Current Applied Physics 13 (2013) 430e440

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Current Applied Physics

journal homepage: www.elsevier.com/locate/cap

Impedance spectroscopy and piezoresponse force microscopy analysis

of lead-free (1
x) K0.5Na0.5NbO3
xLiNbO3 ceramics
Radheshyam Rai a, *, Indrani Coondoo a, Rashmi Rani b, Igor Bdikin c, Seema Sharma b, Andrei L. Kholkin a
a

Department of Materials and Ceramics Engineering and CICECO, University of Aveiro, Campus Universitario de Santiago, 3810-193 Aveiro, Portugal
Ferroelectric Research Laboratory, Department of Physics, AN College, Patna 800013, India
c
Department of Mechanical Engineering and Centre for Mechanical Technology & Automation, University of Aveiro, 3810-193 Aveiro, Portugal
b

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 16 May 2012
Received in revised form
10 September 2012
Accepted 12 September 2012
Available online 18 September 2012

(1
x) K0.5Na0.5NbO3
xLiNbO3 (where x 0.0, 5.0, 5.5, 6.0, and 6.5 wt.%) (KNLN) perovskite structured
ferroelectric ceramics were prepared by the solid-state reaction method. X-ray diffraction patterns
indicate that single phase was formed for pure KNN while a small amount of second phase (K6Li4Nb10O30,
w3%) was present in LN doped KNN ceramics. Phase analysis indicated the change in the crystal
structure from orthorhombic to tetragonal with increase in LN content. The electrical behavior of the
ceramics was studied by impedance spectroscopy technique in the high temperature range. Impedance
analysis was performed using an equivalent circuit model. The impedance response in pure KNN and
KNLN ceramics could be deconvoluted into two contributions, associated with the bulk (grains) and the
grain boundaries. Activation energies for conductivity were found to be strongly frequency dependent.
The activation energy obtained from dielectric relaxation data was attributed to oxygen vacancies. From
PFM we found that the composition with 6.5 wt.% LN displays stronger piezocontrast as compared to
pure KNN implying an evidence of a pronounced piezoelectric coefcient.
2012 Elsevier B.V. All rights reserved.

Keywords:
Ceramics
Impedance spectroscopy
X-ray diffraction
Dielectric properties
Phase transactions

1. Introduction
Recently, much attention in the area of lead-free piezoelectric
ceramics has been focused on (K0.5Na0.5)NbO3 (KNN) which is
a solid solution of ferroelectric potassium niobate (KNbO3) and
antiferroelectric sodium niobate (NaNbO3). KNN is the only known
lead-free system with a perovskite structure, which has a higher
Curie temperature than the commonly used lead zirconium titanate
(PZT). The high Curie temperature, relatively strong electromechanical coupling factor, presence of morphotropic phase boundary
(MPB) and environmentally friendly constituents are several
advantages of KNN system, thus making it a promising lead-free
piezoelectric material. Moreover, following the work of Saito et al.
[1], KNN-based materials in fact outperformed other important Pbfree bismuth sodium titanate (BNT)-based family.
However, a few drawbacks still prevent wide scale industrial use
of KNN-based materials owing to the volatility of the alkali species
at high temperatures [2] and hygroscopic nature of the reactant
powders [3] leading to non-stoichiometry and inhomogeneous
compositions. All these problems require carefully controlled

* Corresponding author.
E-mail address: radheshyamrai@ua.pt (R. Rai).
1567-1739/$ e see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cap.2012.09.009

manufacturing conditions and low reaction temperatures causing

poor densication behavior. The high dielectric losses related to the
A-site vacancies and oxygen deciencies resulting from the evaporation loss of alkali ions are also detrimental to the KNN ceramics
[4,5]. Various methods to overcome the drawbacks pertinent to
KNN have been undertaken targeting mainly the sintering and
densication behavior of KNN-based ceramics. Densication of
KNN ceramics signicantly improved by hot-pressing, with sintered ceramics reaching w99% of the theoretical density and the
resulting piezoelectric constant nearly twice the value of conventionally sintered KNN [6,7]. Dense ceramics with a high piezoelectric constant of 148 pC/N were achieved by Li et al. [8] using
advanced processing methods compared to 90 pC/N for undoped
KNN prepared using conventional methods [9]. Sintering aids like
CuO and Bi2O3 have also been used to modify pure and doped KNN
ceramics in order to improve the mechanical quality factor Qm [10e
12]. Also, numerous compositional engineering approaches have
been explored to optimize the piezoelectric properties of KNN
materials like adding BaTiO3 [13], SrTiO3 [14], LiNbO3 [15], LiTaO3
[16], LiSbO3 [17], and ZnO [18] to form new solid solutions. Among
these (K0.5Na0.5)NbO3
LiNbO3 (abbreviated as KNLN)-based
ceramics was considered as an excellent candidate for lead-free
piezoelectric ceramics because of high piezoelectric properties
such as d33 210e300 pC/N and high Curie temperature (450  C).

