JOURNAL OF APPLIED PHYSICS 108, 024108 共2010兲

Analysis of ferroelectric polarization switching in „NH4…0.39K0.61NO3 films

using nucleation limited switching model
Navneet Dabra,1,a兲 Jasbir S. Hundal,1,b兲 A. Nautiyal,2 K. C. Sekhar,2,c兲 and R. Nath2
1
Department of Applied Sciences, Applied Physics and Materials Science Laboratory, Baba Farid College
of Engineering and Technology, Bathinda, 151001 Punjab, India
2
Department of Physics, Ferroelectric Materials and Devices Research Laboratory, Indian Institute
of Technology Roorkee, Roorkee 247667 Uttarakhand, India
共Received 5 January 2010; accepted 29 May 2010; published online 22 July 2010兲
The polarization switching transients of spray deposited ferroelectric 共NH4兲0.39K0.61NO3 共NKN兲
films has been analyzed with nucleation limited switching 共NLS兲 model by considering domain
growth limited process. The experimentally measured microscopic polarization switching curves
fitted well with NLS model and the characteristic switching times obeyed the Lorentzian distribution
function. The local field variation was found to be minimum at pulse amplitude 15 V, which makes
the polarization reversal more probable. The value of spontaneous polarization, Ps and coercive
field, Ec was found to be 6.58 ␮C / cm2 and 4.10 kV/cm, respectively. The value of Ps from the
switching and P-E loop is in good agreement with each other. The field emission scanning electron
microscopy and atomic force microscopy images of the NKN film reveal the formation of
nanoparticles of NKN. © 2010 American Institute of Physics. 关doi:10.1063/1.3457228兴

I. INTRODUCTION In view of this, NKN has been chosen and an attempt

It is known that the switching process in ferroelectrics is
a very complicated evolution of domain structure. Recently,
the interest in the exploration of switching process in the
ferroelectrics has grown rapidly in view of promising appli-
cations in memory devices. The most popular method is the
measuring of transient current. In principle, the current pulse
data contains a lot of information about domain kinetics. The
polarization switching phenomenon may arise due to the
nucleation of ferroelectric domains at the surface and their
subsequent growth through the bulk by the domain wall mo-
tion and coalescence of the domains.1,2 Various theoretical
models have been developed to explain the switching kinet-
ics in ferroelectric materials.3–5
The pure KNO3 crystals exist in phase II with ortho-
rhombic 共aragonite兲 crystal structure at room temperature
and atmospheric pressure and phase III which is ferroelectric
in region 124– 110 ° C in the cooling cycle. Several attempts
have been made to stabilize phase III of KNO3 at room
temperature.6–12 However, the mixing of NH4NO3 in KNO3
is also known to stabilize the KNO3 ferroelectric phase near
room temperature. Various studies such as dielectric, hyster-
esis, x-ray, and infrared absorption have confirmed the pres-
ence of room temperature ferroelectric phase in
共NH4兲xK1−xNO3 共NKN兲 mixed crystals with concentrations
of 0 ⱕ x ⱕ 0.5 and the polarization was found to be maximum
when x = 0.39.13,14 The ferroelectric switching properties of
共NKN兲 mixed crystals does not seem to have been studied so
far.
a兲
Corresponding author. Electronic mail: navneetdabra@gmail.com.
b兲
Permanent address: Materials Science Laboratory, Department of Applied
Sciences, Giani Zail Singh College of Engineering and Technology, Dab-
wali Road, Bathinda-151001, Punjab, India.
c兲
Present address: Department of Materials Science and Engineering, Yonsei
University, Seoul 120-749, South Korea.
was made to stabilize the ferroelectric phase in this mixed
system at room temperature by preparing its films by spray
deposition technique15 as was done in KNO3 : PVA compos-
ite films.11,12 The polarization switching phenomena in the
spray deposited NKN film has been studied and analyzed
using nucleation limited switching 共NLS兲 model. This analy-
sis provides the vital information of the microscopic param-
eters like switching kinetics, local field and activation field
etc., which provide better understanding of the physical pro-
cess involved in the polarization switching of the NKN films.
II. EXPERIMENT
The 共NH4兲0.39K0.61NO3 crystals were prepared by dis-
solving the purified potassium nitrate and ammonium nitrate
of definite molar ratio in the double distilled water till satu-
ration. The solution was kept in a closed environment for a
few days to allow the crystal of NKN to grow. The crystals
thus obtained were dried, powdered and then used to prepare
the film using spray deposition setup explained elsewhere.15
100 mg of the NKN crystals were dissolved in 50 ml double
distilled water. The solution was poured in the container of
the spray deposition set up and sprayed onto preheated
共150 ° C兲 smooth circular brass substrate. The sample was
annealed in vacuum at 150 ° C for 4 h and then slowly
cooled to room temperature. Circular electrodes of Indium
were deposited by thermal evaporation under the vacuum
⬃2.0⫻ 10−5 mbar onto the upper surface of the sample. The
thickness of the sample was measured by the capacitance
method using the dielectric constant K = 5 and was found to
be 16 ␮m. Modified Sawyer–Tower circuit connected with
digital storage oscilloscope 共HM 407–2, Germany兲 and com-
puter has been used to display the hysteresis loop at room
temperature. The differential dielectric constant, ␧d as a func-
tion of electric field 共E兲 has been derived from the hysteresis

