International Journal of Inorganic Materials 3 (2001) 1205–1210

Doping mechanisms and electrical properties of La-doped BaTiO 3

ceramics

Finlay D. Morrison, Derek C. Sinclair*, Anthony R. West

Department of Engineering Materials, University of Sheffield, Sheffield S1 3 JD, UK

Abstract

The electrical properties of Ba 12x La x Ti 12x / 4 O 3 ceramics where x # 0.20 were investigated by impedance spectroscopy after heat
treatment in O 2 , Ar and air at 13508C. Samples heated in O 2 were electrically insulating with very high maximum permittivities, |25,000
at x50.06 and exhibited significant ‘relaxor-type’ behaviour at x50.10. Samples heated in Ar were semiconducting for all x whereas air
heated samples were electrically inhomogeneous. Semiconductivity in these materials is attributed to oxygen loss as opposed to La-donor
doping.  2001 Elsevier Science Ltd. All rights reserved.

Keywords: Ferroelectric oxides; Electroceramics; Doping mechanisms; Phase transitions

1. Introduction Ba 21 ⇒ La 31 1 e 2 (1)

Tetragonal BaTiO 3 is a ferroelectric perovskite (ABO 3 )
at room temperature that finds applications as a dielectric
material in multilayer capacitors (MLCs) and as an over-
load protection device in electrical appliances. For MLC
applications, dielectric materials need to be electrically
insulating (.10 10 V) and exhibit high permittivity values
(.1000) at room temperature. As overload protection
devices, they are required to be semiconducting (,100 V)
at room temperature and undergo a sharp rise in resistivity
(|4–6 orders of magnitude) when heated above the ferro-
to para-electric (tetragonal to cubic) phase transition
temperature, T c . Such devices are called positive tempera-
ture coefficient of resistance (ptcr) thermistors.
For many years, A- and B-site dopants have been used
to modify the electrical properties of BaTiO 3 , however, in
many cases the doping mechanism(s) and defect chemistry
remain poorly understood and / or controversial. In par-
ticular, the doping mechanism of La in BaTiO 3 has been
widely debated [1–3]. The occurrence of semiconductivity
in lightly-doped (#0.5 atom%) (LaBa)TiO 3 ceramics
prepared in air and quenched from #13508C has led to the
belief that La can act as a ‘donor’ dopant under appropriate
conditions of temperature / oxygen partial pressure (T,
pO 2 ) [1,2] according to the equation
*Corresponding author. Tel.: 144-114-222-5974; fax: 144-114-222-
5943.
E-mail address: d.c.sinclair@sheffield.ac.uk (D.C. Sinclair).
1466-6049 / 01 / $ – see front matter  2001 Elsevier Science Ltd. All rights reserved.
PII: S1466-6049( 01 )00128-3
and general formula Ba 1 2 z La z e z TiO 3 , ([Ba 1 La] / [Ti] 5
1). More heavily doped samples (.0.5 atom%) prepared
under the same conditions are electrically insulating and
this has been attributed [1,2] to a ‘switch’ from the
electronic ‘donor-doping’ to an ionic compensation mecha-
nism, where
Ba 21 1 ]14 Ti 41 ⇒ La 31 (2)
of general formula Ba 12x La x Ti 12x / 4 O 3 ([Ba 1 La] / [Ti] .
1). From the viewpoint of defect chemistry, the driving
force for such a change in cation composition and there-
fore doping mechanism, although not impossible, remains
unclear.
In contrast to the observed electrical properties, lattice
energy calculations [4] and several phase diagram studies
have shown Ti-vacancies to be the primary mode of
compensation [5–7]. Single phase materials can be pre-
pared for x#0.25 at T513508C and pO 2 |20 kPa (1 atm
air). Compositions prepared according to the electronic
compensation mechanism give phase mixtures [7] of
Ba 12x La x Ti 12x / 4 O 3 and other Ti-rich phases such as
Ba 6 Ti 17 O 40 for z.0.01, however, detection limits associ-
ated with the techniques commonly employed in phase
diagram studies make it difficult to rule out a switch in
mechanism from Ti-vacancies to electronic compensation
at low La-contents (z,0.01). Recently we have used a
combination of Electron Probe Micro Analysis (EPMA) /
analytical Transmission Electron Microscopy (TEM) and
1206 F.D. Morrison et al. / International Journal of Inorganic Materials 3 (2001) 1205 – 1210
an Impedance Spectroscopy (IS) [7–9] to probe the
compositional and electrical homogeneity of La-doped
BaTiO 3 ceramics prepared according to both compensation
mechanisms under various conditions of (T, pO 2 ). We see
no evidence for the precipitation of secondary phases for
any Ba 12x La x Ti 12x / 4 O 3 composition heated in O 2 , Ar or
air at #14008C suggesting the primary mode of incorpora-
tion of La into BaTiO 3 at all concentrations is via Ti-
vacancies. Such materials are expected to be electrical
insulators at room temperature given the immobility of
Ti-vacancies, however, in many cases semiconductivity is
observed. We have suggested an alternative mechanism [7],
namely, oxygen loss according to
O 22 ⇒ ]21 O 2 1 2e 2 (3)
is responsible for semiconductivity. The amount of oxygen