R. Rai et al. / Current Applied Physics 13 (2013) 430e440

Until now, however, there is no report on detailed impedance and

piezoresponse force microscopy (PFM) analysis in KNLN ceramics.
Consequently, the purpose of this paper is to investigate the effect
of the amount of LiNbO3 on microstructure, dielectric, electrical and
local piezoelectric properties of KNN ceramics.

compounds were recorded at room temperature using X-ray

powder diffractometer (Rigaku Miniex, Japan) with CuKa radiaA) in a wide range of Bragg angles 2q
tion (l 1.5405 
(20  2q  60 ) at a scanning rate of 2 min
1. SEM micrographs of
the fractured surface of the sintered samples were obtained with
the help of JEM-2000FX (JEOL Ltd) scanning electron microscope
operated at 20 keV. The dielectric properties of the samples were
determined from RT (room temperature) to 450  C using an
impedance analyzer (PSM Impedance Analyzer 1734) from 100 Hz
to 1 MHz. A commercial Atomic Force Microscope (AFM, Multimode, Nanoscope IIIA) was used for the ferroelectric domain
imaging. The microscope was equipped with an external lock-in
amplier (SR-830, Stanford Research) and a function generator
(FG120, Yokogawa). Stiff conducting Si cantilevers (42 Nm
1, PPPNCHR, Nanosensors) were used for the measurements performed
in ambient environment. The tip had the shape of a polygon-based
pyramid with the height of 10e15 mm and the radius rtip z 10 nm at
the apex. The PFM studies were carried out with Uac 5 V and
f 50 kHz applied voltage on the tip.

2. Experimental procedure
Polycrystalline samples of (1
x) K0.5Na0.5NbO3
xLiNbO3
(where x 0.0, 5.0, 5.5, 6.0, and 6.5 wt.%) (KNLN) ceramics were
prepared by the conventional mixed oxide route. The starting
materials were high purity metal oxide or carbonate powders,
K2CO3 (>99.8%), Na2CO3 (>99.8%), Li2CO3 (>99.99%), and Nb2O5
(>99.9%). The powders were weighed according to the stoichiometric proportion for the required compositions and mixed for 48 h
using propan-2-ol and zirconia media. The powders were calcined
at 920  C for 4 h, after that the resulting powders were mixed
thoroughly with a PVA binder solution. Cylindrical pellets were
prepared in a uniaxial press with a 10 mm diameter die at 100 MPa
and then sintered at 1000  C for 4 h and nally cooled to room
temperature at the rate of 180  C/h. Silver paste as electrodes were
applied on the top and bottom surfaces on the samples for the
electrical measurements.
The formation and quality of compounds were veried with Xray diffraction (XRD) technique. The XRD patterns of the

3. Results and discussion

Fig. 1 shows XRD of the KNN
LN ceramics for different
compositions with x 0.0, 5.0, 5.5, 6.0, and 6.5 wt.%. The crystal
structure changes from orthorhombic to tetragonal with increasing

Tetragonal phase
appears

KNN
KNN-5LN
KNN-5.5LN
KNN-6.0LN
KNN-6.5LN

Intensity ( a. u. )

30

40

50

44

60

45

a
b
c

4.04

46

3.0

density

2.8

2.6

4.02

2.4
3

Lattice Parameter (

47

2 (degrees)

2 (degrees)

4.00
2.2

gm/cm

20

(020)

(202)

(113)
(311)

(202)
(020)

(212)
(121)

(002)
(111)

KNN
KNN - 5.0LN
KNN - 5.5LN
KNN - 6.0LN
KNN - 6.5LN

(101)
(010)

Intensity ( a. u. )

431

3.98
2.0
3.96

1.8

1.6

3.94
0

Conc. LN (wt%)
Fig. 1. (a) XRD of the (1
x) K0.5Na0.5NbO3
xLiNbO3 ceramics and (b) enlarged XRD patterns of the ceramics for 2q 44e48 (c) lattice parameter and density of different
compositions x 0.0, 5.0, 5.5, 6.0 and 6.5 wt.% respectively.

