Journal of Alloys and Compounds 615 (2014) 1824

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Journal of Alloys and Compounds

j o u r n a l h o m e p a ge : w w w . e l s e v i e r . co m / l o c a t e / j a l c o m

Microwave dielectric properties of lanthanum based complex

perovskites
a a b b a,
Masood A. Nath , Saroj L. Samal , K. Rama Obulesu , K.C. James Raju , Ashok K. Ganguli
a
Department of Chemistry, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi 110 016, India
b
School of Physics, University of Hyderabad, Hyderabad 500 046, India
abstract

article info The present investigation discusses the synthesis and dielectric properties of three series of oxides of the
formula La2BaTi2M1 xCuxO9 (where M = Mg, Zn and Cd). The reactions have been carried out via solid
Article history: state method and all the compositions crystallize in the disordered cubic perovskite structure. Suitable
Received 1 March 2014 substitution at both A and B sites lead to enhancement in the dielectric properties at high frequencies. The
Received in revised form 31 May relative permittivity and loss tangent have been measured at X-band (8.212.4 GHz) and Ku-band (12.418
2014 Accepted 18 June 2014 GHz) frequencies. The oxides show a dielectric constant of 2030 while the dielectric loss is quite low in the
Available online 2 July 2014 3 4 2
order of 10 10 (at 500 kHz) and 10 at X and Ku-band. There is scope for further investigations in these
systems to realize useful materials for microwave applications.
Keywords:
Perovskites 2014 Elsevier B.V. All rights
Electronic materials reserved.
Dielectric properties
Density

1
Present address: Department of Applied Sciences, Higher College of
Technology-Muscat, P.C 133, Alkhuwair, Muscat, Oman.

1. Introduction http://dx.doi.org/10.1016/j.jallcom.2014.06.12
2 0925-8388/ 2014 Elsevier B.V. All rights
reserved.
Rapid growth of microwave communication systems has stim-
ulated a search for new materials for applications as capacitors,
resonators, filters, oscillators etc [16]. Such components at high
frequency range (GHz) are used for wireless telecommunication
systems, radar, local area network and medical equipments. Among
various components of communication devices, dielectric
resonators are very important and used for carrying desired micro-
wave information. The materials for dielectric resonators are pres-
ently employed as bulk ceramics in microwave communication
devices. The ceramic pieces are designed to be dielectric resona-
tors, resonating at the frequency of the carrier signal to allow that
signal to be efficiently separated from other signals in the micro-
wave band [7]. The resonant frequency of the dielectric component
depends on the dielectric constant of the dielectric and the size of
the resonator. In other words, the size of the resonator at any par-
ticular resonant frequency depends on the inverse of the square
root of the dielectric constant of the dielectric, and thus larger the
dielectric constant the smaller is the ceramic component needed.
Compared to a vacuum cavity, for example (K 1) a dielectric with
K 36 will have the same resonant frequency at 1/6 the size [8].
Thus materials with the highest possible dielectric constant would
seem to be optimal for the task. Ferroelectric

Corresponding author. Tel.: +91 26854715.

E-mail address: ashok@chemistry.iitd.ernet.in (A.K. Ganguli).

materials possess high dielectric constant but are still not suitable
for resonators because there are other requirements for the mate-
rials to be used as resonators. The primary requirement of materi-
als to be used as dielectric resonators are high dielectric constant
(e0 > 25) and high quality factor or low loss (Q = 1/tan d > 5000),
and a temperature coefficient of resonant frequency ( sf) as close to
zero as possible [912]. These properties are interrelated and an
attempt to improve one of the parameters commonly leads to
worsening of the others. Therefore, the challenge is mainly to find
a material with the optimal parameters. Perovskite-related non-
ferroelectric materials are known to be appropriate for microwave
applications. Owing to their ability to form solid solutions with
possibility of wide range of substituting atoms, the perovskite oxi-
des are intensively explored to obtain materials with optimal prop-
erties. Series of low-loss perovskite system have been earlier
investigated for microwave applications [13]. Lanthanum and
strontium based complex perovskites were found to be of great
interest owing to their high quality factor [1418]. These perovsk-
ites have low tolerance factor because of considerable size misfit of
constituents which is reflected by the tilting of corner-shared octa-
hedra, displacement of A-cations and ordering of B-cations.
[16,17,19]. Correlations between structure and microwave dielec-
tric characteristics of perovskite compounds have been discussed
earlier [20,21]. Reaney [3] have established a relationship between
the temperature coefficient of the related permittivity (se) and the
tolerance factor for Ba- and Sr-based complex perovskites of the
2+ 4+
type A (B0n B001 n) O3 as well as their solid solutions. Wise et
al. [22] have attributed tuning of sf in microwave dielectrics to
dilu-tion of the average ionic polarizability and to the onset of an
M.A. Nath et al. / Journal of Alloys and Compounds 615 (2014) 1824

