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Scripta Materialia 64 (2011) 268–271

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Marked increase in Curie temperature upon annealing of

ferroelectric KF-substituted barium titanate
Shinya Tsukada⇑ and Yukikuni Akishige
Faculty of Education, Shimane University, Matsue, Shimane 609-8504, Japan
Received 29 July 2010; accepted 5 October 2010
Available online 21 October 2010

The effect of annealing on Curie temperature (TC) is investigated in ferroelectric KF-substituted BaTiO3 (KF-BT/x). We succeed
in controlling TC of KF-BT/x from 262 to 384 K by annealing in oxygen. The thermal gravimetric analysis suggests that well-
annealed KF-BT/0.10 does not contain F, indicating that the TC is enhanced by the evaporation of F. We propose that these marked
changes in TC are achieved by strengthening the covalency between Ti and O (F) through the annealing.
Ó 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Ferroelectricity; Dielectrics; Perovskites; Annealing; Electrical resistivity/conductivity

Ferroelectric materials are widely used in posi-
tive temperature coefficient resistors, piezoelectric ele-
ments, multilayer and barrier layer capacitors due to
the permanent polarization arising from the atomic dis-
placement [1–3]. Since the permanent polarization dis-
appears above the Curie temperature (TC), the control
of TC in ferroelectric materials is of great importance
for practical applications. A familiar technique to
change TC is ionic doping, which usually lowers the
TC [1,3,4]. However, only a few techniques are known
to raise the TC.
The most technologically popular ferroelectrics are
perovskite oxides represented by ABO3, the properties
of which are sensitive to electrical fields, temperature,
defects and dopants. The pronounced sensitivity of the
ferroelectrics derives from the competition between
long-range Coulomb forces and short-range repulsion
forces, and the disruption of this competition leads to
ferroelectric phase transitions: long-range Coulomb
forces favor ferroelectric ordering (with permanent
polarization), while short-range repulsion forces favor
the paraelectric cubic phase (without permanent polari-
zation). A key for ferroelectricity in the perovskite oxi-
des is the covalency (electronic orbital hybridization)
of the B–O bond in the ABO3 perovskite structure; this
covalency softens the short-range repulsion forces
against the ferroelectric ordering. The importance of
⇑ Corresponding author. Tel./fax: +81 852 32 6304; e-mail: tsukada@
edu.shimane-u.ac.jp
the covalency in ferroelectric perovskite oxides was sug-
gested theoretically [5–9], and subsequently confirmed
by experiments [10,11]. It is not surprising that TC can
be controlled via covalency. In other words, the B–O
covalency is a benchmark for TC control in the process
of ferroelectric material design.
One classic ferroelectric perovskite, BaTiO3, has a
ferroelectric phase transition from the high-temperature
paraelectric cubic phase to the low temperature ferro-
electric tetragonal phase at 396 K (=TC) [12,13]. It has
been pointed out that hybridization between Ti 3d and
O 2p enhances the ferroelectric instability of BaTiO3,
with the Ba–O bond being almost ionic [5,6,9–11]. To
control the covalency, we have focused on the effects
of KF substitution on the ferroelectric behavior in
BaTiO3 (K+ and F substituting for Ba2+ and O2,
respectively) because F has the largest electronegativity
of all elements [14–16]. The covalency of Ti–O must be
weakened by substituting F for O. As it is known that
BaTiO3 grown by the KF flux method shows a lower
TC, KF is very influential [12–16]. On the basis of above
situations, we fabricated KF-substituted BaTiO3
(Ba1xKxTiO3xFx; KF-BT/x) crystals [14,15], nano-
powders and ceramics up to x = 0.15 [17,18]. It was
found that KF decreases the TC to 260 K and that the
dielectric anomaly at TC is markedly enhanced when x
is close to 0.10. These are essential properties for appli-
cations in dielectric, pyroelectric and electrooptic
devices [1–3]. Here we report the effect of annealing on
TC in KF-BT/x (x  0.10 and 0.12), and demonstrate