432

R. Rai et al. / Current Applied Physics 13 (2013) 430e440

Fig. 2. SEM micrograph illustrating typical microstructure for (1
x) K0.5Na0.5NbO3
xLiNbO3 ceramics of different compositions x 0.0, 5.0, 5.5, 6.0 and 6.5 wt.%.

x. Since the crystal structure of KNN (perovskite structure) is very

different from LiNbO3 (ilmenite structure), the single phase
formation suggests that Li and Nb3 have diffused into the KNN
lattice, with Li entering the (Na0.5K0.5) site and Nb5 occupying
the B site, to form a homogeneous solid solution. As x increases,
a tetragonal phase appears and increases continuously. It is also
noted that the diffraction peaks shift slightly toward low diffraction

angles implying an increase in the lattice parameters with

increasing x. This may be attributed to the smaller ionic radii of Li
as compared to those of Na (1.16 
A) and K (1.52 
A). In the
orthorhombic zone, the lattice constants c and a have very close
values, which explains the two peak splitting of (200) reections at
a 2q 45.5 for an orthorhombic structure, rather than three peak
splitting. Lattice constants and density of KNN-LN ceramics

Fig. 3. (a) Variation of dielectric constant, (b) loss (tan d) with temperature (c) plots of peak r and Tc and (d) r and transition temperature vs. doping concentration at 100 kHz for
(1
x) K0.5Na0.5NbO3
xLiNbO3 ceramics of different compositions x 0.0, 5.0, 5.5, 6.0 and 6.5 wt.%.

R. Rai et al. / Current Applied Physics 13 (2013) 430e440

depending on LiNbO3 concentration were calculated as shown in

Fig. 1(c). Lattice constants of KNN ceramics in orthorhombic
symmetry were calculated as a 3.9551 
A, b 3.95765 
A and
c 4.0502 
A, which are similar to the bulk KNN. As x changes the
crystal structures changed from orthorhombic to tetragonal
symmetry, which indicated that MPB coexisted orthorhombic and
tetragonal phase. The small XRD peaks at 33 and 52 for KNN
doped with for x 5.5 and x 6.0% are attributed to an orthorhombic phase of Nb2O5 (O-Nb2O5) corresponding to JCPDS le
number 527-1313. These peaks are probably due to the formation of
Nb-rich second phase leading to the creation of A-site vacancies in
the ABO3 perovskite structure.
Fig. 2 presents the scanning electron micrographs for fractured
surfaces of KNN
xLN with 0.0, 5.0, 5.5, 6.0, and 6.5 wt.%. The
fracture surfaces show homogeneous grains with dense structure.
The grain size of all samples is of the order of 2e4 mm.
The temperature dependence of the permittivity and loss shown
in Fig. 3(a and b) conrms the presence of a phase transition from
orthorhombic to tetragonal at w200  C for pure KNN and tetragonal to cubic at w380  C. However, the composition containing
6.5 wt.% LN, the peak related to phase transition temperature from
the orthorhombic to the tetragonal is not observed. It is probably
located below room temperature as has been observed in the case
of 7% lithium doped KNN ceramics [19]. It is also observed that with
6.5 wt.% LN in KNN, the dielectric permittivity is reduced while the
Curie temperature increased (Fig. 3c and d). The loss tangent (tan d)
is also found to decrease with LN addition. A-site vacancy created
by the Nb rich phase (as is evident from XRD spectra), increases the

dielectric loss factor for x > 5.5% while the room temperature
dielectric constant value and the dielectric loss value are almost
unaffected by the introduction of vacancies. The A- and B-site
elements have valence states of 1 and 5, respectively, while
oxygen has
2. In KNN ceramics, Nb is believed to be incorporated
at the B-site of the perovskite lattice and therefore acts as an
acceptor. Oxygen vacancies are formed and when they combine
with Nb ions, defect dipoles are created. These defect dipoles move
along the direction of polarization and are based on the principle of
symmetry conforming of point defects and lead to hard doping
effects. It is well known that piezoelectrics with low permittivity
are useful for energy harvesting because the gure of merit
describes the operation of the energy harvesting system [20].
According to this, a material with low permittivity will have high
voltage induced by strain. In this regard, the composition with
6.5 wt.% LN is expected to exhibit a higher hij.
Fig. 4(a and c) shows variation of the real part of impedance
(Z0 ) as a function of frequency (103e106 Hz) for different
temperatures and compositions. The pattern shows a sigmoidal
variation as a function of frequency in the low frequency region
followed by a saturation region in the high frequency region. This
suggests of the manifestation of the mixed nature of polarization
behavior in the material. The merger of the real part of impedance
(Z0 ) in the frequency domain for all temperatures indicates
a possibility of the release of the space charge as a result of
lowering in the barrier properties of the material. These results
indicate that the electrical conduction will increase with rise in
temperature and the phenomenon is dependent on the release of

b 400

5LN
5.5LN
6LN
6.5LN

RT
80

433

5LN
5.5LN
6LN
6.5LN

RT

300

z"(k)

