Appl Phys A (2010) 99: 941–946
DOI 10.1007/s00339-010-5699-8
Polarization switching properties of spray deposited CsNO3 :
PVA composite films
Arvind Nautiyal · K.C. Sekhar · N.P. Pathak ·
Navneet Dabra · Jasbir S. Hundal · R. Nath
Received: 14 December 2009 / Accepted: 1 April 2010 / Published online: 29 April 2010
© Springer-Verlag 2010
Abstract The ferroelectric and switching properties of
spray deposited cesium nitrate: poly (vinyl alcohol) compos-
ite films at different substrate temperatures (Ts ) have been
studied. The optimum value of remanent polarization was
obtained in the film deposited at Ts = 200°C, which may be
due to larger structural distortion (c/a ratio) and less poros-
ity as revealed by x-ray diffraction and field emission scan-
ning electron microscope (FESEM) analysis. The switch-
ing current transients have been analyzed by nucleation lim-
ited switching model (NLS) with the Lorentzian distribution
function. This model gives excellent agreement with the ex-
perimental polarization current throughout the whole time
range. The switching parameters were determined in the
composite films deposited at different Ts and found to be
optimum at Ts = 200°C. The effect of pulse amplitude on
A. Nautiyal () · K.C. Sekhar · R. Nath
Department of Physics, Ferroelectric Materials and Devices
Research Laboratory, Indian Institute of Technology Roorkee,
Roorkee 247667, Uttarakhand, India
e-mail: nautyphysics@gmail.com
R. Nath
e-mail: rnathfph@iitr.ernet.in
A. Nautiyal · N.P. Pathak
Radio Frequency Integrated Circuits Research Laboratory,
Department of E & CE, Indian Institute of Technology Roorkee,
Roorkee 247667, Uttarakhand, India
N. Dabra · J.S. Hundal
Applied Physics & Materials Science Laboratory,
Department of Applied Sciences, Baba Farid College
of Engineering & Technology, Bhatinda, Punjab, India
Present address:
K.C. Sekhar
Department of Materials Science & Engineering,
Yonsei University, Seoul 120-749, South Korea
the domain switching properties has also been studied and
analyzed. The peak value of polarization current exhibits an
exponential dependence on the external applied field.
1 Introduction
The polarization reversal phenomenon takes place by apply-
ing an external electric field and this property can be utilized
for memory device application. The polarization switching
may arise due to the nucleation of ferroelectric domains at
the surface and their subsequent growth through the bulk
by the domain wall motion and coalescence of the domains
[1–3]. Many theoretical models have been developed to ex-
plain the switching kinetics in ferroelectric materials [4–7].
The nucleation limited switching (NLS) model [8–10] is
based on the statistics of nucleation and growth of the re-
versed domains and has been proposed as an alternative ap-
proach to the KAI model [4].
The ferroelectric ceramics belonging to the XNO3
(X = K, Cs etc.) family have been considered for memory
applications due to their high Pr and low dielectric con-
stant values. These ceramics have coercive field of order
kV/cm, and to use them in the devices operating at rela-
tively low voltage needs fabrication in the film form. These
materials can be produced in film form by embedding in
suitable polymer matrix. The dielectric study in nanograin
size barium titinate and PVA matrix has shown enhanced
dielectric strength [11]. On the other hand and KNO3 —
polymer composite films have shown enhancement in the
ferroelectric properties [12]. The polymer composite films
with ferroelectric switching properties may be suitable for
non-volatile memory devices [13, 14].
Cesium nitrate (CsNO3 ) in crystal form has been ob-
served to exhibit the ferroelectric phase in trigonal sym-
942 A. Nautiyal et al.