loss is too small to detect using Thermogravimetry but has
a significant influence on the colour and electrical prop-
erties of La-doped BaTiO 3 ceramics. The presence of
Ti-vacancies may facilitate the ease with which oxygen
can be removed from the lattice but this needs to be
confirmed. It is noteworthy, however, that oxygen loss in
other dielectric-based barium titanates, e.g. Ba 2 Ti 9 O 20 and
BaTi 4 O 9 is readily accepted [10] and is known to enhance
dielectric losses through the introduction of electrical
conductivity via Eq. (3). Here we outline some recent
results on Ba 12x La x Ti 12x / 4 O 3 ceramics heated at 13508C
in O 2 , Ar and air where the electrical behaviour has been
probed by IS and can be explained in terms of oxygen loss
as opposed to a switch in mechanism from Ti-vacancies to
La-donor doping.
2. Experimental
Samples were prepared according to the formula
Ba 12x La x Ti 12x / 4 O 3 with a range of x-values up to 0.20.
Appropriate amounts of BaCO 3 (Aldrich, 99.98%), La 2 O 3
(Aldrich, 99.99%) and TiO 2 (Aldrich, 99.91%) were
mixed in acetone with an agate mortar and pestle until dry.
The powders were placed in an alumina boat lined with Pt
foil and fired in flowing oxygen. Firing schedules were
10008C overnight to decarbonate, 12008C for 3 h and
13508C for 3 days, with daily regrinding for 5 min in an
agate planetary ballmill. X-ray diffraction (XRD) and
EPMA (using a Cameca SX 51 with appropriate standards)
were used to confirm the phase purity / lattice parameters
and cation composition of all samples. Pellets for IS were
prepared by uniaxial pressing of powders to 200 MPa in an
8-mm stainless steel die. The green bodies were placed in
an alumina boat lined with Pt foil and heated overnight at
13508C in flowing O 2 , Ar or laboratory air. Electrodes
were fabricated from Au paste and foil, and were fired to
8008C to remove organics and harden the Au residue.
Measurements above 258C were performed in a horizontal
tube furnace whose temperature was controlled to |18C.
Sub-ambient temperatures were obtained using an Oxford
instruments cryostat controlled by an Oxford ITC4 tem-
perature controller. Impedance measurements were made
over the frequency range 10 22 –10 7 Hz using a combina-
tion of Solartron 1250 / 1287 and Hewlett-Packard 4192A
instrumentation with an applied voltage of 100 mV. All
data were corrected for sample geometry. Microstructural
properties such as grain size distribution and morphology
were determined using an ISI SS40 SEM. Samples were
either in the form of fractured pellets or polished, etched
specimens all of which were carbon coated to avoid
charging under the electron beam. Further characterisation
was provided by TEM using a JEOL 2000X TEMSCAN
microscope operating at 200 kV with an analytical facility
(Link AN 10 / 85S) to probe sample homogeneity.
3. Results and discussion
XRD, SEM and EPMA showed all samples to be single
phase. XRD patterns for x#0.04 were fully indexed on the
tetragonal BaTiO 3 cell whereas for x.0.04 patterns were
fully indexed on the cubic BaTiO 3 cell. Smooth variations
in lattice parameters and unit cell volume at room tempera-
ture were observed as a function of x [11]. SEM indicated
that compositions 0 # x # 0.06 displayed similar micro-
structures with an average grain size of |3–4 mm, whereas
the grain size increased for x.0.06 with a reasonably
uniform grain size of |7–10 mm being obtained for
x50.20 [11]. Pellet densities, calculated from pellet di-
mensions and theoretical X-ray density were in excess of
|95% for all compositions. The starting compositions and
measured EPMA values were within experimental errors
for all x and no secondary phases were detected. The
electrical properties of samples prepared at 13508C under
various pO 2 are discussed in the following sections.
3.1. x 50 – 0.20, pO2 |10 5 Pa (1 atm O2 )
All samples were off-white in appearance and electrical-
ly insulating at room temperature (.10 7 V). Due to their
high resistance it was not possible to extract bulk and grain
boundary resistance, R, and capacitance, C, values below
3008C using IS. The effective parallel capacitance, Cp ,
could be measured as a function of frequency below
|3008C, and in general gave rise to a high frequency
plateau, Chf which gives a close representation of the bulk
capacitance in this temperature range [11]. Capacitance,
Chf , and permittivity, ´ 9, data, where ´ 9 5 Chf /´0 , and ´0 is
the permittivity of free space were extracted over a wide
temperature range for compositions x#0.10, Fig. 1(a).
Undoped BaTiO 3 (x50) showed typical behaviour, ex-
hibiting an ´ 9max of |10,000 at T c 51378C and a small
maximum associated with the orthorhombic to tetragonal
phase transition temperature, T 0 / t , at |108C. On increasing
 F.D. Morrison et al. / International Journal of Inorganic Materials 3 (2001) 1205 – 1210 1207

