M A TE RI A L S C H A RAC TE RI ZA T ION 6 2 ( 2 01 1 ) 1 0 0 0–1 0 0 6

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Electrical properties of lanthanum doped barium

titanate ceramics

M.M. Vijatović Petrovića,⁎, J.D. Bobića , T. Ramoškab , J. Banysb , B.D. Stojanovića

a
Institute for Multidisciplinary Research, Belgrade University, Kneza Višeslava 1, Belgrade, Serbia
b
Faculty of Physics, Vilnius University, Sauletekio al. 9, Vilnius, Lithuania

AR TIC LE D ATA ABSTR ACT

Article history: Pure and lanthanum doped barium titanate (BT) ceramics were prepared by sintering pellets
Received 7 April 2011 at 1300 °C for 8 h, obtained from nanopowders synthesized by the polymeric precursor
Received in revised form 9 May 2011 method. XRD results showed formation of a tetragonal structure. The presence of dopants
Accepted 19 July 2011 changed the tetragonal structure to pseudo-cubic. The polygonal grain size was reduced up
to 300 nm with addition of lanthanum as a donor dopant. Determined dielectric properties
Keywords: revealed that lanthanum modified BT ceramics possessed a diffused ferroelectric character
Barium titanate in comparison with pure BT that is a classical ferroelectric material. In doped BT phase
Dopant transition temperatures were shifted to lower temperatures and dielectric constant values
Soft chemical synthesis were much higher than in pure BT. A modified Currie Weiss law was used to explore the
Microstructure connection between the doping level and degree of diffuseness of phase transitions.
Electrical properties Impedance spectroscopy measurements were carried out at different temperatures in order
to investigate electrical resistivity of materials and appearance of a PTCR effect.
© 2011 Elsevier Inc. All rights reserved.

1. Introduction from classical ferroelectric to diffuse ferroelectric or to relaxor,

Barium titanate (BT) is a ferroelectric material with a perovskite
structure important in the field of electronics. Properties of this
material are mainly based on its ferroelectric phase transition.
The broadness of the temperature interval where the material
acts as a ferroelectric depends on various factors such as
pressure, temperature and time of sintering, grain size, defects,
type of added dopant (if any), etc. [1,2].
Substitution of the barium or titanium ion with small
concentrations of ions with a similar radius could lead to
structure and microstructure changes and furthermore modi-
fication of dielectric and ferroelectric properties. The possibility
of easy substitution is enabled due to the capability of the
perovskite structure to host different sized ions in the BT lattice.
Some dopants shift transition temperatures of BT or induce
broadening of the ε–T curve and many of them cause
diffuseness of the ferroelectric transition [3]. The degree of
diffuseness of the transition could show the continuous change
depending on the type of dopant incorporated in the BT lattice.
Literature data have shown that partial substitution of Ba or Ti
ions with dopants such as Zn, Y, Sb cause the formation of
diffuse transition and Sn, Ce, Zr, Bi, Hf [4] cause the appearance
of ferroelectric relaxor behavior.
Pure barium titanate is an electrical insulator at room
temperature. On the other hand, the presence of dopants in
the BT lattice could cause lowering of the materials electrical
resistivity. The dopant concentration is a very important
factor. It can lead to the appearance of semi-conductivity,
while a critical concentration reverts the material to insulator
again. The PTCR effect as a consequence of grain boundary
phenomena is typical for semi-conducting barium titanate
[5,6].
In the present investigation, we have studied the electrical
properties of lanthanum doped BT ceramics, by monitoring the
variation of its dielectric constant with temperature (−175 to
175 °C) and analysing the influence of lanthanum concentration

⁎ Corresponding author. Tel.: +381 11 2085039; fax: + 381 11 2085062.

E-mail address: miravijat@yahoo.com (M.M.V. Petrović).

