Current Applied Physics 11 (2011) 1322e1325

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Current Applied Physics

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Effect of dopant and DC bias potential on dielectric properties of polyvinyl alcohol

(PVA)/PbTiO3 - composite films
Girish M. Joshi a, *, S.M. Khatake a, S. Kaleemulla a, N. Madhusudhana Rao a, Teresa Cuberes b
a
Material Science Division, School of Advanced Sciences, VIT University, Vellore-632014, TN, India
b
Laboratory of Nanotechnology (LNN), University of Castilla-La-Mancha (UCLM), Almadén, Spain

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

Article history: Composite films of Polyvinyl alcohol (PVA) mixed with Lead Titante Oxide (PbTiO3) were prepared.
Received 18 October 2010 Dopant incorporated and DC bias induced electrical parameters were disclosed with respect to pure PVA
Received in revised form film. The results demonstrate dielectric polarization is not only directly proportional to PbTiO3% of
24 March 2011
dopant but also external DC bias potential at 30
C based on Maxwell Wagner theory. Hence these
Accepted 25 March 2011
Available online 1 April 2011
properties highly applicable as super-capacitor film and humidity sensor applications.
Ó 2011 Elsevier B.V. All rights reserved.
Keywords:
Polymer composite film
Dielectric
In and out plane
DC bias potential

1. Introduction dominated by many extrinsic factors like grain boundary, surface

The smart memory alloy made up of ferroelectric ceramic
functions on the principle of piezo-electricity. It exhibit impulse
response by deformation under external electrical or mechanical
field. BaTiO3, PbTiO3, SrTiO3, CaTiO3, CsNO3 belong to the class of
pervoskite material, highly useful for electronics industry due to
dielectric, piezo-electric and ferroelectric properties and sustain-
able at high temperature. Therefore it is used in the area of fabri-
cation of thin film electronic components, tailoring percolative
capacitors and optoelectronic devices [1e3]. The poled crystal of
PbTiO3 in composition with Mg and Nd oxides demonstrate
temperature independent dielectric and piezo-electric properties
applicable to design a device operable at cryogenic conditions [4].
PbTiO3 is having the transition temperature (TC) 490
C and high
value of dielectric constant [5]. The comparative study of PbTiO3
doped ionic entities show effect on its critical radius ratio corre-
lated to shift of transition temperature. The bulk electrical capaci-
tance of PbTiO3 originates from its grain boundaries [6]. Properties
of polycrystalline electro ceramic materials are highly dependent
on micro-structure and the grain boundary properties may be
significantly differ from each other. Also, it is often observed that
the electrical response from a material is not an intrinsic and it is
* Corresponding author. Tel.: þ91 9894566487 (mobile).
E-mail address: girish.joshi@vit.ac.in (G.M. Joshi).
layers and electrodeematerial interface etc [7]. The gas sensitivity
and selectivity response proved by ternary transition metal oxides
(CrTiO3), due to its variation of resistance to reactive gases. Hence,
to increase the range of selectivity of these sensors for desired gas is
achieved by doping suitable ions in the host material at an elevated
temperature [8]. High permittivity ceramics have been traditionally
used to fabricate high voltage capacitors due to their high break
down voltage. However, they suffer poor mechanical strength and
therefore it is neither be exposed to high electrical fields nor
effectively minimized size. Modern research in thin films of metal
oxide Al2O3 (Aluminum Oxide) may provide high dielectric
strength and permittivity. Furthermore, technology has to be
developed for producing such materials at controlled thickness of
capacitors for commercial applications. Hence, an intermediate
approach taken in to account for the synthesis of composite
material, which combines the superior mechanical, break down
and fabrication properties of polymer with excellent thermal and
dielectric properties of ceramic. A composite material would thus
be formed by introducing the fine powder of ceramics in to the
matrix of suitable polymer. Based on the novel properties of PbTiO3
Ferro-ceramic, it was doped by varying percentage weight with
polymer PVA and composite films were synthesized. Polymer PVA
is having unique chemical and physical properties [9,10]. The effect
of molecular weight (MW) on dielectric properties of PVA films was
reported with very interesting experimental conditions. The report
highlight varying molecular weight induced polarization process is

1567-1739/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cap.2011.03.068
 G.M. Joshi et al. / Current Applied Physics 11 (2011) 1322e1325 1323

synthesize composite film in the ratio of 10, 20, and 40% (by
a 300 30
0v weight). Complete dissolution of the mixture (distilled water as
10 v
15 v solvent) obtained at 70
C, for 1 h. Then the mixed solution poured
200 20 v 20
25 v in the petri dish, under controlled evaporation condition for 30 h at
30 v room temperature (30
C). With uniform thickness (20 mm) whitish

Cp (nF)
100 35 v 10
40 v composite films were pilled off.