octahedral tilt transition above room temperature. Microwave loss in ceramics is known to result from both extrinsic factors (porosity,
impurities, grain boundaries etc) and intrinsic ones (lattice absorp-tion due to crystal anharmonicity) [23,24]. Usually, the extrinsic
contribution can be minimized using proper processing conditions. Change of lattice anharmonicity and associated dielectric loss in solid
solutions depends on the variation of crystal symmetry, namely a change of cell distortion, octahedral tilting, cation order-ing etc. Thus there
are several factors affecting the Q-factor (Q = 1/ Dielectric loss).

Among various dielectric compositions, complex perovskite compounds such as Ba(Mg 1/3Ta2/3)O3 [2528] and Ba(Zn1/3Ta2/3)O3 [29
33] are known to have the best microwave dielectric properties. However, significant efforts are being pursued to develop new mate-rials
with high dielectric constant and low cost (prepared at low sintering temperature). We have been interested in designing com-plex oxide
materials related to the perovskite structure with tetra and pentavalent ions as the B and B 0 ions in the A(B1/3B02/3)O3 oxides [3440]. In
addition we have varied the A-ions to obtain oxides of the type A2A0B2B0O9 and A2A0B2(B01 xB00x)O9. The above formula may also be
written as (A2/3A01/3)(B2/3B01/3)O3 corresponding to a disordered cubic structure. The specific systems investigated in this study are
La2BaTi2M1 xCuxO9 (where M = Mg, Zn and Cd) dielectric materials. The basic dielectric parameters ( e, sf and Q) have been determined
and compared with existing microwave materials.

2. Experimental procedure

Oxides with compositions La 2BaTi2Zn1 xCuxO9, La2BaTi2Mg1 xCuxO9 and La2BaTi2Cd1 xCuxO9 (where x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0) were prepared by the solid
state method. Stoichiometric amount of La 2O3 (Aldrich 99.9%), BaCO3 (Loba Chemie 99.0%), TiO2 (Aldrich 99.9%), ZnO, MgO and CdO (CDH 99.9%), were thor-oughly
mixed and ground in an agate mortar to obtain a homogeneous mixture. The rare earth oxides were preheated at 900 LC before weighing. The mixtures were loaded in a
ceramic boat and fired at 950 LC for 12 h. The above mixture was then further calcined at 1100 LC for 24 h and 1200 LC for 6 h with intermittent grinding. The powder was
then mixed with 5% PVA (w/v), pressed into a disk (8 mm diameter and 24 mm thickness) which was then sintered at 1250 LC for 12 h. For dielectric measurements the
disks were coated with silver paste for electrical contacts. The measurements were carried out with an LCR-meter (Agilent, 4284L) using the par-allel plate method with the
help of two copper rods on either side of the plate and the whole setup was kept in a furnace. The data were collected within a frequency range of 250500 kHz and at
various temperatures ranging from room temperature to 300 LC.

For microwave measurements the powder was mixed with PVA and pressed into rectangular disks (10.16 mm 22.86 mm) and compressed under a pressure of 10 kPa to
fit into the X-band wave-guide (test set, Agilent model X11644A, WR-90), backed by a metal sheet. The measurements were carried out by inserting the samples inside the
*
X-band waveguide. In order to determine the complex permittiv-ity at X-band frequency (8.212.4 GHz), the complex scattering parameters (S ) cor-responding to
reflection modes (S11 or S22) were measured using a vector network analyzer (VNA, Agilent model PNA-L N5230A). The real and imaginary parts of com-plex permittivity
(er = e0 j00 ) was calculated from scattering parameters by means of material measurement software (Agilent software module 85071) as described in [41]. The reflection
losses of the samples were also measured directly.