Z'(k)

60

40

200

100

20

0
10

100

1000

10

20
0

5LN
5.5LN
6LN
6.5LN

400 C

1000

10

5LN
5.5LN
6LN
6.5LN

At 400 C

z"(k)

15

Z'(k)

100

Frequency (kHz)

Frequency (kHz)

0
10

Frequency (kHz)

100

1000

10

100

1000

Frequency (kHz)

Fig. 4. (a, c) Variation of real part impedance (Z0 ) and (b, d) imaginary part of the impedance (Z00 ) of (1
x) K0.5Na0.5NbO3
xLiNbO3 (where x 0.0, 5.0, 5.5, 6.0, and 6.5 wt.%)
ceramics with frequency at different temperatures.

434

R. Rai et al. / Current Applied Physics 13 (2013) 430e440

the space charge. The extent of steepness in the low frequency

region is observed to have a very strong dependence of Z0 on the
composition irrespectively of temperature. Further, the impedance value is observed to increase rst in the low frequency region
with rise in temperature followed by a relative decrease at
subsequently higher temperatures. The result may be related to
a change in the charge-ordering pattern with temperature; the
effect showing clearly perceptible change in its behavior in the
low frequency region. A decreasing trend of Z0 with temperature
rise suggests the presence of negative temperature coefcient of
resistance (NTCR) in the material in the low frequency region but
tends to merge in the high frequency region at almost all
temperatures. These results indicate a possibility of increase in ac
conductivity with increasing temperature in the high frequency
region, possibly due to the release of space charge. Fig. 4(b and d)
exhibits frequency and temperature dependence of imaginary
part of impedance (Z00 ) for KNLN solid-solutions. The trend of the
variation of Z00 with frequency is the typical of the presence of the
electrical relaxation in the materials which is temperaturedependent. The asymmetric broadening of the peaks suggests
the presence of the electrical process in the material with a spread
of relaxation time. The shifting of the peaks indicates that the net
relaxation time is decreasing with the increase in temperature. In
low temperature/frequency range, Z00 has very high value for all
the compositions which decreases with increasing frequency and
attains low values. This is an interesting (unusual) trend in the
variation of Z00 with frequency/temperature for KNLN ceramic
samples. The appearance and nature of peaks at a characteristic
angular frequency umax ( 2pfmax) provides information on the
type and strength of the dielectric relaxation phenomenon

occurring in the material. The nature of this pattern suggests the

presence of a weak dielectrical relaxation above 400  C in KNLN
system. At low temperatures (400  C), the spectrum shows
a monotonous decrease having dispersive nature in the low
frequency region followed by a plateau at higher frequencies. This
observation clearly testies the presence of electronic, dipolar and
space charge polarizations in the material, and the appearance of
the peak(s) being a result of dipolar contribution.
Fig. 5(a and c) shows the variation of real part of modulus as
a function of frequency at different temperatures for all compositions of KNLN. The variation of M0 with frequency for all the
samples shows a dispersion tending toward MN (the asymptotic
value of M0 at higher frequencies) and dispersion shifts toward
higher frequency side with increasing temperature. Monotonous
dispersion with increasing frequency at lower temperatures may be
due to the short range mobility of charge carriers. It comprises of
the features such as a very low value (approaching to zero) of M0 in
the low frequency region and a continuous dispersion with
frequency. Such results may possibly be related to a lack of
restoring force governing the mobility of the charge carriers under
the action of an induced electric eld. This behavior supports that
as the frequency increases; each ion moves a shorter and shorter
path of electric eld, until the electric eld changes so rapidly that
the ions only rattle within the connement of their potential
energy wells. The value of M0 decreases with increasing temperature in the studied frequency range. Fig. 5(b and d) depicts variation
of imaginary part of modulus (M00 ) with frequency. High frequency
range side represents that ions are separately conned to their
potential wells, and the ion can make only the localized motion
within the wells [21,22].