0021-8979/2010/108共2兲/024108/5/$30.00 108, 024108-1 © 2010 American Institute of Physics

Author complimentary copy. Redistribution subject to AIP license or copyright, see http://jap.aip.org/jap/copyright.jsp
024108-2 Dabra et al. J. Appl. Phys. 108, 024108 共2010兲

FIG. 1. 共Color online兲 The typical hysteresis loop and ␧d versus E curve of
NKN film at room temperature.

loop. The polarization switching transients have been studied

by applying the bipolar square signal to the sample. The
atomic force microscopy 共AFM兲 and field emission scanning
electron microscopy 共FE-SEM兲 have been employed to in-
vestigate the microstructure of the sample and morphology
studies have also been included and correlated.

III. RESULTS AND DISCUSSION

A. Hysteresis loop „P-E… studies
The hysteresis loop 共P-E兲 of the spray deposited
共NH4兲0.39K0.61NO3 共NKN兲 film has been recorded at room
temperature at a frequency of 50 Hz using sinusoidal field.
The differential dielectric constant, ␧d = 1 / ␧0共dP/ dE兲
as a function of electric field 共E兲 has also been derived
from the hysteresis loop. Figure 1 shows the typical
hysteresis loop 共P-E兲 and ␧d versus E curve of the NKN
sample at room temperature. The spontaneous polarization
共Ps兲 ⬃6.58⫾ 0.21 ␮C / cm2 and coercive field 共Ec兲
⬃4.10⫾ 0.10 kV/ cm were obtained. The ␧d versus E curve
exhibit nonlinear behavior that arises due to the phenomenon
of domain switching in the ferroelectric materials and peak
of ␧d are observed in the vicinity of coercive field 共Ec兲. The
percentage of back switching16 is estimated from the follow-
ing equation:

冉 冊
Pr
percentage of back switching = 1 − ⫻ 100,
Ps
where Pr and Ps are remanent and saturation polarizations.
The back switching 共⬃29.70%兲 was calculated from the hys-
teresis loop characteristics using the Eq. 共1兲. It is well known
that the polarization in ferroelectrics has contribution from
both 180° and non-180° domain switching. The low percent-
age of back switching in the present sample suggests the
presence of relatively more 180° domain switching than non-
180° domains.17
B. Microstructural characterization
The FE-SEM and AFM have been employed to investi-
gate the microstructure of the NKN samples. Figure 2共a兲
depicts the FE-SEM image and Fig. 2共b兲 depicts the two-
dimensional 共2D兲 AFM image of the NKN film. The FE-
SEM and AFM image 共measured area 5 ⫻ 5 ␮m2兲 depicts
the formation nanoparticle of NKN 共size ⬃70 nm and
FIG. 2. 共Color online兲 共a兲 FE-SEM image, 共b兲 2D AFM image, and 共c兲 3D
AFM image of spray deposited NKN film.
共1兲
⬃72 nm, respectively兲 in the spray deposited NKN film.
The root mean square value of surface roughness was found
to be ⬃380 nm 关Fig. 2共c兲兴. However, some defects such as
pores, clusters, and line imperfections were observed in the
FE-SEM and AFM images which are shown in Fig. 2. These
defects which could be a limiting factor for further domain
switching in the NKN film.
C. Polarization switching
The polarization switching response of the NKN sample
was studied by applying the bipolar square pulses at 50 Hz at
different pulse amplitudes. The switching current transients
were measured across a 100 ⍀ load resistance connected in
series with the sample. The discrete points in Figs. 3共a兲–3共f兲
show the experimentally observed switching transients of
NKN samples at different pulse amplitudes. The polarization

Author complimentary copy. Redistribution subject to AIP license or copyright, see http://jap.aip.org/jap/copyright.jsp
024108-3 Dabra et al. J. Appl. Phys. 108, 024108 共2010兲

FIG. 3. 共Color online兲 The experimental bell shaped switching current transients curves of 共NH4兲0.39K0.61NO3 sample at 共a兲 10, 共b兲 11, 共c兲 12, 共d兲 13, 共e兲 14,
and 共f兲 15 V bipolar pulses.

switching current peak 共imax兲 occurs at time tm. The current

peaks found to be become sharp and shifts to lower time with
increase in the applied pulse amplitude. The imax starts to
increase from 90 to 717 ␮A and tm decreases from 94 to
51 ␮s as the applied voltage increases from 10 to 15 V. This
might be due to the creation of more stabilized domains in
addition to the existing domain switching. The imax values
showed exponential dependence on the reciprocal of electric
field4 and given as

imax = i0 exp −冉 冊 ␣i
E
, 共2兲

where ␣i is the activation field. Figure 4 shows the semilog

of imax versus reciprocal of electric field. The slope of the
Fig. 4 gave the ␣i ⬃ 20.2 kV/ cm. FIG. 4. 共Color online兲 The semilog of imax vs reciprocal of electric field.

