequency is increased conforming small polar on hopping.
When the temperature is increased, there will be easy transition of charge
carriers from valence band to conduction band due to small size of particles
in the sample, and hence conductivity increases.7,12 The high values of σac for
particles with small grain size are a direct confirmation of the theory.

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FIGURE 7.3  Variation of (a) dielectric constant with frequency, (b) tanδ with frequency,
and (c) σac with frequency of CeO2 for temperatures from 303 to 423 K.

7.4 CONCLUSIONS

CeO2 nanoparticles with average size 9 nm were synthesized using chemical

precipitation method. The dielectric properties of CeO2 were determined as a
function of frequency from 100 Hz to 10 MHz for temperatures ranging from
303 K to 423 K. At lower frequency, έ and tanδ have higher values while at
higher frequency, the values reach steady lower values. Similar variation is
observed when the temperature is raised but the values are shifted upwards.
Conductivity increases as frequency is increased conforming small polaron
hopping. It is concluded that the material synthesized by room tempera-
ture chemical precipitation in the nano range shows enhanced dielectric
properties.

ACKNOWLEDGMENT
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The authors are grateful to KSCSTE, Thiruvananthapuram for providing
financial support.
 Synthesis, Characterization, and Electrical Properties 67

KEYWORDS

•• nanoparticles
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•• cerium nitrate
•• dielectric constant
•• frequency
•• conductivity

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REFERENCES

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