Fig. 5. (a, c) Plot of real part of modulus (M0 ) and (b, d) imaginary part of modulus (M00 ) with frequency of (1
x) K0.5Na0.5NbO3
xLiNbO3 (where x 0.0, 5.0, 5.5, 6.0, and 6.5 wt.%)
ceramic.

R. Rai et al. / Current Applied Physics 13 (2013) 430e440

Fig. 6(aee) shows complex impedance spectrum (Nyquist plot)

of samples of different compositions at 300, 350, 400, 425 and
450  C, respectively. We have tted the experimental data (Fig. 6f)
for all the compositions with the equivalent circuit using
commercially available software Z Simp Win Version 2. There is
a close agreement observed between experimental and tted data.
It is observed that at lower temperatures a single semi-circular arc
appears. This single semicircular arc suggests the presence of grain
interior (bulk) property of the material [23]. However, at higher
temperatures, another arc is present, and the spectrum comprises

two semicircular arcs with their centers lying below the real axis for
all compositions (temperatures above 400  C). The high frequency
semi-circle (rst arc) can be attributed to the bulk (grain interior)
properties of the material arising due to a parallel combination of
bulk resistance (Rb) and bulk capacitance (Cb). The low frequency
(second) semicircular arc of the impedance spectrum at elevated
temperatures (pattern at 425 and 450  C, respectively) has been
attributed to the presence of grain boundary arising due to
a parallel connection of grain boundary resistance (Rgb) and
capacitance (Cgb). Two semi-circular arcs of the impedance

600

5LN
5.5LN
6LN
6.5LN

300 C
500

435

250

350 C

5LN
5.5LN
6LN
6.5LN

200

400

z"(k)

z"(k)

150

300

100

200
50

100

0
0

200

400

z'(k)

600

5LN
5.5LN
6LN
6.5LN

20

150

200

250

5LN
5.5LN
6LN
6.5LN

425 C
6

15

z"(k)

z"(k)

100

z'(k)

25

400 C

50

10

0
0

10

15

20

25

z'(k)

z'(k)

5LN
5.5LN
6LN
6.5LN

450 C

Z measured- 5LN
Z calculated- 5LN
Z measured- 5.5LN
Z calculated- 5.5LN
Z measured- 6LN
Z calculated- 6LN
Z measured- 6.5LN
Z calculated- 6.5LN

20

'' ()

z"(k)

15

(Q)

(Q)

(R)

(R)

10

0
0

z'(k)

10

15

20

' ()

Fig. 6. (aef). Variation of real and imaginary part of impedance of different (1
x) K0.5Na0.5NbO3
xLiNbO3 (where x 0.0, 5.0, 5.5, 6.0, and 6.5 wt.%) ceramics at 300, 350, 400, 425
and 450  C respectively.

436

R. Rai et al. / Current Applied Physics 13 (2013) 430e440

Table 1
The value of bulk resistance (Rb), grain boundary resistance (Rgb), bulk capacitance
(Cg) and grain boundary capacitance (Cgb) of LN doped KNN ceramics of different
compositions x 0.0, 5.0, 5.5, 6.0 and 6.5 wt.%.
x

Temp ( C)

Rg (kU)

Rgb (kU)

Cg (nF)

Cgb (nF)

400
425
450
400
425
450
400
425
450
400
425
450

4.668
2.174
1.539
13.133
2.029
1.468
3.680
2.249
1.942
9.348
3.845
1.970

7.087
2.978
2.279
22.459
2.978
1.879
4.885
3.228
3.667
14.596
6.438
3.139

3.683
5.765
2.346
2.859
4.536
2.102
4.006
3.504
2.530
1.839
4.471
2.144

2.426
3.732
1.921
1.672
3.089
1.642
3.081
2.441
1.334
1.178
2.670
1.345

5.5

6.5

spectrum may be due to grain bulk and grain boundary contributions, which is consistent with the brick-layer model for a polycrystalline material [24]. These semicircular arcs can be expressed
in terms of an equivalent circuit (Fig. 6f) built up by cascading of
two parallel resistance and capacitance connected in series (RC
circuits), each being responsible for a semi-circle. As a result, both
the grain bulk and the grain boundary phenomena occur simultaneously with increasing temperature. This effect may be related to
the change in microstructure governed predominantly by the
thermal state of the material, which throws a signicant light on
the relationship of temperature-dependent microstructure and
electrical properties of the materials. The intercept of the semicircular arc on the real axis gives the dc resistance of the material. It
is seen from Fig. 6 that the dc resistance decreases with the increase
in temperature as well as the LN content in the KNN ceramics. The

Fig. 7. (aee) Variation of real and imaginary part of modulus with temperature of (1
x) K0.5Na0.5NbO3
xLiNbO3 (where x 0.0, 5.0, 5.5, 6.0, and 6.5 wt.%) ceramics.