Author complimentary copy. Redistribution subject to AIP license or copyright, see http://jap.aip.org/jap/copyright.jsp
024108-4 Dabra et al. J. Appl. Phys. 108, 024108 共2010兲

TABLE I. The effect of applied pulse amplitude on switching parameters of the NKN film.

V imax t1 Ps
共V兲 共␮A兲 tm w 共␮s兲 共␮C / cm2兲

15 717 51 0.241 165 6.39

14 560 62 0.262 180 6.05
13 460 68 0.286 205 5.70
12 382 72 0.318 229 5.10
11 287 81 0.351 248 4.5
10 90 94 0.381 280 2.75

The area under the bell shaped curve is equivalent to

switched charge Qs and expressed as F共log t0兲 =
k
冉 w
␲ 共log t0 − log t1兲2 + w2
, 冊 共5兲

Qs = 冕0
ts
i共t兲dt = 2PsA,
where Ps is the spontaneous polarization and A is the elec-
trode area. The values of Ps derived from Eq. 共3兲 are in good
agreement with the Ps calculated from the hysteresis loop
共P-E兲 and its variation with pulse amplitude is shown in
Table I.
NLS model was proposed18 to explain the switching ki-
netics in ferroelectric films. This model is based on the as-
sumption that the film can be represented as an ensemble of
regions where the switching process takes place indepen-
dently and provided by nucleation and domain growth.18 Re-
cently, It was reported that the switching kinetics in poly
crystalline Pb共Zr, Ti兲O3 films based on the NLS model is
limited by domain growth process.18 The time dependence of
polarization current has been expressed by considering the
Lorentzian distribution function of characteristic time t0 of
domain growth in the definite regions of the film as18
共3兲 where F共log t0兲 is the distribution function for log t0, k is the
Normalized constant, w is the half-width at half maximum,
and t1 is the peak time of the Lorentzian distribution func-
tion. The solid line curves in Figs. 3共a兲–3共f兲 corresponding to
the NLS theory given by Eq. 共4兲 showed excellent fit to the
experimental switching data as depicted in the Fig. 3. The
values of parameters t1 and w are obtained from these fitting
curves and presented in Table I. The excellent fit would mean
that the composite film as a whole can be treated as an en-
semble of regions where the switching process takes place
independently. The existence of independent switched re-
gions can be understood from the saturation of Ps with ap-
plied pulse amplitude. This is because each region will con-
tribute to the reversal of polarization only if the applied
voltage is above the coercive voltage of individual region.
The Lorentzian distribution functions using Eq. 共5兲 with ob-
tained fitting values of t1 and w for the composite films at
different pulse amplitudes are shown in the Fig. 5. The value
of log t1 and w is minimum for the film deposited at 15 V.
The broadening of F共log t0兲 indicates the increase in local

再 冕 冋 再 冉 冊 冎册
field variation 共Fig. 5兲. The variation in the local field could
+⬁ n be related to the dipole defects which arise due to structural
d t
i共t兲 = 2APs 1 − exp − defects such as porosity, clusters and line imperfections as
dt t0

冎
−⬁
seen in Fig. 2. These dipole defects hinders the domain re-
orientation and causes more local field variation between the
⫻F共log t0兲d共log t0兲 , 共4兲 switching media and the nonswitching media sites for the
domain wall motion.19 The nonuniform distribution of local
field causes the variation in the value of t0 for local switching

FIG. 5. 共Color online兲 The Lorentzian distribution function vs logarithmic

characteristic switching time t0 of the switching current transients curves of
共NH4兲0.39K0.61NO3 sample at 共a兲 10, 共b兲 11, 共c兲 12, 共d兲 13, 共e兲 14, and 共f兲 15 FIG. 6. 共Color online兲 The plots of log t1 vs reciprocal of field 共1/E兲 for the
V bipolar pulses. spray deposited NKN film.