Fig. 1. Capacitance, Chf and permittivity, ´ 9, data as a function of temperature for 0 # x # 0.10, (a). Cp and ´ 9 data as a function of temperature and
frequency for x50.10, (b).

x, two types of dielectric behaviour were observed. For
x|0.06, ´ 9max increased to a value of |25,000, d´ 9max
remained sharp and T c and T 0 / t were both displaced to
lower temperatures. For x$0.06, ´ 9max decreased and
became increasingly broad with increasing x. For x50.08,
T 0 / t can be observed as a shoulder on the low temperature
side of ´ 9max however, for x.0.10 it was not possible to
detect two phase transition temperatures from Chf data.
Across the series, Cp showed an increasing degree of
frequency dependence below T c . Such a response is
indicative of ferroelectric ‘relaxor-type’ behaviour and can
clearly be observed in fixed frequency measurements of
x50.10, Fig. 1(b). A more complete analysis of the
permittivity behaviour using Curie–Weiss plots and
Smolenskii’s and Uchino’s expressions for ‘relaxor-type’
behaviour is reported elsewhere [11].
Variations in T c and T 0 / t as a function of x are shown in
Fig. 2(a) and (b), respectively along with those for other A-
and B-site dopants. Both transition temperatures decrease
rapidly, with T c showing a linear dependence on x with a
rate of 2248C per atom% La 31 , Fig. 2(a). For x$0.08 T c
and T 0 / t coalesce, Fig. 2(c). At temperatures above 3008C
bulk and grain boundary conductivity data could be
extracted from complex impedance (Z*) plots using IS.
Bulk conductivity data, sb 5 1 /R b , are shown in the form
of an Arrhenius plot, Fig. 3, and reveal two main features.
Firstly, there is a large change in Activation Energy, E a ,
from |1.56 eV for undoped BaTiO 3 (x50) to a value
between 0.64 and 0.72 eV for doped compositions and
secondly there is no systematic trend in sb with x.
Electrically insulating Ba 12x La x Ti 12x / 4 O 3 compositions
prepared in O 2 show some interesting electrical behaviour,
Figs. 1 and 3. Unfortunately, it is not possible to attribute
specific effects to either A- or B-site effects alone as the
ionic doping mechanism involves partial replacement of
Ba with the smaller La ion on the A-site but with
concomitant creation of B-site vacancies. Nevertheless,
this mechanism has a dramatic effect on T c and T 0 / t and on