1044-5803/$ – see front matter © 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2011.07.013
 M A TE RI A L S C H A RAC TE RI ZA T ION 6 2 ( 2 01 1 ) 1 0 0 0–1 0 0 6
on the diffuseness of ferroelectric transition. Impedance
spectroscopy was used to determine the contribution of each
microstructure component to the total resistivity of the BT
material.
2. Experimental
A modified Pechini process was used to prepare nanopow-
ders of pure (BT) and barium titanate doped with 0.3 (BTL3)
and 0.5 mol% (BTL5) of lanthanum [7]. Titanium tetra-
isopropoxide (Ti[OCH(CH3)2]4, Alfa Aesar, 99.995%), barium
acetate (Ba(CH3COO)2), Alfa Aesar, 99.0–102.0%) and lanthanum
nitrate hexahydrate (La(NO3)3·6H2O, Alfa Aesar, 99.99%) were
used as sources of metal ions. Solutions of titanium citrate and
barium citrate were prepared using ethylene glycol (EG) and
citrate acid (CA) as solvents (M (metal ion):CA:EG= 1:4:16). After
mixing of the obtained citrate solutions lanthanum nitrate salt
was added, the transparent yellow solution was heated up to
140 °C until it changed to dark-brown glassy resin. Decomposition
of organic resin was performed at 250 °C for 1 h and 300 °C for 4 h,
forming a black solid mass which was pulverized in an agate
mortar and pestle. Thermal treatment of the formed precursor
was performed at 500 °C/4 h, 700 °C/4 h and 800 °C/2 h [8].
Nanopowders with particles ~ 25–40 nm were uniaxially
pressed into disks of 10 mm in diameter at a pressure of
196 MPa. Sintering was performed at 1300 °C for 8 h with a
heating rate of 10 °C/min.
X-ray diffraction measurement was carried out in order to
determine the crystal structure phase (Philips PW1710 diffrac-
tometer) and scanning electron microscopy (Tescan VEGA
TS 5130MM) was used to analyze the microstructure. The
density of barium titanate ceramics was obtained by measuring
dimensions and mass of the samples and calculating
ρ = 4·m/d2·h·π (where m is the mass, d is the average diameter
and h is the height of the sintered samples). Samples were
prepared for electrical measurements by polishing followed by
applying silver electrodes on both sides of the samples.
Measurements were carried out on a LCR meter (model 4284 A,
Hewlet-Packard). Electrical measurements determined values
for the real (ε′) and imaginary (ε′′) part of permittivity. The
dielectric loss tangent of barium titanate ceramics was derived
by calculating tan δ = ε′′/ε′. The total ac resistivities at different
temperatures were extracted from complex impedance spec-
trum (Nyquist plots) obtained from variations of imaginary Z′′
(Z′′ = ε′/2πf ε0 *(ε′′2 + ε′2)) and real parts, Z′ (Z′ = ε′′/2πf ε0 *(ε′2 + ε′′2))
of impedance values calculated from the obtained permittivity
data.
3. Results and Discussion
X-ray diffraction measurements (Fig. 1) showed formation of a
tetragonal crystal structure in BT ceramics identified by the
appearance of characteristic diffraction peaks (JCPDS files no.
05-0626). It was noticed that tetragonality decreased with
increasing lanthanum concentrations suggesting the formation
of defects in the BT lattice. This caused structure changes due to
the smaller lanthanum ion stabilizing the cubic form as
predicted by Goldschmidt's tolerance factor [9].
1001
Microstructures of barium titanate samples are given in
Fig. 2. Polygonal grains with a size around 3.5, 0.7 and 0.3 μm
were observed in pure BT, BTL3 and BTL5, respectively. These
results point out that lanthanum as a donor dopant influenced
a grain size reduction. The porosity of doped BT samples was
high; therefore, densities of doped samples were much lower
than the density of pure BT.
The temperature dependence of the dielectric constant of
barium titanate ceramics is presented in Fig. 3. The three
phase transitions (cubic to tetragonal—TC-T, tetragonal to
orthorhombic—TT-O, orthorhombic to rhombohedral—TO-R)
characteristic for barium titanate can be observed in BT and
BTL3, although phase transition peaks of the BT sample seem
to be sharper than those observed in BTL3 ceramics. On the
other hand, in the case of BTL5, the transition from cubic to
tetragonal can be noticed but low temperature transitions
cannot be clearly observed. It appears that these structural
transitions were merged into one broad peak. This occurrence
is often called a “pinching effect” [1,9]. It seems that as the
concentration of lanthanum increased BT with classical
ferroelectric phase transitions changed to ferroelectric with
diffuse phase transitions [1,9–11]. From Fig. 3 it can be noticed
that the positions of phase transition peaks have shifted to
lower temperatures, TC-T was 120 °C for pure BT, 111 °C for
BTL3 and 96 °C for BTL5 and TT-O was 14 °C for pure BT, and
9 °C for BTL3 and BTL5 whereas TO-R was − 74 °C for all
samples. It is known that some dopants shift the transition
temperature rather than affect the shape of the dielectric
spectrum [1,4,10], but in the investigated BT material we can
see that lanthanum as a donor dopant affected both. Shifting
of the Curie temperature is often connected with grain size
changes and SEM micrographs of obtained BT ceramics
indicated that lanthanum influenced grain size reduction
[12]. A possible explanation of these phenomena can be found
in defect chemistry. Depending on the accepted charge
compensation mechanism of ion substitution in the BT crystal
lattice vacancies VTi, VBa and VO are possible defects [9,12,13].