metry below 154◦ C and paraelectric phase with cubic sym- 3 Results and discussion
metry above this temperature [15, 16]. There are only few
reports on the ferroelectric and structural properties of in 3.1 Structural properties
CsNO3 [17]. The composite films of CsNO3 and PVA
were prepared using the ultrasonic spray-pyrolysis tech- The x-ray diffraction (XRD) pattern of CsNO3 : PVA com-
nique which can give uniform composite films of smaller posite films deposited at different Ts were studied. Figure 1
thickness than solvent cast method [18]. shows the typical XRD pattern of composite film deposited
In the present paper, the study of switching kinetics in at Ts = 200◦ C. The (h k l) values of all diffracted peaks
CsNO3 : PVA of spray deposited composite films has been were indexed with matching JCPDS data (file No. 09-0403).
reported. The switching kinetics has been analyzed using The (h k l) values suggest that the spray deposited compos-
NLS models to get insight into dynamics of nucleation ite films of CsNO3 has triogonal structure at room temper-
process and domain growth during the switching process. ature with lattice parameters, a = 10.81 Å and c = 7.72 Å
(at Ts = 200◦ C) which are in reasonable agreement with the
values quoted in literature [21]. The lattice parameters val-
2 Experimental ues at different Ts were calculated and the values of the c/a
ratio are given in Table 1. The c/a ratio is found to be max-
The ultrasonic spray-pyrolysis method was used for the de-
imum in film deposited at Ts = 200◦ C, which implies more
position of the composite films of CsNO3 : PVA. A com-
asymmetric nature and may enhance the ferroelectric prop-
mercial ultrasonic nebulizer, operating frequency 1.7 MHz,
erties [22]. Hence the change in c/a ratio value is taken the
was used to nebulize the CsNO3 : PVA composite solution.
measure of the structural distortion in the composite films.
The ultrasonic nebulizer generates the high frequency wave
Figure 2 shows the FESEM images of composite films
which generates an aerosol by electronic oscillator. The
deposited at different Ts . The visual examination of these
aerosol generated by the ultrasonic wave was sprayed on to
images suggests that at lower deposition temperature (up to
the heated substrate using air as carrier gas through glass
150◦ C) the CsNO3 particle are not grown well [Fig. 2(a–b)]
pipe of diameter 10 mm.
which leads to porosity. However, when Ts ≥ 175◦ C the
The composite films of CsNO3 and PVA were deposited
CsNO3 particles were grown in nearly spherical shape and
onto a clean and smooth circular brass disks with diameter
exhibit homogeneous dispersion in PVA matrix [Fig. 2(c)].
of 1.5 cm using ultrasonic spray pyrolysis with the help of
The clustering of grains is observed at higher temperature
ultrasonic nebulizer. The purified CsNO3 powder and PVA
(Ts = 225◦ C), which may create porosity between the inter-
were dissolved in equal proportion in 50 ml of double dis-
stitial regions of CsNO3 grains [Fig. 2(d)].
tilled water at 40◦ C. A solution flow rate of 1 ml/min was
used for the deposition of the films. The distance between
substrate and nozzle was kept at 4 cm and the solution was 3.2 Ferroelectric properties
sprayed 5 times with a period of four minutes at a gap of
2 minute on the circular brass substrate. The composite films The hysteresis (P-E) loop characteristics of the spray de-
were deposited at the different elevated substrate tempera- posited composite films of CsNO3 : PVA were studied at
tures (Ts ) in the range 100–225◦ C and these films were post a frequency of 50 Hz as shown in Fig. 3. The optimum
annealed at their deposition temperatures for 24 hours. The value of Pr = 5 µC/cm2 was obtained in the composite
temperature of the substrate is controlled by PID tempera- film deposited at Ts = 200◦ C, which may be due to well
ture controller with an accuracy of ±1◦ C. The thickness of
the composite films was estimated to be about 15 µm us-
ing the capacitance method. The circular indium electrode
of diameter 2 mm were vacuum deposited at a pressure of
2 × 10−5 mbar. The indium gave good ohmic contact and
adhesion with ferroelectric materials and hence it was cho-
sen for the electrode metal [19, 20].
The x-ray diffraction (XRD) scans of the composite films
were taken using advanced Bruker D8 diffractometer and
the surface morphology was investigated using the field
emission scanning electron microscope (FESEM). The P-E
loop characteristics have been studied using the modified
Sawyer-Tower circuit. The switching current transients of
composite films were measured across a resistance of 200  Fig. 1 Typical XRD pattern of composite film deposited at
connected in series with the films. Ts = 200◦ C
Polarization switching properties of spray deposited CsNO3 : PVA composite films 943

Table 1 The effect of deposition temperature on switching parameters of the composite films

Sl no Substrate im tm (µs) ts (µs) t1 (µs) Ps ω c/a

temperature (◦ C) (mA) (µC/cm2 ) ratio

1 100 0.8584 28.15 222 88.6 1.3 0.24 0.7016

2 125 1.13 25.53 156 74.2 1.32 0.233 0.7059
3 150 1.294 24.07 153 67.6 1.52 0.198 0.7084
4 175 1.52 21.86 145 60 1.71 0.19 0.7115
5 200 2.5 15.9 102 40 2.0 0.175 0.7142
6 225 0.98 26.86 207 84 1.42 0.237 0.7051