0 0
2.2. Elelctrical characterization
-100 -10
PVA Composite films were characterized by using Aglient 4282-
A precision LCR meter (diameter 40 mm and 20 mm thickness of the
10 100 1k 10k 100k 1M
film). The relative dielectric constant confirmed by measuring the
Frequency (Hz)
out plane capacitor (Cp) and in plane capacitor (Cs). Inbuilt DC bias
b 250 25 potential was applied in the range of 0e40 V along the 20 Hz to
0v 1 MHz AC frequency, at 30
C [11].
200 10 v 20
15 v
20 v
150 25 v 15 3. Results and discussion

Cp (nF)
30 v
35 v
100 40 v 10
3.1. Dielectric constant (3) of the composite films
50 5
Properties of polymer composite films depend on the solubility
0 0 of dopant concentration and its chemical functionality. However,
10 100 1k 10k 100k 1M
Frequency (Hz)
a 1200 120
c 400 40
1000
0 v
10 v 100
0 v 15 v
10 v 800 20 v
80
300 30 25 v
15 v

Cs (nF)
30 v
20 v 600 35 v 60
25 v 40 v
Cp (nF)

30 v 400 40
200 20
35 v
200 20
40 v
0 0
100 10
-200 -20
10 100 1k 10k 100k 1M
0 0 Frequency (Hz)
10 100 1k 10k
Frequency (Hz)
100k 1M
b 5000 0 v 500
10 v
15 v
Fig. 1. Out plane 3 vs. frequency of (a) 90:10 (b) 80:20 and (c) 60:40 PVA/PbTiO3 4000
20 v
400
composite films. 25 v
3000 30 v 300

Cs (nF)
35 v
40 v
completely based on DC bias potential operated across it. However, 2000 200
lower molecular weight (LMW) of PVA exhibit higher magnitude of
1000 100
dielectric constant and for the high molecular weight (HMW) of
PVA vice versa [11]. 0 0
Therefore, it motivate to select the LMW PVA as host material
10 100 1k 10k 100k 1M
due to its higher dielectric property to synthesize the composite
Frequency (Hz)
films with PbTiO3 dopant, in the ratio of 10, 20, 40% by varying
weight criteria. c 8000 0 v 800
In the present investigation out (perpendicular) and in (parallel) 10 v
plane dielectric constant and dielectric loss of PVA doped PbTiO3 15 v
6000 20 v 600
composite films were studied as function of frequency with DC bias 25 v
potential at 30
C temperature and the electrical magnitudes were 30 v
Cs (nF)

35 v
4000 400
disclosed over 0% doped (Pure PVA film). Further high transition 40 v
temperature induced polarization response is in progress.
2000 200

2. Experimental 0 0

10 100 1k 10k 100k 1M

2.1. Synthesis of composite film
Frequency (Hz)

PVA granules (1700e1800 gm/mole) supplied by SD Fine Chem. Fig. 2. In plane 3 vs. frequency of (a) 90:10, (b) 80:20 and (c) 60:40 PVA/PbTiO3
Mumbai, and PbTiO3 powder (make Aldrich) as dopant used to composite films.
1324 G.M. Joshi et al. / Current Applied Physics 11 (2011) 1322e1325

Table 1
Comparative electrical parameters of pure PVA with doped PbTiO3 composite films.