It was assumed that for low lanthanum concentrations the
main compensation mechanism is electronic, with a light blue
colored sample and n-semiconducting type. The formation of
oxygen vacancies due to oxygen loss during the sintering
process is also possible and it can also lead to the emergence
of semiconducting properties. Further addition of lanthanum
affects the mechanism change to ionic in dark blue and
semiconducting samples where titanium vacancies are likely
to be found besides oxygen vacancies. The Curie temperature
shift could also be connected with the fact that during
substitution of Ba2+ (1.35 Å) with smaller La3+ (1.15 Å) the
tetragonal structure becomes weaker and formation of
titanium vacancies destroyed Ti–O–Ti linkages responsible
for ferroelectricity.
It is well known that the dielectric permittivity of a normal
ferroelectric above the Curie temperature obeys the Curie–
Weiss law described by:
ε = C=ðT−TC Þ ðT > TC Þ;
where C is the Curie–Weiss constant and TC is the Curie
temperature [14]. Fig. 4 shows the inverse of ε as a function of
temperature at 100 kHz. Diagrams corresponding to BT and
1002 M A TE RI A L S C H A RAC TE RI ZA T ION 6 2 ( 2 01 1 ) 1 0 0 0–1 0 0 6
Fig. 1 – X-ray diffraction patterns of BT, BTL3 and BTL5 ceramics sintered at 1300 °C for 8 h.
BTL3 indicate that far above the Curie temperature dielectric
permittivity follows the Curie–Weiss law and at the Curie
temperature ε has a maximum value (TC = Tmax). However, in
the sample BTL5 deviation from this law could be clearly
noticed starting at the temperature Tdev. Based on literature
data [10,11,13,14], the existence of a certain degree of phase
transition diffuseness in doped samples was assumed. The
modified Curie–Weiss law was used for further analysis:
1=ε−1=εmax = ðT−Tmax Þγ=C;
where γ and C are modified constants, εmax is the dielectric
constant maximum at the transition temperature Tmax [14].
The constant γ gives information about the character of the
phase transition and it varies between 1 in the case of a
normal ferroelectric and 2 for relaxor materials. The constant
γ represents the slope of the graph between ln(1/ε − 1/εmax) and
ln(T − Tmax) and is an indicator of the diffuseness or disorder of
the transition (Fig. 5). In the present case, the value of constant
γ increases with dopant concentration increase and the
obtained results are shown in Table 1. The value of constant
γ in BTL5 is quite high, but this material cannot be classified as
a relaxor due to the fact that the transition temperature
position does not change with frequency, which is the main
characteristic of relaxors [10,14].
Dielectric constant values also change with changes in
dopant concentration. As the dopant concentration grows the
dielectric constant increases. The existence of smaller grains
in doped samples could be a possible reason for the dielectric
constant increase. It can be assumed that very low concen-
trations of lanthanum are completely incorporated in the BT
lattice as proposed by other authors [15], influencing the
dielectric constant increase. The temperature dependence of
dielectric losses at 100 kHz presented in Fig. 3b shows that
with dopant addition tan δ increases. Obtained dielectric
losses for doped BT ceramics are very high that is possibly
connected with the high porosity of lanthanum doped
samples as mentioned previously.
Variation of the imaginary part of impedance (Z′′) as a
function of the real part (Z′) gives the complex impedance
spectrum (Nyquist plots). The shapes of these plots are
dependent on temperature and they are presented in Fig. 6.
The complex impedance spectrum of pure BT is an almost
straight line with a large slope indicating the insulating
behavior of the sample. In doped samples the impedance
 M A TE RI A L S C H A RAC TE RI ZA T ION 6 2 ( 2 01 1 ) 1 0 0 0–1 0 0 6
Fig. 2 – SEM photographs of (a) BT, (b) BTL1, (c) BTL5 barium
titanate powders.
1003
Fig. 3 – Temperature dependence of (a) dielectric constant
and (b) dielectric losses at 100 kHz for BT, BTL3 and BTL5.
complex plane showed a single arc at different temperatures,
indicating that the electrical process occurring in the material
has a single relaxation possibly due to the grain contribution.
Since the impedance spectroscopy is characterized by the
appearance of semicircular arcs that change with rise in
temperature, measuring in wider frequency and temperatures
ranges can give much more information about contributions of
the grain boundary and electrode. In our investigation, mea-
surements were carried out up to 175 °C and the concentration
of added lanthanum was low. Therefore, the expected grain
boundary contribution is not noticeable from obtained Nyquist
plots. However, the total resistivities obtained from impedance
measurements were used to study its temperature dependence
which is presented in Fig. 7. The total resistivity of both
compositions BTL3 and BTL5 exhibited a modest PTCR jump
( ≥ 1 orders of magnitude) when heated through its Curie
temperature. Similar results were obtained by Markovec and
co-authors [16] who showed that addition of up to 2.5 mol% La
influenced appearance of a PTCR effect. Higher dopant concen-
trations lead to emergence of an NTC effect. According to
literature data [17,18], the PTCR effect in semiconducting donor-
1004 M A TE RI A L S C H A RAC TE RI ZA T ION 6 2 ( 2 01 1 ) 1 0 0 0–1 0 0 6