Fig. 2. Variation of T c , (a) and T 0 / t , (b) as a function of x and comparison of La and Zr doping, (c).
1208 F.D. Morrison et al. / International Journal of Inorganic Materials 3 (2001) 1205 – 1210
Fig. 3. Arrhenius plot of bulk conductivity data for 0 # x # 0.20.
the general permittivity characteristics. The rate of de-
crease of T c and T 0 / t are greater than for any other
reported A- and B-site dopant, as shown in Fig. 2. La-
doping causes T c and T 0 / t to coalesce at |x50.10 and this
is similar to the well known effect of B-site Zr-doping,
however for the latter they coalesce at |508C as opposed
to 21308C, Fig. 2(c). The general permittivity characteris-
tics across the series are also similar to Zr-doping. This is
anticipated as replacement of ferroelectric active TiO 6
octahedra by Ti-vacancies (La-doping) or by non-fer-
roelectric ZrO 6 octahedra (Zr-doping) should disrupt the
cooperative linking between TiO 6 units. Decoupling the
ferroelectric-active corner sharing octahedra may assist
reorientation of the ferroelectric domains close to T c at low
dopant levels and may explain the substantial rise in ´ 9max ,
for x#0.06. The origin of the relaxor phenomenon in
La-doped compositions is unclear, however, as the effect
increases with x, it may result from aggregation of defects,
Fig. 4. R T as a function of temperature for x50.03 heated at 13508C in Ar and air, (a). Arrhenius plot of bulk and grain boundary conductivity data for
x50.20 heated at 13508C in Ar, (b).
resulting in a compositional fluctuation model similar to
that used to describe other relaxor materials [12]. The
distinct change in Ba for bulk conductivity data between
un-doped and doped compositions suggests a different
conduction mechanism exists in La-doped materials, how-
ever the data show no systematic trend with x, Fig. 3. This
suggests the conduction mechanism is not related directly
to the La-content and instead may be associated with
oxygen vacancies or with some unknown impurity / defect
state.
3.2. x 50.03 and 0.20, pO2 |10 Pa (1 atm Ar)
Both compositions were single-phase by EPMA / ana-
lytical TEM and were semiconducting at room tempera-
ture. Total resistance values, R T , where R T 5 R b (bulk) 1
R gb (grain boundary) of |0.52 and 6.2 kV were obtained
from the low frequency intercept of Z* plots for 0.03 and
0.20, respectively. Z* plots showed a single semicircular
arc (C52–5 nF, consistent with a semiconducting grain
boundary component) which dominated R T with a non-
zero (|10–12 V), high frequency intercept on the Z9 axis
[9]. The non-zero intercept was attributed to a semicon-
ducting bulk component as has been reported previously in
the analysis of Z* plots for commercial ptcr-BaTiO 3
ceramics [13]. x50.03 exhibited a modest ptcr effect when
heated above T c at |648C, Fig. 4(a). R T |R gb over the
measured temperature range, especially above T c . Large
R gb values made it difficult to estimate R b above T c . In
contrast, resistance data for x50.20 showed no sign of a
ptcr effect and instead, conductivity data obeyed the
Arrhenius law at low temperatures where bulk and grain
boundary data could be extracted from Z* plots, Fig. 4(b).
 F.D. Morrison et al. / International Journal of Inorganic Materials 3 (2001) 1205 – 1210
Ea for bulk and grain boundary components were low, with
values of 0.09 and 0.20 eV, respectively.
The existence of a ptcr effect in x50.03 is dependent on
many factors. Firstly, the sample contains semiconducting
grains and undergoes a ferro- to para-electric phase
transition over the measured temperature range (T c |648C,
Fig. 2(a)). Secondly, the grain boundary regions are more
resistive than the grains and this permits the development
of Schottky barriers at the grain / grain boundary interfaces.
A ptcr effect is observed only if the Schottky barrier
potential height can be suppressed by the spontaneous
polarisation of the ferroelectric domains within the grains
to produce a semiconducting R T below T c . These con-
ditions are satisfied for x50.03 heated in Ar at 13508C and
a modest ptcr effect is observed. For x50.20, T c (if it
exists) was below the measured temperature range and
therefore no ptcr effect observed.
It has previously been widely accepted [14] that ptcr