Parameter 0% filled 90:10 80:20 60:40

In plane Capacitance (Cs) 12 nF, 0 V, 20 Hz 673 pF, 25 V, 1 kHz 553 pF, 0 V, 1 kHz 6 nF, 0 V, 50 Hz
Out Plane Capacitance (Cp) 81 nF, 40 V, 20 Hz 26 pF, 10 V, 100 Hz 805 nF, 40 V, 100 Hz 789 nF, 15 V, 50 Hz
Dielectric Constant out plane 120, 0 V, 20 Hz 268.93, 10 V, 100 Hz 219.12, 30 V, 20 Hz 358, 0 V, 50 Hz

Dielectric Constant In plane 150, 0 V, 20 Hz 1200, 0 V, 20 Hz 5200, 40 V, 50 Hz 8000, 15 V, 50 Hz

Dielectric Loss ( ) 3, 40 V, 20 Hz 1.89, 0 V, 20 Hz 1.69, 0 V, 1 kHz 7.6, 30 V, 50 Hz
In plane Resistance (Rs) 284 k U, 30 V, 20 Hz 122 k U, 0 V, 50 Hz 178 k U, 0 V, 20 Hz 72 k U, 0 V, 50 Hz
Outplane Resistance (Rp) 390 k U, 20 V, 20 Hz 328 k U, 15 V, 50 Hz 122 k U, 0 V, 50 Hz 950 k U, 0 V, 50 Hz
Impedance (Z) 312 k U, 20 V, 20 Hz 215 k U, 0 V, 20 Hz 249 k U, 15 V, 20 Hz 356 k U, 0 V, 50 Hz

Reactance (X) 140 k U, 0 V, 20 Hz 163 k U, 10 V, 20 Hz 108 k U, 0 V, 20 Hz 256 k U, 0 V, 20 Hz

Conductance (G) 56 mSec, 0 V, 100 kHz 1.23 mSec, 40 V, 1 MHz 10.31 mSec, 40 V, 1 MHz 809 mSec, 40 V, 1 MHz
Susceptance (B) 463 mSec, 40 V, 100 kHz 2.65 mSec, 40 V, 100 MHz 9 mSec, 40 V, 100 Hz 12 mSec, 0 V, 50 Hz
Admittance (Y) 24 mSec, 40 V, 10 kHz 2.92 mSec, 40 V, 1 MHz 12 mSec, 40 V, 100 Hz 840 mSec, 40 V, 1 MHz
Phase angle (q) 1000, 40 V, 1 MHz 650, 10 V, 100 kHz 81.40, 0 V, 100 kHz 1650, 0 V, 100 kHz
Quality factor (Q) 25, 40 V, 10 kHz 3.36, 20 V, 1 kHz 7, 10 V, 100 kHz 25, 40 V, 1 MHz

the filler induced micro-structure of composite films playing crucial

role in view of various applications [12,13]. The electrical mecha-
nism of composite film in the form of the bulk property reveals the
micro structural details. Specially the dielectric properties not only a 2.0 0v
based on external stimuli such as temperature, humidity, pressure, 10 v
exposure to ionic radiation, but also it depends on operating elec- 15 v
1.5 20 v
trical signal magnitude (AC in addition to DC). Specially molecular 25 v
Dielectric Loss

weight dependence electronic polarization of PVA chain applicable 30 v

35 v
as bio-compactable material [11]. Therefore, the relative dielectric 1.0 40 v
constant evaluated by the following relations,
0.5
3 ¼ Cp  9:96  109 for out plane (1)

0.0
3 ¼ Cs  9:96  109 for in plane (2)
10 100 1k 10k 100k 1M
Where Cp and Cs is parallel and series capacitor measured across Frequency (Hz)
the composite film. The plots of out plane dielectric constant of
PVA/PbTiO3 composite films as function of frequency, for 10, 20, b 0v
5 10 v
and 40% doped PbTiO3 shown in Fig. 1(a), (b) and (c) respectively.
15 v
The out plane dielectric constant (3) magnitude is directly propor- 20 v
4 25 v
tional to the out plane capacitor (Cp) measured across the
Dielectric Loss

30 v
composite film for all samples. For 10% doped PbTiO3 the maximum 35 v
3 40 v
Cp value observed was 30 nF and the relative dielectric constant is
around 300. The maxima were observed for 10 V bias potential and 2
polarization process is independent of external DC bias potential.
For 20% doped PbTiO3 the maximum Cp value was observed 25 nF 1
and the relative dielectric constant is 250. As the DC bias voltage
increases, the out plane Cp and 3 magnitude decreases. Polarization 0
Splitting (PS) was observed at lower frequency 20 Hz. For further 10 100 1k 10k 100k 1M
increase in frequency, magnitude of polarization decreases. For 40% Frequency (Hz)
doped PbTiO3 the maximum Cp value observed is 350 nF and the c 10
relative dielectric constant is 3500. With clear PS at low frequency 0v
10 v
20 Hz and the magnitude of polarization inversely proportional to 8 15 v
the applied bias potential. Fig. 2(a), (b) and (c) shows the plots of in 20 v
25 v
Dielectric Loss