Fig. 2 FESEM images of

composite films deposited at
(a) Ts = 125, (b) Ts = 150,
(c) Ts = 200, (d) Ts = 225◦ C

grown connected grains and more c/a ratio. The value of
Pr = 2.75 µC/cm2 was obtained in case of solvent cast film.
The increased Pr in spray deposited films may be due to a
higher c/a ratio and bigger grain size compared to solvent
cast film [18].
The frequency dependence of hysteresis loop in the op-
timized composite film deposited at Ts = 200◦ C was also
studied in the frequency range 50 Hz–1 kHz. The Pr as a
function of frequency is as shown in inset of Fig. 3. The
frequency dependence of Pr shows considerable decrease in
Pr up to 400 Hz, which may due the space charge effect to
the total polarization [23, 24]. However, at higher frequen-
cies the space charge contributions to polarization is negligi-
ble and Pr is predominantly a ferroelectric polarization and
found to be 2 µC/cm2 .
4 Polarization switching
The switching response in the composite films was studied
using the bi-polar square pulses at 1 kHz. The switching cur-
rent was measured through a resistor of 200  connected in
series with the sample.
944
Fig. 3 Hysteresis loop of the composite films deposited at different
Ts . Inset figure shows the frequency dependence of polarization of the
composite film deposited at Ts = 200◦ C
Fig. 4 The theoretical fit (solid line) of the NLS model to the experi-
mental switching transients (discrete points) of the composite film de-
posited at (a) Ts = 200, (b) Ts = 175, (c) Ts = 150, (d) Ts = 125,
(e) Ts = 225, (f) Ts = 100◦ C. The corresponding Lorentzian distribu-
tion functions are shown in the inset figure
4.1 Effect of deposition temperature
The effect of the substrate temperature on the polarization
switching was studied in the temperature range 100–225◦ C.
The discrete points in Fig. 4 show the observed switching
transients at different substrate temperature. The observed
polarization current may be due to nucleation of new ferro-
electric domains, their propagation by the domain wall mo-
tion and coalescence. The peak value of polarization current
(im ) occurs at time (tm ) and the switching time (ts ) is taken
as the time at which the current is equivalent to 0.1im [25].
The values of im , tm and ts at different Ts are given in Ta-
ble 1 and are found to be optimum in the composite films de-
posited at Ts = 200◦ C which may be due to smaller porosity
and high c/a ratio value. The spontaneous polarization was
estimated from the area under the curve [26] and found to
be maximum in the film deposited at Ts = 200◦ C, which is
in good agreement with the value estimated from P-E loop
[Table 1].
A. Nautiyal et al.
Fig. 5 The theoretical fit (solid line) of the NLS model to the exper-
imental switching transients (discrete points) of pure CsNO3 film and
its Lorentzian distribution function (inset)
The switching response of spray deposited pure CsNO3
film possessing optimum ferroelectric polarization [27] is
shown Fig. 5. Table 1 shows that there is improved ferroelec-
tric response in the composite films deposited at Ts = 200◦ C
as compared to the pure films of CsNO3 (ts = 130 µs,
t1 = 52.6 µs, ω = 0.20).
The switching kinetics of the composite films were an-
alyzed using nucleation limited switching (NLS) model
[8–10] based on the statistics of nucleation and growth of the
reversed domains as an alternative approach to KAI model
proposed by Ishibashi and Tagaki [4]. According to the NLS
model, the film can be represented as an ensemble of regions
where the switching process takes place independently. The
time dependence of polarization current has been expressed
by considering the Lorentzian distribution function of char-
acteristic time t0 of domain growth in the definite regions of
the film as [28]
 +∞    n 
d t
i(t) = 2Ps A 1 − exp −
dt −∞ t0

× F (log t0 )d(log t0 ) (1)
where F (log t0 ) is the distribution function for log t0 given
by
 
B ω
F (log t0 ) = (2)
π (log t0 − log t1 )2 + ω2
where B is the normalized constant, ω is the half-width at
half maximum, and t1 is the peak time of Lorentzian distri-
bution function.
The NLS model (Eq. 1) gave an excellent fit to the exper-
imental switching data of the composite films deposited at
different Ts (continuous curves of Fig. 4) and of pure CsNO3
film (continuous curve of Fig. 5) in the whole time range
and corresponding fitting parameters t1 and ω are given in
Table 1. This implies that the switching process takes place
Polarization switching properties of spray deposited CsNO3 : PVA composite films 945

