J. Am. Ceram. Soc.
, 92 [4] 834–838 (2009)
Journal
Ferroelectric Phase Stability Studies in Spray Deposited KNO3:PVA
Composite Films
Applied Physics and Materials Science Laboratory, Department of Applied Sciences, Baba Farid College of Engineering
Kopple C. Sekhar, Arvind Nautiyal, and Rabinder Nath
Ferroelectric Materials and Devices Research Laboratory, Department of Physics, Indian Institute of Technology,
The composite films of potassium nitrate (KNO3):poly(vinyl al-
cohol) (PVA) have been prepared at different temperatures by
spray-deposition technique. Ferroelectric hysteresis loops were
traced at room temperature for the composite films using mod-
ified Sawyer and Tower circuit. The X-ray diffraction studies
confirm the existence of ferroelectric phase III of KNO3 in the
composite films at the room temperature, where this phase in
pure KNO3 films is known to exist in the temperature range
1101–1241C. The composite films deposited at 2001C shows the
optimum remanent polarization, PrB17 lC/cm2. The Pr was
studied in the frequency range 10 Hz–1 kHz. The stability of the
Pr in the composite films exhibits improved fatigue compared
with that of quenched KNO3 films. The capacitance–voltage (C–
V) characteristics exhibits butterfly features which supports the
presence of ferroelectric phase in the composite films. The
atomic force microscopy images show that the composite films
have uniform dispersion of KNO3 particles in the PVA matrix.
I. Introduction
P OTASSIUM NITRATE (KNO3) is an interesting material because
of its ferroelectric properties in one of its phases.1–6 The pure
KNO3 crystals exists in phase II with orthorhombic (aragonite)
crystal structure at room temperature and atmospheric pressure.
It changes to phase I (rhombohedral crystal structure) above
1301C.4,5 On cooling, phase I of KNO3 does not directly revert
back to phase II but through an intermediate metastable phase
III, which is ferroelectric in region B1241–1101C, on further
cooling it changes to phase II.4,5 The ferroelectric phase III
which appears only in the process of cooling results from the
shift by 0.55 Å of the nitrate groups from the centre of the unit
cell, which creates dipoles and hence spontaneous polarization
along the c-axis.4,7 The phase III has attracted much attention
because of its extremely useful ferroelectric properties.5 It has
been reported that the exact temperature region over which
phase III exists at atmospheric pressure, not only depends on the
previous treatment of the specimen, but also strongly on the
cooling rate.
Many studies such as far infrared,4,7 neutron diffraction,8 in-
elastic neutron scattering,9 Raman spectroscopy,1,10,11 X-ray,11–13
differential scanning calorimetric,14–16 dielectric,5,17 electrical17
and thermal conductivity,18 and ferroelectric,19–22 have been
carried out in past by many researchers to examine the nature
of the phase transitions in KNO3.
D. C. Lupascu—contributing editor
Manuscript No. 24773. Received May 26, 2008; approved January 8 2009.
w
Author to whom correspondence should be addressed. e-mail: jshundal@yahoo.com
834
DOI: 10.1111/j.1551-2916.2009.02976.x
r 2009 The American Ceramic Society
Navneet Dabra and Jasbir S. Hundalw
and Technology, Bathinda, Punjab, India
Roorkee, Uttarakhand, India
The stabilized phase III of KNO3 in thin film form have ad-
vantages such as, low operating voltage,23 fast switching re-
sponse,23,24 small size and cost effectiveness.25,26 These are being
used as ferroelectric capacitors, memory element, nonvolatile mem-
ory devices (NV-RAMs), and dynamic random access memories.23
Several attempts have been made to stabilize phase III
of KNO3 at room temperature in thin fused films,19 with the
application of high pressure,5 mixing it with starch,13 poly-
vinyl fluoride,25 poly(vinyldiene fluoride) (PVDF),26 carbon,27
and silicon carbide.28,29 The KNO3–polymer composite films
showed a considerable improvement in the ferroelectric proper-
ties and phase stabilization.25,26 The surface electric field effect,1
strain,30 departures from the stoichiometry,31 enhancement of
ferroelectric phase with decreasing thickness20 have been studied
in past that explain the phase stabilization in the material even in
the thermodynamically unstable regions.
Usually, the ceramic–polymer composites have been prepared
by embedding ceramic particles in a suitable polymer matrix by
melt press,25,26 sol–gel,32 solvent cast,33,34 and intercalation tech-
niques.35 However, it was found that under suitable conditions
the solvent cast technique yields uniform composition of ce-
ramic and polymer due to proper interactions that occur at mo-
lecular level.36 Recently, the spray-pyrolysis37 and ultrasonic
nebulizer38 techniques have been used to prepare the thin films
of various pure ceramics.
In the present article, KNO3:poly(vinyl alcohol) (PVA) com-
posite films have been prepared using spray-deposition tech-
nique where PVA can provide an appropriate environment to
KNO3 to retain its ferroelectric phase III at room temperature.
Moreover, PVA has high viscosity, common aqueous solubility
as KNO3 and it can also give the mechanical strength39 to the
composite films in comparison with the pure KNO3. The ferro-
electric behavior was studied by tracing the hysteresis loop and
capacitance–voltage (C–V) characteristics. The surface morpho-
logical and structural studies have been carried out using atomic
force microscopy (AFM), and X-ray diffraction (XRD).
II. Experimental Procedure
The crystals of purified KNO3 supplied by E. Merck (India) Ltd.
(Mumbai, India) were dissolved in the double distilled water till
saturation level and kept in a closed environment for a few days.
The crystals grown in the solution were dried and powdered and
then used to prepare the composite films. Different weight per-
cent of KNO3 and PVA weighing a total of 200 mg were dis-
solved in 50 mL of double-distilled water at 401C while stirring.
PVA is known to have maximum aqueous solubility without
precipitation at 401C.36,39 The deposition of the composite films