In order to determine the dielectric properties at Ku band (1218 GHz), we adopted the multiline method [42,43] for determining the propagation constant from the
measured scattering parameters. The real and imaginary complex permit-tivity has been calculated from the complex propagation constant. In this method, two sample
pieces of different lengths were machined to appropriate dimensions in order to fill the cross section of a Ku- band wave-guide. The wave guide sample holder is connected
to the Agilent E8361C PNA Network Analyzer through a coaxial to wave guide adapter after a full two port calibration with the coaxial to wave guide adapters. The complex
propagation constant c = a + jb is determined from the measured scattering parameters using the procedures explained in Mark [42] and Sudheendran et al. [43] and the
dielectric parameters of the samples were calculated using Eqs. (1) and (2) given below;

2 p2

0 b a&
2
e x l0 e0
e

00 2ae0 1

where a is the longer width of the wave guide, x is the angular frequency,p l0 and e0 are the free space permeability and permittivity and k = 2p/k and k = x l0 e0 e0 .

The density of all the samples was measured with the help of Gas Pycnometer (AccuPyc-II 1340 from Micromeritics) by using helium gas. The instrument mea-sures
the density and other parameters in 10 cycles. Powder X-ray diffraction (PXRD) data was collected using Cu K a source with Ni-filter using a Bruker D8-Advanced X-ray
diffractometer. Data for Rietveld refinement were collected in the 2h range of 10L70L. A step size of 0.02L and a step time of 5 s per step were employed. Rietveld
refinement was carried out using both Topas and GSAS soft-ware. The background was modeled by a shifted Chebyschev polynomial of the first kind with 12 variables and
the peak profile was simulated with the pseudo-Voigt function. The refinement involved the cell parameter, scaling factor, twelve terms of background fitting, unit cell and
the isotropic thermal parameters for all atoms.

The surface morphology and composition of the samples were investigated using a Scanning Electron Microscope, Model EVO 50 fitted with a Bruker-AXS Energy
Dispersive X-ray System (Model QuanTax 200). High resolution transmission elec-tron microscopy (HRTEM) study was carried on one of the compositions La 2BaTi2 Mg1
2
xCuxO9 using a TECNAI G 20 (FEI) electron microscope operated at 200 kV.

3. Results and discussion

Fig. 1 shows the powder X-ray diffraction data of La 2BaTi2M0.8 Cu0.2O9 (M = Zn, Mg, Cd). Analysis of PXRD data of La 2BaTi2Zn1 x
CuxO9, La2BaTi2Mg1 xCuxO9 and La2BaTi2Cd1 xCuxO9 (x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0) as shown in Fig. 1 and Fig. S1 indicate that the
compounds of these three series of oxides form a disordered perovskite (Pm-3m) phase (some compositions show BaO (0.5 1%) as a
secondary phase). Rietveld refinement studies of one of the compositions (La 2BaTi2Zn0.2Cu0.8O9), were carried out (Fig. 2) using GSAS
software. Refinement parameters included the scale factor, background coefficient, profile coefficients and isotropic thermal displacement
parameters. The refinements produced sat-isfactory agreement factors R wp (weighed residual factor), Rp (Bragg factor) and R exp (expected
error). The site occupation factor was refined Ti, Cu, and Zn at the 1b site. The refined occupancies, the thermal parameters, the reliability
parameters, Rp and Rwp values, for La2BaTi2M0.2Cu0.8O9 (M = Zn, Mg and Cd) compounds along with all necessary crystallographic data
are given in Table 1.

Fig. 1. PXRD patterns of La2BaTi2M0.8Cu0.2O9 (M = Zn, Mg, Cu).