Author complimentary copy. Redistribution subject to AIP license or copyright, see http://jap.aip.org/jap/copyright.jsp
024108-5 Dabra et al.
FIG. 7. 共Color online兲 The plot of w vs ␣dm / E2 in NKN film.
of different regions in the composite films. The distribution
of local field due to defects is given by19
冉 冊
k ⌫
F共log Ē兲 = , 共6兲
␲ Ē2 + ⌫2
where Ē is the local field, k is the normalized constant and ⌫
is the half-width at half maximum of the local field distribu-
tion F共log Ē兲, related to the concentration of the pinning
sites. The log t1 and w were related to the microscopic quan-
tities as
␣dm
log t1 ⬇ , 共7兲
E 8
冉 冊
␣dm
w⬇⌫ , 共8兲
E2
where ␣dm is the activation field for domain wall motion.
Figure 6 shows the plots of log t1 versus reciprocal of field
共1/E兲 for the spray deposited NKN film. The linear trend in
the plots is seen. The ␣dm value estimated from the slope of
the Fig. 6 is found to be 17.80 kV/cm and this value is close
to ␣i calculated from Fig. 4. Figure 7 shows the plot of w
versus ␣dm / E2 in NKN film. The ⌫ value was estimated from
the slopes of the plot 共Fig. 7兲 and found to be 4.66 kV/cm.
This activation field may be due to the interaction between
structural defects, porosity 共as depicted in the Fig. 2兲 and
Author complimentary copy. Redistribution subject to AIP license or copyright, see http://jap.aip.org/jap/copyright.jsp
J. Appl. Phys. 108, 024108 共2010兲
ferroelectric domains. The effect of the applied pulse ampli-
tude on switching parameters is indexed in the Table I.
IV. CONCLUSIONS
The hysteresis loops, nonlinear behavior of differential
dielectric constant, polarization switching curves confirm the
existence of ferroelectric phase in NKN sample at room tem-
perature. The FE-SEM and AFM images reveal the forma-
tion of nanoparticles of NKN in the films. The NLS model
based on domain growth limited switching process has found
to be suitable to explain the switching properties. The loga-
rithmic characteristic switching time obeyed the Lorentzian
distribution. The variation of local field was found to be
minimum in the NKN samples at 15 V thus polarization
reversal becomes more probable.
ACKNOWLEDGMENTS
The authors N. Dabra and Jasbir S. Hundal acknowledge
the Chairman, Baba Farid College of Engineering and Tech-
nology, Bathinda for providing the research facilities in the
college.
1
F. Jona and G. Shirane, Ferroelectric Crystals 共Dover, New York, 1993兲.
2
J. F. Scott, Ferroelectric Memories 共Springer, New York, 2000兲.
3
H. M. Duiker and P. D. Beale, Phys. Rev. 41, 490 共1990兲.
4
Y. Ishibashi and Y. Takagi, J. Phys. Soc. Jpn. 31, 506 共1971兲.
5
V. Shur, E. Rumyantsev, and S. Makarov, J. Appl. Phys. 84, 445 共1998兲.
6
J. F. Scott, M. Zhang, R. B. Godfrey, C. Araujo, and L. McMillan, Phys.
Rev. A 35, 4044 共1987兲.
7
S. Swaminathan and S. Srinivassan, Acta Crystallogr. 31, 628 共1975兲.
M. J. Harris, Solid State Commun. 84, 557 共1992兲.
9
S. Sawada, S. Nomura, and Y. Asao, J. Phys. Soc. Jpn. 16, 2486 共1961兲.
10
H. M. Lu and J. R. Hardy, Phys. Rev. B 44, 7215 共1991兲.
11
N. Dabra, J. S. Hundal, K. C. Sekhar, A. Nautiyal, and R. Nath, J. Am.
Ceram. Soc. 92, 834 共2009兲.
12
N. Dabra, J. S. Hundal, K. C. Sekhar, A. Nautiyal, and R. Nath, IEEE
Trans. Ultrason. Ferroelectr. Freq. Control 56, 1627 共2009兲.
13
T. Yanagi and S. Sawada, J. Phys. Soc. Jpn. 18, 1228 共1963兲.
14
T. Yanagi, J. Phys. Soc. Jpn. 20, 1351 共1965兲.
15
K. C. Sekhar, A. Nautiyal, and R. Nath, J. Appl. Phys. 105, 024109
共2009兲.
16
F. Xu, S. T. Mckinstry, W. Ren, B. Xu, Z. L. Xie, and K. J. Hemker, J.
Appl. Phys. 89, 1336 共2001兲.
17
M. H. Lente and J. A. Eiras, J. Appl. Phys. 89, 5093 共2001兲.
18
A. K. Tagantsev, I. Stolichnov, and N. Setter, Phys. Rev. B 66, 214109
共2002兲.
19
J. Y. Jo, H. S. Han, J. G. Yoon, T. K. Song, S. H. Kim, and T. W. Noh,
Phys. Rev. Lett. 99, 267602 共2007兲.