of KNO3:PVA have been done in ambient atmosphere with the
spray-deposition set up assembled in the laboratory. The aver-
age thickness of each film was found to be 14 mm. The smooth
April 2009
well-polished circular brass disks of diameter 1 cm and thickness
2 mm were used as substrates for the deposition of the compos-
ite films at different temperatures. It has been reported that the
PZT and derived PZT glass–ceramics thin films deposited on the
different metal substrates shows excellent ferroelectric, electrical,
and dielectric properties.40–42 The composite films were pre-
pared at temperatures 1501, 2001, and 2501C. Each film was then
annealed at their respective deposition temperatures for 2 days
and then slowly cooled down to room temperature.
Circular electrodes of Indium24 having cross-sectional area
B1.867  102, 3.253  102, and 5.726  102 cm2 were depos-
ited by thermal evaporation under the vacuum B2.0  105 mbar
onto the respective composite films. Modified Sawyer–Tower cir-
cuit43 connected with computer has been used to display the hys-
teresis loop characteristics. The values of the Pr were calculated
for different electrode areas. The dependence of Pr on frequency
of applied signal and reversal cycles has also been investigated.
X’Pert-Pro X-ray diffractometer (PANalytical, B.V Lelyweng,
the Netherlands) with Ni-filtered CuKa radiation of wavelength
0.154 nm was used for XRD studies of the composite films. AFM
has been used to investigate the morphology and microstructure
of the composite films. The capacitance–voltage (C–V) charac-
teristics were recorded at room temperature using Keithley (590
model) C–V analyzer (Keithley Instruments, Cleveland, OH).
III. Results and Discussions
(1) Structural Properties
(A) XRD: The XRD measurements were performed to
obtain the information about the existence of the ferroelectric
phase III in the composite films deposited at different temper-
atures. Figure 1 shows the X-ray scans of pure KNO3 powder,
composite films of KNO3:PVA (containing 50 wt% of KNO3)
deposited at different temperatures and pure PVA film. It was
reported by Schaffer and Mikkola22 that KNO3 exhibits the
diffraction peak at 2y 5 29.801 for (003) reflection for the phase
III and 2y 5 29.451 for (012) reflection for the phase II. The most
common diffraction peaks of phase II at 2y 5 23.571, 23.831,
29.401, 32.331, and 32.821 were observed in the KNO3 powder
for the planes of (h k l) values (111), (021), (012), (102), and
(l 0 l)
(e)
(012)
(d)
Relative Intensity (a.u)
(012)
(c)
(012)
(b)
(111)
(021)
(002)
(a)
10 20
2θ(deg.)
Fig. 1. X-ray scans of the (a) pure potassium nitrate (KNO3) powder
and KNO3:poly(vinyl alcohol) (PVA) composite films (containing
50 wt% of KNO3) prepared at temperature, (b) 1501C, (c) 2001C,
(d) 2501C, and (e) pure PVA Film.
KNO3:PVA Composite Films 835
(112), respectively. The XRD peak corresponding to phase III
was not seen in the XRD pattern of pure KNO3 powder. The
composite films exhibit the ferroelectric phase III peak at
2y 5 29.711 corresponding to (003) reflection and another peak
at 2y 5 29.521 for (012) reflection for the phase II in addition to
the peak around 2y 5 19.61 that corresponds to PVA.44 The
earlier X-ray studies by other workers also suggest the existence
of ferroelectric peak around 2y 5 29.81 in addition to peak cor-
responding to phase II around 2y 5 29.51 in mixed KNO3 sys-
tems.22,26,43,45 The composites films of the KNO3:PVDF are also
known to exhibit enhanced phase III peak at 2y 5 29.81.26
Therefore, the present X-ray studies suggest that the new peaks
could be due to the ferroelectric phase III.
Figure 2 shows the expanded XRD scans of pure KNO3
powder and the composite films prepared at different tempera-
tures. The peak of ferroelectric phase III in the composite films
were found to occur in the range of 2y 5 (29.7170.01)1 and that
of phase II within 2y 5 (29.5270.01)1. Such small shift in the
diffraction peaks have also been reported earlier in KNO3:starch
and KNO3:PVDF composite samples.13,26 The relative intensity
of phase III to phase II was estimated and was found to be 1.68,
2.63, and 1.53 in the composite films prepared at 1501, 2001, and
2501C. It was maximum for the composite films prepared at
2001C. Thus, it is inferred that the composite film deposited at
2001C have more stable ferroelectric phase. The average crys-
tallite size was determined using Scherrer relation46
0:91l
t¼ (1)
bðyÞcos y
where b(y) is the full-width at half-maximum of the peak, l is
the wavelength of X-rays used in X-ray scan and t is the average
crystallite size. The crystallite size was found to be 76.8, 79.2,
and 84.5 nm for the composite films prepared at temperatures
1501, 2001, and 2501C, respectively. The crystallite size was
found to increase with the deposition temperature. It has been
reported in literature that large crystallite size of the phase III in
the composite film of KNO3:PVDF is responsible for producing
stable ferroelectric phase at room temperature.26
(B) AFM: The surface morphology of the composite
films (containing equal proportions of KNO3 and PVA) has
been analyzed by AFM. Figure 3 shows the two- and three-
dimensional images depicting 5 mm  5 mm area of these com-
posite films prepared at the temperatures 1501, 2001, and 2501C,
respectively. The AFM images of the composite films prepared
at 1501 and 2001C clearly show well-grown spherical-shaped
(003)
KNO3 particles, which are homogenously dispersed in PVA ma-
Brass
Brass
trix and average grain size was estimated to be 186 and 230 nm.
(012)
(a)
(003)
Brass
(003)
(b)
Brass
(c)
(d)
Relative Intensity (a.u)
(003)
Brass
Brass
(012)
(012)
(112)
(102)
30 40 29.2 29.4 29.6 29.8 30.0 30.2
2θ (deg.)
Fig. 2. Expanded X-ray scans of the (a) pure potassium nitrate (KNO3)
powder and KNO3:poly(vinyl alcohol) (PVA) composite films (contain-
ing equal proportions of KNO3 and PVA) prepared at temperatures,
(b) 1501C, (c) 2001C, and (d) 2501C.
836 Journal of the American Ceramic Society—Dabra and Hundal Vol. 92, No. 4