Fig. 2. Rietveld plots showing observed, calculated and the difference pattern for La 2BaTi2Zn0.2Cu0.8O9.
20 M.A. Nath et al. / Rietveld refinement data for the composition x = 0.8 of each series, crystal system:
Journal of Alloys and Compounds 615 (2014) 1824 cubic, space group: Pm3m and Uiso: isotropic thermal parameter of the atoms.

Position
a ()
3
V ( )
Atoms
Ba 1a site occupancy
2
Uiso ( )
La 1a site occupancy
2
Uiso ( )
Ti 1b site occupancy
2
Uiso ( )
Zn/Mg/Cd 1b site occupancy
2
Uiso ( )
Cu 1b site occupancy
2
Uiso ( )
2
O 3c Uiso ( )
Rp (%)
Rwp (%)
2
Reduced v

Fig. 3 shows typical SEM micrographs of the fracture surface

Fig. 3. SEM micrograph of La 2BaTi2Mg1 xCuxO9 for (a) x = 0, (b) x =
0.4, (c) x = 0.6 and (d) x = 1.0. Inset of (a) shows HRTEM indicating (1
1 1) lattice plane.
Table 1
of various compositions of La2BaTi2Mg1 xCuxO9. A dense and
homo-geneous microstructure without secondary phases was
observed. A minor variation of the grain size is observed with
composition while the density increases with increase in copper
content (Fig. 3). The average grain size of all the compositions
varies from 0.5 to 1.5 lm.
The variation of experimental and theoretical density with com-
position is shown in Fig. 4 and the values are given in Table 2. The
experimental density matches well with that of the theoretical
density. Fig. 5 shows the variation of volume with number of
cycles of density measurements for La 2BaTi2Mg1 xCuxO9. The
variation of volume is very small and the difference in
experimental density with the number of cycles is about 0.050.1
3
g/cm . The density of all the samples increase with the copper
content (9599%) as confirmed from the SEM micrograph (Fig. 3).

The temperature dependence of dielectric constant of La 2BaTi2

Zn1 xCuxO9 compounds is shown in Fig. 6 and other two series of
compounds are shown in Figs. S2 and S3. It is seen that the
dielectric constant varies from approximately 2050 in the

Fig. 4. Variation of experimental and theoretical density with composition for

La2BaTi2Mg1 xCuxO9.
M.A. Nath et al. / Journal of Alloys and Compounds 615 (2014) 1824

Table 2
Experimental and theoretical density of La 2BaTi2Mg1 xCuxO9 at room temperature (25 LC).

Composition
(X)

0
0.2
0.4
0.6
0.8
1.0

Fig. 5. Variation of volume with no. of cycles for La 2BaTi2Mg1 xCuxO9.

Fig. 6. Variation of dielectric constant with temperature at 100 kHz for La 2BaTi2Zn1 xCuxO9.

Table 3
e, tan d and theoretical sf values at room temperature (25 LC) and at 500 kHz.

temperature range of 50300 LC. Since the polarizing power of cat-ion increases with decrease in ionic size, hence the dielectric con-stant is
expected to be slightly larger for magnesium than zinc and cadmium doped compounds. However, a marked difference has
2+ 2+ 2+ 2+
not been observed due to small difference in polarizing power and ionic radius of Mg , Zn , Cd , and Cu ions in a 6-coordinate
(octahedral) environment. The dielectric constant values are almost stable till 250 LC and increase to some extent at higher tem-perature.
The dielectric constant and dielectric loss values, given in Table 3, show slight increase with the copper content for most of the
compositions. Fig. 7 and Figs. S4 and S5 show the temperature dependence of dielectric loss and the inset shows the frequency dependence
of dielectric loss of the same solid solutions. It is inter-esting to note that the loss factor of all compositions is very low and ranges between
0.0007 and 0.01. However, it shows an increase at elevated temperatures. As expected, there is a decrease in dielectric constant and loss with
frequency in almost all the compositions.