R. Rai et al. / Current Applied Physics 13 (2013) 430e440

values of the electrical parameters by tting the measured data

with the equivalent circuit at 400  C are given in Table 1. The
observed depressed semicircular arcs having centers lying below
the real impedance (Z0 ) axis is due to the presence of distributed
phase elements. The relaxation process associated with this
observation is non-ideal in nature. The non-ideal behavior originated from several factors grain orientations, like grain size
distributions, grain boundaries, atomic defect distribution and
stressestrain phenomena.
A relative comparison of the complex impedance spectrum and
modulus spectrum for all the concentrations of LN in KNN shows
one arc in the modulus pattern with different radii (Fig. 7) whereas
two arcs in the impedance spectrum. This result may be explained
in term of the capacitance effect by the fact that in an equivalent
circuit comprising of two parallel RC circuit elements (connected in
series), the resistance of one may be much lower than that of the
other, but the two capacitance values may not be too different
leading to a well resolved arc pattern in the modulus spectrum
unlike that in the impedance pattern [23, 24]. Furthermore, the
modulus spectrum shows a notable change in the shape with
increasing temperature suggesting a probable change in the
capacitance value of the KNLN material as a function of temperature as well as concentration of LiNbO3. This suggests that the
dielectric behavior of the solid-solution is controlled by the LiNbO3
addition.
The variation of normalized complex electric impedance with
normalized frequency is shown in Fig. 8. This is known as a master
curve, which enables us to shed light on the dielectric behavior of
the material as a function of temperature. The overlap of the curves

437

at different temperatures into a single master curve indicates that

the relaxation describes the same mechanism at different
temperatures. This behavior is represented by the non-exponential
type of conductivity relaxation [25]. A non-exponential type
conductivity relaxation suggests the possibility that the ion
migration takes place via hopping mechanism accompanied by
a consequential time dependent mobility of other charge carriers of
the same type in the vicinity. The master modulus shows (1) the
slight shift in the impedance peak pattern, (2) the similar shape and
pattern with slight variation in full width at half maximum
(FWHM) with increasing temperature, and (3) the asymmetric
nature of the curves which is a characteristic of the nonexponential behavior of conductivity. The FWHM of the peaks is
wider than that of the Debye peak, which also suggests the presence of non-Debye-type relaxation phenomena.
Fig. 9 shows the variation of AC conductivity (sac) with
temperature at 10 kHz frequencies for all samples. The nano
appreciable variation of sac with temperature indicates the
multiple relaxations. The ac conductivity is dependent on the
capacitance of the sample given by the expression.

sac 60 00
where 0 is the vacuum dielectric constant, 6 is the angular
frequency, 0 and 00 are the real and imaginary part (the dielectric
loss) of the dielectric permittivity. The AC conductivity increases
with increase in temperature showing a negative temperature
coefcient of resistance (NTCR) behavior. Arrhenius equation was
used for the calculation of activation energy for the ceramics,

Fig. 8. (aed) Impedance scaling behavior of (1
x) K0.5Na0.5NbO3
xLiNbO3 (where x 0.0, 5.0, 5.5, 6.0, and 6.5 wt.%) ceramics in the master curves.

438

R. Rai et al. / Current Applied Physics 13 (2013) 430e440

Fig. 9. Temperature dependence of the sac of (1
x) K0.5Na0.5NbO3
xLiNbO3 (where x 0.0, 5.0, 5.5, 6.0, and 6.5 wt.%) ceramics at 10 kHz frequencies.

s s0 Ea =kB T
sac is the AC conductivity, Ea is the activation energy, kB is the
Boltzmann constant, T is the temperature in Kelvin scale and s0 is
the dc conductivity.
The activation energy calculated at 10 kHz in the temperature
range (390e330  C) and (200e150  C) is between 1.30 eV and
0.55 eV respectively. The low value of activation energy obtained
could be attributed to the inuence of electronic contribution to the
conductivity; The increase in conductivity with temperature may
be attributed to the oxygen vacancies due to the loss of oxygen
during the sintering process and leave behind free electrons
making them n type semiconductor [26e28]. In oxide ferroelectrics, doubly charged oxygen vacancies are the most mobile charges
and play an important role in the conduction process. The volatilization of A-site elements (Na and K) will result in the deciency in
A-site cations, and thereafter the generation of oxygen vacancies
due to the valence balance, which may alter the lattice distortion
and thus inuence the dielectric behavior of these ceramics.
Fig. 10(a) shows a representative AFM image of the ceramic
sample. Following the topography acquisition, the AFM was
switched to the piezoresponse force microscopy (PFM) regime in
which the conducting tip is scanned in contact mode while an ac
voltage (Vac) is applied between the tip and Ag electrode (Fig. 10b).