5.0
(a)
4.5 (a)
4.0
nm
3.5 100
3.0 80
60
2.5
40
2.0 m
m 20
1.5 0 5
5
4 4
1.0
3 3
0.5 2 2
1 1
0 0 0
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
m
5.0
(b) (b)
4.5
4.0 nm
100
3.5
80
3.0 60
2.5 40
μm 20
2.0 0
5
1.5 5
4
4 4.5
1.0 3 3 3.5
2 2.5
0.5 2
1 1 1.5
0 0.5
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 0 0
m
5.0
5.0 (c)
4.5
(c)
4.0
nm
3.5
300
3.0 250
200
2.5 150
100
2.0
50 μm
1.5
μm 0
5 5
4 4
1.0 3 3
2 2
0.5
1 1
0 0
0
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
m
Fig. 3. The two- and three-dimensional atomic force microscopic images of the composite films (containing equal weight percentage potassium nitrate
and poly(vinyl alcohol)) prepared at temperatures (a) 1501C, (b) 2001C, and (c) 2501C.

The root mean square (rms) roughness of the composite
films deposited at 1501 and 2001C was found to be 74 and
61 nm, respectively. However, the interconnected clusters of
KNO3 grains were seen in the AFM image of the composite
film deposited at 2501C. The average grain size was found to be
290 nm with very large rms roughness of 170 nm. This might be
due to melted PVA, which creates the clustering of KNO3 par-
ticles in the composite films.
exist between the neighboring domains. These forces are known
to weaken as the particle size increases.40 This in turn facilitate
more domains to orient in the field direction at elevated tem-
perature causing large Pr. The composite films deposited at
1.2
Normalizied Polarisation