plane dielectric constant of PVA/PbTiO3 as function of frequency, for 6 30 v

10, 20, and 40% doped PbTiO3 by weight respectively. The magni- 35 v
40 v
tude of in plane dielectric constant (3) is directly proportional to the 4
in plane capacitor (Cs) across the composite films. For 10% dopant
PbTiO3 the in plane capacitance value is 120 nF with 3 ¼ 1200. The 2
dielectric trend is inversely proportional to applied bias magnitude.
More interestingly the sample dopant 20% at the lower frequency 0
20 Hz have shown increase in magnitude of in plane capacitance
10 100 1k 10k 100k 1M
value 550 nF and with dielectric constant 3 ¼ 5500, however, for
Frequency (Hz)
20% PbTiO3 dopant concentration the magnitude of 3 is directly
proportional to the applied bias potential. The polarization trend Fig. 3. Loss ( ) vs. frequency f (a) 90:10, (b) 80:20 and (c) 60:40 of PVA/PbTiO3
shift from 20 Hz to 100 Hz with its higher magnitude 3 ¼ 8000 composite film.
 G.M. Joshi et al. / Current Applied Physics 11 (2011) 1322e1325
observed incase of 40% 40% PbTiO3 dopant shown in Fig. 2(C). The
shift of polarization frequency is due to increase in dopant% and the
polarization magnitude is directly proportional to the applied DC
bias potential.
3.2. Dielectric loss of the composite films
It is important to consider the losses in ac capacitors. Most of
the dielectrics (except vacuum) have two types of losses. One is the
conduction loss, representing the flow of actual charge through the
dielectric. The other is a dielectric loss due to movement or rotation
of the atoms or molecules in an alternating electric field. Capacitors
are made for ac, dc, and pulse applications. The ac case is the most
general since ac capacitors will work (or at least survive) in dc and
pulse applications, where voice versa may not be true. Dielectric loss
trend was measured directly across the 0% filled (pure PVA film)
with magnitude 2.82 at 40 V bias potential for lower frequency
20 Hz (also the magnitude of dielectric loss is directly proportional
to the DC bias potential for pure PVA film) as shown in the Table 1.
The dielectric loss magnitude as function of frequency, for 10,
20, and 40% doped PbTiO3 composite films by weight were shown
in Fig. 3(a), (b) and (c) respectively. For 10% doped PbTiO3
composite film the loss value was observed maximum at lower
frequency 20 Hz at 0 V and the loss value is inversely proportional
to applied bias potential. For further increase in frequency up to
1 kHz it decreased and then local loss maxima was observed at
10 kHz. But, no significant effect of biasing was observed at higher
frequency, the values shown in Fig. 3(a).
In the Fig. 3(b), the loss trend for 20% PbTiO3 doped composite
film is shown, the loss trend is directly proportional to the bias
potential and found maximum ( ¼ 5.2) at 20 Hz frequency at 40 V
bias potential. For further increase in frequency the loss magnitude
decreases. For 40% doped PbTiO3 composite film the loss trend
independent of bias potential at 50 Hz frequency but directly
proportional to the applied bias potential with loss value ( ¼ 8.8)
and second loss peak was observed at 100 kHz frequency which
may due to the dopant% shown in Fig. 3(c) the advantage of these
properties were better than that of the individual type ac, dc and
1325
pulsed capacitors. The external control of polarization to obtain the
desired magnitude electrical magnitude is highly crucial for
applications point of view [14e16].
4. Conclusions
Significant improvement of dielectric constant observed due to
PbTiO3 dopant%. The dielectric constant trend in both planes is
directly proportional to the PbTiO3% and the external DC bias
potential applied across the film. The higher magnitude of in plane
dielectric constant is due to larger area of composite films. For
concentration of PbTiO3 dielectric loss trend is inversely propor-
tional to the DC bias potential and for higher vice versa. However
higher concentration of dopant increases the loss magnitude of this
composite film. This property of “Resolved Dielectric Polarization
(RDP)” may be used as dielectric sensor, super-capacitor film or
humidity sensor.
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