In these conditions, we could measure both out-of-plane (OOP) and

in-plane (IP) polarization components [29]. After the scan we were
able to detect IP signal due to a shear component of the piezotensor
(d15), corresponding to the polarization parallel to the surface
sample, and OOP that reects polarization perpendicular to the
surface [normal component of the piezotensor (d33)]. Comparison
of the topography (Fig. 10a) and PFM (Fig. 10b and c) images attests
that the polishing scratches and other corrugations of the sample
surface are not reected on the corresponding PFM images thus
giving an evidence of the piezoelectric nature of the contrast. For
OPP component (Fig. 10b), the contrast is roughly proportional to
the effective d33 coefcient and determined by the projection of the
polarization vector P on the normal N to the ceramic surface. The
dark and bright contrasts correspond to the polarization head
directed to the sample bulk or to the surface, respectively. IP piezoresponse image (Fig. 10c) is complementary to the OPP picture
and reects the effective shear d15 piezoelectric coefcient
proportional to the corresponding IP component of the
polarization.
Ferroelectric domain distributions distributions of the pure and
6.5 wt.% LN concentration samples are shown in Fig. 11(a and b).
The different grains of the respective materials are represented by
the colored regions in the gure. The histograms of the OPP PFM
signal from images are represented in Fig. 11c. It has a clear
asymmetric shape with a maximum slightly shifted toward the

Fig. 10. AFM images of KN 6.5 LN ceramic samples: (a) topography, (b) OPP PFM, and (c) IP PFM. Uac 5 V, f 50 kHz.

R. Rai et al. / Current Applied Physics 13 (2013) 430e440

439

Fig. 11. OPP PFM images of pure (a) and 6.5 wt.% LN (b), (c) and (d) represent the LN concentration dependence of the piezoresponse histograms of out-of-plane (OPP) signal
representing piezoelectric activity.

negative or positive values. It means that the number of grains with

the polarization head terminated at the free surface exceeds the
number of oppositely oriented dipoles. Under large magnication,
a shoulder on the positive slope was observed that may represent
a maximum in the number of grains having the same effective
piezoelectric coefcient. Since the sign of the piezosignal is referred
to the direction of the polarization projection onto the samples
normal, it can be inferred that all investigated samples have
average non-zero piezoresponse in the unpoled state. In our denition, it corresponds to the polarization direction directed from
the free surface into sample (self-polarization effect). This corresponds to the peak shift as observed in Fig. 11c. The shifts to positive
and negative values is related to different signs of self-polarizations
and related to the preferred orientation of surface domains. The
effective piezoelectric coefcient, d33eff was determined from the
peak half width (Fig. 11d). It is observed that the composition with
6.5 wt.% LN displays stronger piezocontrast as compared to pure
KNN implying an evidence of a pronounced piezoelectric coefcient. A broad response in Fig. 11(c) for 6.5 wt.% LN corresponds to
the trend shown in Fig. 11(d).

higher temperature side on increasing LN concentration, (ii)

decrease in dielectric constant and loss on increase in LN content,
(iii) follows Arrhenius relation in higher temperature region, (iv)
bulk or grain conduction up to 400  C, (v) grain boundary
conduction up to 450  C, (vi) temperature dependent relaxation
phenomena. The activation energy values obtained for different LN
content suggest that the electrical conduction in KNLN is mainly
due to the mobility of the ionized oxygen defects. We observed that
the composition with 6.5 wt.% LN displays stronger piezocontrast as
compared to pure KNN implying an evidence of a pronounced
piezoelectric coefcient.
Acknowledgments
The authors are grateful to the Foundation for Science and
Technology of Portugal (FCT) for nancial support within the
projects PTDC/CTM-CER/115085/2009 and PTDC/FIS/108025/2008.
The work is partly supported by the EU network Enermat.aa. Seema
Sharma wish to acknowledge Department of Science and Technology, Govt of India (SR/S2/CMP-39/2006), India for the nancial
support under a research project scheme.