1.0
(2) Electrical Properties
(A) Hysteresis Loop Measurements: The ferroelectric 0.8
hysteresis loops (P–E) of the composite films were traced using
modified Sawyer and Tower circuit.43 Figure 4 shows the de- 0.6
pendence of normalized Pr in composite films deposited at
2001C, containing different weight percent of KNO3. The value 0.4
of Pr was found to be maximum in the composite films with
equal proportion of KNO3 and PVA.
0.2
Figure 5 shows the P–E loops of the composite films (com-
prising of equal weight percentages of KNO3 and PVA) prepared 10 20 30 40 50 60 70 80 90 100
at different temperatures. The value of Pr was estimated in each wt. % of KNO3
composite film and the optimum value was found to beB17 mC/
cm2 for the films prepared at substrate temperature 2001C. This Fig. 4. Composition dependence of the normalized polarization in
might be due to the distance dependent repulsive forces, which potassium nitrate:poly(vinyl alcohol) composite films.
April 2009 KNO3:PVA Composite Films 837

45
150°C
1.5
30 200°C

Normalizied polarization
250°C
1.2
P(μC/cm 2) 15

0
0.9

−15
0.6
−30

−45 0.3
−8 −6 −4 −2 0 2 4 6 8
0.0 5.0x105 1.0x106 1.5x106 2.0x106
Electric field (kV/cm) Reversal cycles(n)
Fig. 5. Hysteresis loops of the potassium nitrate (KNO3):poly(vinyl Fig. 7. Normalized polarization versus number of reversal cycles for
alcohol) composite films (containing 50 wt% of KNO3) at 50 Hz pre- the optimized potassium nitrate:poly(vinyl alcohol) composite films.
pared at temperatures (a) 1501C, (b) 2001C, and (c) 2501C.