independently in the different region of the films as proposed

in the NLS model. These regions of the films will contribute
to the switching of polarization only if the field in that region
is above the coercive voltage [29]. The Lorentzian distribu-
tion functions were obtained from Eq. 2 using the fitted val-
ues of t1 and ω for the composite films and the pure CsNO3
film and are shown in inset of Figs. 4 and 5 respectively. The
values of log t1 and ω are minimum in the film deposited at
Ts = 200◦ C as compared to the pure CsNO3 films [Table 1].
The broadening of F (log t0 ) indicates the increase in lo-
cal field variation. The F (log t0 ) is related to the concen-
tration of dipole defects inside the films and these dipole Fig. 6 The theoretical fit (solid line) of the NLS model to the ex-
defects acts as pinning sites for the domain wall motion. perimental switching transients (discrete points) of the composite
Differences in the dipole defect density distribution in the film (Ts = 200◦ C) at different pulse amplitude ((a) = 15, (b) = 14,
(c) = 13, (d) = 12, (e) = 11, (f ) = 10 V). The corresponding
film should yield a distribution of local field. This causes
Lorentzian distribution functions of the composite films deposited at
the variation in the value of t0 for local switching of different Ts = 200◦ C are shown in the inset
regions in the ferroelectric films. The minimum broadening
in Lorentzian distribution function (Fig. 4) of the compos-
ite film deposited at Ts = 200◦ C suggests that the average
value of the local field over the switching media (CsNO3
grains) in composite films is relatively high as compared to
the pure CsNO3 films. This may be due to the presence of
less porosity in composite films (Fig. 2) as compared to the
pure CsNO3 films [27]. The presence of porosity strongly
hinders the domain reorientation and causes more local field
variation between the switching media and the nonswitch-
ing media (defects and porosity). Therefore, the decrease in
the average local field acting on the switching media in the
pure CsNO3 film significantly reduces the fraction of total
domain switching. Fig. 7 The plots of log(im ) vs. 1/E (curve a) and log(t1 ) vs. 1/E
(curve b)
4.2 Effect of pulse amplitude

The effect of pulse amplitude on switching kinetics of film Table 2 shows that as the pulse amplitude is increased
deposited at Ts = 200◦ C was also studied to get information from 1.5 times, the im has increased 2.2 times, while tm has
about activation field. Figure 6 shows the NLS theoretical fit decreased 2 times which may due to the contribution of new
to the experimental switching data of the composite films at switched regions. The exponential dependence of im on the
different pulse amplitudes and the corresponding Lorentzian reciprocal of field [30],
distribution functions in the inset of Fig. 6. The fitting para-  
αi
meters log t1 and ω are related microscopic parameters such im = i∞ exp − (6)
E
as [28]
αdm where αi is the activation field, is shown in Fig. 7 (curve (a)).
log t1 ≈ , (3) The value of αi is found to be 4.4 kV/cm in low field re-
E
gion and 8.4 kV/cm in high field region. This suggests that
αdm Γ switching is mainly governed by the nucleation in the low
ω≈ (4)
E2 field region, and by the domain growth in the high field re-
where αdm is activation field for domain wall motion and gion.
Γ is the half-width at half maximum of local field distrib- Figure 7 (curve (b)) shows the plot of log t1 versus 1/E
ution F (log E). The mathematical relation between Γ and and αdm is found to be 10 kV/cm, which is same in low
F (log E) is given by [28]: and high field regions. The plot of ω verses 1/E 2 shows
  two linear parts (figure not shown), which corresponds to
 =A
F (log E)
Γ
. (5)
the activation field, related to concentration of pinning sites.
π E + Γ 2 The Γ values were obtained as 1.22 kV/cm in high field
946 A. Nautiyal et al.

Table 2 The effect of pulse amplitude on switching parameters of the composite films

Sl no Voltage (V) im (mA) tm (µs) ts (µs) t1 (µs) Ps (µC/cm2 ) ω

1 15 2.5 15.9 102 40 2.0 0.175

2 14.5 2.3 18.45 105 43 2.0 0.186
3 14 2.18 19.0 112 46 1.95 0.196
4 13.5 2.0 20.99 120 49.3 1.91 0.207
5 13 1.8 22.0 142 54.6 1.87 0.213
6 12.5 1.72 23.52 150 61 1.83 0.232
7 12 1.61 26.07 181 75 1.8 0.24
8 11.5 1.51 28.0 200 86 1.76 0.245
9 11 1.42 30.32 222 96 1.72 0.2545
10 10.5 1.35 32.87 230 107 1.67 0.26
11 10 1.26 35.54 255 120 1.65 0.27

region and 0.45 kV/cm and in low field region. This may be
due to the presence nonuniform distribution of defects in the
films.
5 Conclusions
The optimization of ferroelectric properties of spray de-
posited CsNO3 : PVA composite films as a function of sub-
strate temperature gave the optimum at Ts = 200◦ C and is
correlated to higher c/a ratio and less porosity. The switch-
ing properties of composite films were found to be enhanced
as compared to the pure CsNO3 . The NLS model based on
domain growth limited switching process is found to be suit-
able to explain the switching properties. The logarithmic
characteristic switching time obeyed the Lorentzian distri-
bution. The width of Lorentzian distribution function (lo-
cal field variation) in the composite film deposited at 200◦ C
is minimum, and thus polarization reversal becomes more
probable.
Acknowledgement The author Arvind Nautiyal acknowledges the
financial support provided by Council of Scientific and Industrial Re-
search (CSIR), India.
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