Fig. 5 – ln(1/ε − 1/εmax) and ln(T − Tmax) plots for all lanthanum
doped BT ceramics at 100 kHz.

grain size and grain size distribution, secondary phases, nature

and place of impurities, crystal lattice disorder, defects, etc.
[17,19–21]. Adding of different concentrations of lanthanum
lead to grain size reduction, formation of defects (especially Ti
vacancies [19–21]) and therefore emergence of a PTCR jump.
Nevertheless, Hamamoto and co-authors [22] investigated the
influence of voltage on the PTCR jump in the range from 0.05 to
1.5 V and they noticed that at the lowest voltages the PTCR jump
was the highest and 3 orders of magnitude. The voltage of our
measurements was 4 V and this can be the reason for such a low
PTCR jump in our case. Thus, another view of the obtained
impedance spectrum does not exclude the possibility of over-
lapping of the two semicircles that correspond to grain and grain
boundary contributions and the lack of measurements in a
wider temperature and frequency ranges probably disenable
dividing these resistivity contributions.

4. Conclusion

The present work reports the results of an investigation of

electrical properties of pure and lanthanum doped polycrys-
talline ceramics prepared from nanopowders obtained by a
modified Pechini process. The deeper dielectric properties
indicated that the BT ferro-para phase transition changed
from classical to the diffuse kind as the concentration of
lanthanum increased. This assumption was confirmed by the

Table 1 – Dielectric constant at room and Curie temperature,

Fig. 4 – Inverse dielectric constant at 100 kHz as a function of dielectric losses values and diffuseness factor for all samples
temperature for BT, BTL3 and BTL5. at 100 kHz.
Sample ε′(Troom) ε′ (TC) tan δ γ

BT 814 1274 0.013 1.18

doped BT is a grain boundary phenomena. The resistivity of a
BTL3 1600 1655 0.086 1.24
material depends on transport processes that occur in grains BTL5 5113 5240 0.186 1.78
and grain boundaries. The free carrier motion is influenced by
 M A TE RI A L S C H A RAC TE RI ZA T ION 6 2 ( 2 01 1 ) 1 0 0 0–1 0 0 6 1005

Fig. 6 – Complex impedance spectrum of (a–c) BTL3 and (d–e) BTL5 ceramics at different temperatures.

determined diffuseness factor obtained from the modified
Curie–Weiss law where the diffusivity increased with increas-
ing of the lanthanum content. As a consequence of Ba2+
substitution with the smaller La3+ ion and possible formation
of cation vacancies, the transition temperatures were shifted
to lower temperatures causing the so-called pinching effect.
BTL compounds exhibited high diffuseness and a very high
dielectric constant at such a low doping level and on the other
hand quite high dielectric losses. Impedance analysis showed
one semicircle, indicating grain contribution in the total
resistivity but overlapping is still possible due to appearance
of a PTCR effect which suggested the existence of grain
boundary resistivity.
Acknowledgements
The authors gratefully acknowledge the Ministry of Science
and Technological Development Republic of Serbia for the
financial support of this work (project III 45021), the Lithuanian
Research Funding Institution—Faculty of Physics, Vilnius and
COST 539.
1006 M A TE RI A L S C H A RAC TE RI ZA T ION 6 2 ( 2 01 1 ) 1 0 0 0–1 0 0 6
Fig. 7 – Resistivity as a function of temperature for BTL3 and
BTL5 ceramics.
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