4. Conclusions
(1
x) K0.5Na0.5NbO3
xLiNbO3 (x 0e6.5 wt.%) lead free
piezoelectric ceramic has been synthesized by conventional solid
state reaction technique. The effect of different amounts of Li and
Nb content on the phase structure and electric properties of KNLN
ceramics were systematically investigated. XRD studies showed the
transition from orthorhombic to tetragonal above x 5.5 wt.% of
LN. Detailed studies of dielectric and electrical properties indicate
that the material exhibits: (i) shift of Curie temperature toward

References
[1] Y. Saito, H. Takao, T. Tani, T. Nonoyama, K. Takatori, T. Homma, T. Nagaya,
M. Nakamura, Nature 432 (2004) 84e87.
[2] E. Hollenstein, M. Davis, D. Damjanovic, N. .Setter, Appl. Phys. Lett. 87 (2005)
182905.
[3] H.L. Du, Z.M. Li, F.S. Tang, S.B. Qu, Z.B. Pei, W.C. Zhou, Mater. Sci. Eng. B 131
(2006) 83.
[4] P.C. Goh, K. Yao, Z. Chen, J. Am. Ceram. Soc. 92 (2009) 1322.
[5] N. Hagh, A. Safari, J. Electroceram. 18 (2007) 339.
[6] R.E. Jaeger, L. Egerton, J. Am. Ceram. Soc. 45 (1962) 209.

440
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]

R. Rai et al. / Current Applied Physics 13 (2013) 430e440

R.P. Wang, R.J. Xie, T. Sekiya, Y. Shimojo, Mater. Res. Bull. 39 (2004) 1709.
J.F. Li, K. Wang, B.P. Zhang, L.M. Zhang, J. Am. Ceram. Soc. 89 (2006) 706.
J.G. Hao, Z.J. Xu, R.Q. Chu, Mater. Chem. Phys. 118 (2009) 229.
M. Matsubara, T. Yamaguchi, W. Sakamoto, J. Am. Ceram. Soc. 88 (2005) 1190.
J.G. Hao, Z.J. Xu, R.Q. Chu, J. Mater. Sci. 44 (2009) 6162.
J.G. Hao, Z.J. Xu, R.Q. Chu, J. Electron. Mater. 39 (2010) 347.
Y. Guo, K. Kakimoto, H. Ohsato, Jpn. J. Appl. Phys. 43 (2004) 6662e6666.
Y. Guo, K. Kakimoto, H. Ohsato, Solid State Commun. 129 (2004) 279e284.
Y. Guo, K. Kakimoto, H. Ohsato, Appl. Phys. Lett. 85 (2004) 4121e4123.
Y. Guo, K. Kakimoto, H. Ohsato, Mater. Lett. 59 (2005) 241e244.
S.J. Zhang, R. Xia, H. Hao, H.X. Liu, T.R. Shrout, Appl. Phys. Lett. 92 (2008)
152904.
[18] S.H. Park, C.W. Ahn, S. Nahm, Jpn. J. Appl. Phys. 43 (2004) 1072e1074.
[19] E. Hollenstein, D. Damjanovic, N. Setter, J. Eur. Ceram. Soc. 27 (2007) 4093.

[20] R. Elfrink, J. Micromech. Microeng. 19 (2009) 094005.

[21] R.N.P. Choudhary, Dillip K. Pradhan, C.M. Tirado, G.E. Bonilla, R.S. Katiyar,
Phys. Status Solidi (b) 244 (2007) 2254e2266.
[22] A. Shukla, R.N.P. Choudhary, Physica B Condens. Matter 406 (2011) 2492e
2500.
[23] D.C. Sinclair, A.R. West, J. Appl. Phys. 66 (1989) 3850.
[24] A. Shukla, R.N.P. Choudhary, A.K. Thakur, J. Phys. Chem. Solids 70 (2009) 1401.
[25] A. Shukla, R.N.P. Choudhary, Curr. Appl. Phys. 11 (2011) 414.
[26] J.R. Macdonald, Impedance Spectroscopy, Emphasizing Solid Materials and
Systems, Wiley Interscience Publ., New York, 1987.
[27] S. Poykko, D.J. Chadi, Appl. Phys. Lett. 76 (2000) 499e501.
[28] S. Steinsvik, R. Bugge, J. Gjonnes, J. Tafto, T. Norby, J. Phys. Chem. Solids 58
(1997) 969e976.
[29] N. Balke, I. Bdikin, S.V. Kalinin, A.L. Kholkin, J. Am. Ceram. Soc. 92 (2009) 1629.