The KNO3:PVDF composite films could not be prepared by

2501C gave lower Pr though the average crystallite and grain
sizes are slightly larger than those of the composite films depos-
ited at 2001C. The decrease in Pr might be due to melted PVA,
which create the porosity between the KNO3 clusters. The value
of Pr was calculated for different electrode areas and was found
to be 17.070.5 mC/cm2. Thus, Pr was observed to be almost
independent of electrode area. The deposition temperature does
not appear to affect the coercive field (Ec) in these composite
films. The ferroelectric composite films deposited at 2001C con-
taining equal proportions of KNO3 and PVA show compara-
tively better results, hence, the composite films prepared under
these conditions were used for further studies.
The frequency dependence of Pr in the optimized composite
film was studied in the frequency range of 10 Hz–1 kHz, as
shown in Fig. 6. It was found that the value Pr at 300 Hz de-
creases to 0.84 times its peak value at 10 Hz (inset of Fig. 6).
Further increase in the frequency of the applied field does not
affect Pr much, it remains B17 mC/cm2. The decrease in Pr with
frequency may be due to steady decrease in the contribution of
space charge effect36 to the total polarization. However, the
space charge contribution become negligible at higher frequen-
cies and Pr may really be due to ferroelectric domains switch-
ing.36
The value of the PrB17 mC/cm2 in the optimized KNO3:PVA
composite films prepared by spray-deposition technique is more
than three times as reported in the poled KNO3:PVA films
prepared by solvent cast technique47 and about twice that ob-
served in pure fused KNO3 films.22 This value of Pr is slightly
lower than that reported for KNO3:PVDF composite films.26
spray-deposition technique for want of common solvent.
(B) Fatigue Study: Figure 7 shows the normalized po-
larization versus number of reversal cycles in the KNO3:PVA
composite film prepared under the optimum conditions. The
value of normalized polarization at 2  106 reversal cycles re-
duces to 0.65 times of its initial value. Thus, these composite
films show better fatigue life span than the fused KNO3 films in
which Pr drops to 50% after 105 cycles,20 but this value of life
span is still less than that of other competitive materials in this
category.
(C) Capacitance–Voltage (C–V) Characteristics: Figure 8
shows the typical C–V characteristics (frequency B100 kHz) stud-
ied at room temperature for the composite films (containing
50 wt% of KNO3) prepared at 1501, 2001, and 2501C, respec-
tively. The voltage was swept from 15 to 115 V in the forward
bias and from 115 to 15 V in the reverse bias with a step bias
of 1V. The capacitance shows a strong bias dependence and ex-
hibit nonlinear behavior. The two sharp peaks at 4 and 15 V
were observed in all the composite films and the values of Cmax
were measured to be 0.16, 0.21, and 0.12 nf, respectively, for the
composite films prepared at 1501, 2001, and 2501C. The composite
film prepared at 2001C exhibited better dielectric properties. These
sharp peaks may be attributed to the polarization switching phe-
nomena.36,43 The initial increase in the capacitance with bias volt-
age may be due to orientation of domains in the field direction.
Moreover, the maxima in C–V curves occur in the vicinity of co-
ercive voltage (Vc). In the neighborhood of coercive voltage the
domain walls are known to be more active due to nucleation of
new domains or the maximization of the domain wall mobility.
Thus, the contribution from the domain wall motion to the di-

40 (a)
(b)
30 0.24 (a)
(c)
(b) +5V
20 (d) (c) –4V
(e) 0.20
P(μC/cm2)

10
Capacitance (nf)

0 0.16
–10
–20 0.12

–30
0.08
–40
–8 –6 –4 –2 0 2 4 6 8 0.04
Electric field (kV/cm) –15 –10 –5 0 5 10 15
Voltage (V)
Fig. 6. Hysteresis loops of the optimized potassium nitrate (KNO3):
poly(vinyl alcohol) (PVA) composite film at frequency. (a) 10 Hz, Fig. 8. C–V characteristics of the potassium nitrate (KNO3):poly(vinyl
(b) 50 Hz, (c) 100 Hz, (d) 300 Hz, and (e) 1 kHz. (Inset) Frequency alcohol) composite films (containing 50 wt% of KNO3) prepared at
dependences of Pr in the optimized KNO3:PVA composite film. temperatures (a) 1501C, (b) 2001C, and (c) 2501C.
838 Journal of the American Ceramic Society—Dabra and Hundal
electric properties is the greatest48 resulting in the sharp peaks
around Vc in C–V characteristics. The decrease in the capacitance
in the forward and reverse cycles could be due to the reduction
in domain moment.48,49 The strong bias dependence of capaci-
tance with applied voltage can be useful in tunable microwave
applications and voltage controlled oscillators in electronics.36
The butterfly features of C–V curves in the composite films like
other ferroelectric films strongly corroborate the presence of the
ferroelectric nature of the composite films at room temperature.
IV. Conclusions
The composite films of KNO3:PVA containing equal propor-
tions of KNO3 and PVA prepared by spray-deposition tech-
nique show improved Pr and stability of ferroelectric phase III
at room temperature. The X-ray diffraction studies on these
films reveal more intense phase III peak relative to phase II
peak. The optimum value of Pr is obtained for the films depos-
ited at 2001C. The hysteresis loop and the C–V characteristics
confirm the existence of ferroelectric phase III in KNO3:PVA
composite films at room temperature.
Acknowledgments
The authors acknowledge the Chairman, Baba Farid College of Engineering
and Technology, Bathinda for providing the research facilities in the college and
Director, Sophisticated Analytical Instrumentation Facility (SAIF), Panjab Uni-
versity, Chandigarh for providing the facility for the X-ray scans.
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