effects can be obtained only for La contents ,0.5 atom%
where La is assumed to act as a donor dopant. Our results
for x50.03 (3 atom %) demonstrate that it is possible to
obtain ptcr effects at much higher La-contents. The crucial
issue is to control R gb by limiting the amount of adsorbed
oxygen (acceptor states) in the grain boundary regions. If
the concentration of acceptor states is too high, the
spontaneous polarisation below T c cannot reduce the
Schottky barrier height potential at the grain / grain bound-
ary interfaces, R gb is insulating and a ptcr effect is not
observed. IS results for x50.03 heated in air at 13508C
(where more oxygen can be adsorbed at the grain
boundaries compared to Ar-heated samples) showed the
presence of a semiconducting grain component of 10–12
V, however, R T |R gb .10 7 V at room temperature [8] and
no ptcr effect was observed, Fig. 4(a). In practice, R gb is
normally controlled by altering the cooling rate for sam-
ples heated in air, however it can also be controlled by
varying the pO 2 of the gas ambient, Fig. 4(a). Using the
Fig. 5. Schematic electrical microstructures for La-doped ceramics prepared at 13508C in various atmospheres. Shading represents semiconducting regions.
1209
latter approach it is possible to obtain ptcr behaviour in
La-doped BaTiO 3 ceramics with x40.005.
3.3. 0, x #0.20, pO2 |20 kPa (1 atm air)
Samples treated in air showed intermediate electrical
properties compared to those heated in O 2 and Ar [8,9].
Oxygen loss gives rise to oxygen gradients which can
result in at least three electro-active regions contributing to
the total (dc) resistance of the ceramics. The presence (or
absence) of these regions depend on many factors includ-
ing the ceramic microstructure (grain size, pellet density)
and cooling rate. At least two distinct types of electrical
microstructure have been identified and these are illus-
trated schematically in Fig. 5. They can consist of oxygen
deficient, semiconducting grain interiors, with partially
oxidised grain surfaces and oxidised, insulating grain
boundaries, Fig. 5(a). Such ceramics may be dc insulators
or exhibit ptcr effects depending on the concentration of
adsorbed oxygen at the grain boundary regions. Alter-
natively, they may be inhomogeneous on a more macro-
scopic level and contain a semiconducting pellet ‘core’,
containing oxygen-deficient bulk and grain boundary re-
gions, covered by an oxidised insulating ‘skin’ at the pellet
surfaces, Fig. 5(b). These are normally dc insulators but
can become semiconducting on removal of the insulating
surface layer by polishing the pellet surfaces. Details of the
IS results for air-heated ceramics are reported elsewhere
[7,9]. For the sake of completeness, schematic electrical
microstructures for O 2 and Ar heated ceramics are also
included in Fig. 5.
4. Conclusions
Single phase Ba 12x Lax Ti 12x / 4 O 3 compositions exhibit
an impressive and diverse range of electrical characteris-
1210 F.D. Morrison et al. / International Journal of Inorganic Materials 3 (2001) 1205 – 1210
tics; however, it is important to either suppress or control
the loss of oxygen from ceramics to obtain the desired
electrical properties. Accessible properties of these materi-
als are:
(a) Very high permittivity values and ferroelectric ‘relax-
or’ behaviour for ceramics prepared at 13508C in O 2 where
oxygen loss is negligible and samples are electrically
insulating.
(b) Semiconducting materials for all x when heated in
Ar at 13508C leading to small amounts of oxygen loss.
(c) Electrically inhomogeneous ceramics caused by
oxygen gradients in samples heated in air at 13508.
Finally, we stress that we see no evidence for a switch in
La-doping mechanism from ionic to electronic compensa-
tion under the conditions employed in this study, i.e.
T513508C and pO 2 .10 Pa (1 atm Ar). Experiments at
higher temperatures and lower pO 2 are now in progress to
determine under which conditions, if any, a switch in
mechanism occurs and La acts as a direct donor dopant.
Acknowledgements
The authors would like to thank the EPSRC for support,
Dr Alison Coats (Aberdeen University) for EPMA and Dr
Eric Lachowski (Aberdeen University) for TEM.
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