The microwave dielectric properties at X-band frequency (8.2 12.4 GHz) was measured using a Vector Network Analyser. The real and
complex part of permittivity has been calculated from the scattering parameters (S 11) by the NicholsonRoss procedure (Materials
Measurement Software of Agilent). Fig. 8, Fig. 9 and Fig. S6 respectively show the variation of complex permittivity and loss tangent (tan d
= e00/e0) with composition for Mg, Zn and Cd based oxide compounds. The real part of the complex permittiv-ity relates to the stored
energy within the material while the imag-inary part is related to the dissipation (loss) of energy and results mostly from electric-dipole
2
polarization at microwave frequencies. The positive ions at their respective position surrounding the neg-ative O ions contribute to the
dielectric constant through their dipolar polarization and dielectric loss through the dipole relaxa-tion. The complex permittivity data at X-
band frequency is in good agreement with the low frequency (500 kHz) data. However, both permittivity and loss tangent of some of the
compositions show some oscillatory behavior owing to the data deduction procedure used by the NicholsonRoss algorithm of Materials
Measurement software of Agilent Technologies. The possible reason for the oscil-latory behavior in the dielectric data over the X-band is the
occur-rence of transmission resonances over the measurement range which is not compensated for in the NicholsonRoss algorithm. At
integral multiples of kg/2 (where kg is the wavelength inside the material) there will be a maximum transmission of power and since the
automated algorithm being used by Material Mea-surement Software is not taking into account this aspect, at such frequencies we will
observe a reduced value of dielectric constant. At k g/4 distances, the algorithm we will get an increased value for the dielectric constant as at
this frequency the material will act like a quarter wave transformer. The result is a wave like response over the frequencies. However the
values of the dielectric parameters at frequencies where there is no oscillatory behavior belongs to the intrinsic property of the material and
it agrees well with the low frequency results indicating that these materials do not show any major dielectric relaxation in the frequency
range from
 Composition (X) La2
e
0 33
0.2 31
0.4 26
0.6 29
0.8 33
1.0 31
22 M.A. Nath et al. / Journal of Alloys and Compounds 615 (2014) 1824
Fig. 9. Variation of permittivity with frequency for La 2BaTi2Mg1
xCuxO9 and the inset shows the frequency dependence of loss
tangent of the above series of oxides.

100 kHz to the X-band frequencies (8.212.4 GHz),

which is an important requirement for materials
which exhibit low losses at high frequencies. To
avoid this oscillatory behavior in the Ku (12.418
GHz) band of frequencies, the measurement was
done using the multiline method where such
oscillations are known to be absent. A comparison of
both the measurement procedures in

Fig. 7. Variation of dielectric loss with temperature at 100 kHz

for La2BaTi2Zn1 x CuxO9. Inset shows the frequency dependence
of loss of the above series of oxide.

Fig. 8. Variation of permittivity with frequency for La 2BaTi2Zn1

xCuxO9 and the inset shows the frequency dependence of loss
tangent of the above series of oxides.
the same frequency range is the subject matter of
another study. Moreover, it is important to note that
all the compositions are non magnetic, hence lr = 1
and l0 = 0.
Fig. 10 shows the variation of permittivity and
loss tangent with frequency for some of the
compositions of the three series in the Ku band. Here
as expected, the dielectric data is completely free
from the oscillatory response resulted from the usage
of Nichol-sonRoss algorithm. This reinforces the
earlier conclusion that the observed oscillatory
behavior is the result of the Nicholson Ross
algorithm than the result of any intrinsic material
properties. However, NicholsonRoss algorithm got
the advantage that it requires only one pellet
thickness for the measurement. Also, by this
procedure one can elucidate both the complex
dielectric per-mittivity and magnetic permeability
from a single set of measure-ments. Often this is the
first procedure to be carried out to obtain the
approximate values of the permittivity and
permeability of a new material.
The complex permittivity measured in the Ku
band (12.4 18 GHz) increases with the increase in
density and copper content as discussed above. The
values of complex permittivity and loss at Ku-band
frequency are given in Tables S1S3. It is important
to note that the dielectric properties (dielectric
constant and loss) are still in the range of materials
used in wireless electronic sys-tems. These results
are encouraging towards our motive of synthe-sizing
new materials for the increasingly important higher
frequencies in the X- and Ku-band. The dielectric
constant of the materials synthesized has been
compared with the known values in the literature.
The dielectric constant of BZT (Ba(Zn1/3Ta2/3)O3),
BNT (Ba(Nb1/3Ta2/3)O3), BMT (Ba(Mg1/3Ta2/3)O3)
[32,4447] and similar materials in the frequency
range of 100 kHz to 6 GHZ reported is 2030 with
similar microwave applications. In our study of
simultaneous substitution at both A and B site of the
perovskite, we have achieved the similar values of
dielectric con-stant with comparatively low loss and
at the Ku-band frequency (1218 GHZ).
Moreover the dielectric properties obtained at
Ku-band are sta-ble with the increase in frequency.
However, both permittivity and loss decrease with
increase in frequency. This suggests that the
polarizability and the resulting electric displacement
decreases with increasing frequency, a behavior
exhibited by low loss dielec-trics at high frequencies.
This also indicates that the hopping of electrons
decrease with increasing frequencies. At the same
time, since the multiline procedure gives a clear data
it could be observed that even the smallest change in
the dopant (in type or concentration) gives a clear
signature in the microwave data. The dielectric
constant is clearly frequency independent
irrespective of the doping while the loss is becoming
frequency dependent in some cases. The frequency
independent behavior in the dielectric constant
shows that this system has the potential to yield good
dielectric resonator materials with further fine tuning
in doping to arrive at very low loss tangent values. In
all cases, without Cu, the loss parameters are most
attractive. This suggests that Cu could be introducing
multivalent states into the system resulting in hop-
ping and polarization flipping leading to higher
values of dielectric loss as well as dielectric constant.
Also, introduction of Cu in most of the compositions
make the dielectric loss frequency dependent, thus
heralding the onset of relaxation behavior.
Temperature coefficient of resonant frequency
(sf) in the units of ppm/LC is a measure of drift of
the temperature of resonant fre-quency and is given
by
sf 1=2se aL
3
where se is the temperature coefficient of
permittivity and aL is the linear expansion
coefficient. Using this equation and assuming the
value of aL, as in most of the cubic perovskite
ceramics [48] as 10 ppm/LC, approximate values of
sf have been calculated theoreti-
 M.A. Nath et al. / Journal of Alloys and Compounds 615 (2014) 1824

Fig. 10. Variation of permittivity and loss tangent with frequency for La 2BaTi2Zn1 xCuxO9 La2BaTi2Mg1 xCuxO9 and
La2BaTi2Cd1 xCuxO9.

cally and the values are given in

Table 3. It is important to note
that
se and sf have a remarkable
dependence on crystal structure of
com-
plex perovskites [1]. For low
tolerance factor perovskites, (t <
0.97)
positive temperature coefficient
of dielectric constant (TCKs) of
50
1
ppmLC or larger are observed
and there is a sharp crossover to
1
large ( 200 ppm LC or larger)
negative TCKs in very small
interval
of 0.97 < t < 0.99 associated
with an accompanying change
in the
type of structural distortion.
Thus sf values given in Table 3
fall in
the permissible range for similar kind of materials used in commu-
nication technology. These
values are positive for some of
the com-
positions and negative for rest of the compositions. Dielectric
constant (er), temperature
coefficient of dielectric constant
(se)
 and temperature coefficient of
resonant frequency (sf) are
plotted
as a function of composition x
as shown in Fig. 11.

4. Conclusions

We have been successful in

synthesizing materials with
disor-
dered cubic perovskite structure.
These materials exhibit low loss
at high frequencies, especially
for applications as dielectric
resona-
tors in wireless technology. The
simultaneous substitutions at
both
A- and B- sites of La2BaTi2M1
xCuxO9 lead to enhanced
dielectric
constant and low loss at higher
frequency. The dielectric data
has
been determined in detail along
with morphological studies and
density measurements. The high
frequency data in the GHz range
is in good agreement for the use
of such type of materials in
wire-
Fig. 11. (a) se, (b) sf and (c) er as a function of X for La 2BaTi2Zn1 xCuxO9. less applications.
24 M.A. Nath et al. / Journal of Alloys and Compounds 615 (2014) 1824
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