1359-6462/$ - see front matter Ó 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2010.10.007
 S. Tsukada, Y. Akishige / Scripta Materialia 64 (2011) 268–271
a marked increase in TC due to the evaporation of F. Be-
cause it is uncommon to substitute O for other elements
in ferroelectric perovskite oxides, we believe that the
present results could be a clue to the development of
the next generation of novel materials.
Transparent single crystals of KF-BT/x (x  0.10 and
0.12) with a slight yellow color were prepared by a flux
technique using fine powders of BaCO3 (Yamanaka
Semiconductor, 99.9%), TiO2 (Mitsuwa Chemical,
99.98%) and KF (Honeywell, 99.9%). Details of the
technique are provided in Refs. [14,15]. The difference
in TCs in the same batch is less than 3 K, which is much
smaller than the change in TC discussed in this report.
The crystals were then annealed at 1273, 1373 and
1473 K for 12 h in an O2 atmosphere. The complex
dielectric constant e* = e0  je00 of the as-grown and an-
nealed samples were measured using an LCR meter (HP,
4284A) in the cubic [1 0 0] direction. The measurements
were performed on heating at 2 K min1. Silver paste
(Dupont, #7095) was fired on the main faces of a capac-
itor specimen for the electrodes, and gold wires with a
diameter of 50 lm were attached to the faces. The dielec-
tric measurements were performed on more than two
samples for checking the repeatability. Thermal
gravimetric analysis (TGA; Shimazu, TGA-51H) on
KF-BT/0.10 particles (prepared by a sol–gel method as
described in Refs. [17,18]) and BaTiO3 (Aldrich,
99.995%) was carried out in an N2 gas flow to investi-
gate what happens at higher temperatures.
The temperature dependences of e0 and e00 are shown
in Figure 1a for the as-grown (a.g.) and annealed (at
1273 and 1473 K) KF-BT/0.10 single crystals (hereafter,
the samples are denoted KF-BT/x (Ta), where Ta is the
x = 0.10
(a) x 10 83
30 Hz 2 x 10
3 700 K, although it is known that the e0 of a BaTiO3 sin-
a.g.
4 1
10 kHz
0 0
8
annealed at 2 F acts as a donor in KF-BT/x; therefore, the result
ε"
ε'
4 1273 K 1 on KF-BT/0.10 (a.g.) in Figure 2a indicates that KF
0 0
8 2
annealed at
4 1473 K 1
0 0
200 300 400 200 300 400
Temperature (K)
x = 0.12
(b) x 10 6
3
30 Hz x 102
1
3 a.g.
10 kHz
0 0
6 Temperature (K)
annealed at 1
ε"
ε'
3 1273 K
0 0
6 10 -3
annealed at
1 10 -4
3 1273 K
1473 K
0 0
200 300 400 200 300 400
Temperature (K)
Figure 1. Temperature dependence of the complex dielectric constants
e0 (left) and e00 (right) of (a) KF-BT/0.10 and (b) KF-BT/0.12 under
different annealing conditions. a.g. (as-grown) denotes KF-BT/x
without annealing. The annealing time is 12 h.
269
annealing temperature). Three anomalies are clearly
seen in the e 0 of KF-BT/0.10 (a.g.). They correspond
to the structural phase transitions from the lowest ferro-
electric rhombohedral phase to the ferroelectric ortho-
rhombic phase at 217 K, to the ferroelectric tetragonal
phase at 273 K and to the paraelectric cubic phase at
323 K (=TC). By the KF substitution with x = 0.10,
the TC of BaTiO3 is suppressed to 323 K, and the three
phase transitions get closer. No particular frequency dis-
persion is found in KF-BT/0.10 (a.g.). Interestingly, the
TC increases with annealing. The TC is 342 K in KF-BT/
0.10 (1273 K), 384 K in KF-BT/0.10 (1373 K) and
371 K in KF-BT/0.10 (1473 K). Furthermore, each
phase transition temperature separates, as is found in
BaTiO3 after annealing. Note that frequency dispersion
appears at higher temperatures in the annealed samples,
which must be attributed to the electrical conduction.
Not only KF-BT/0.10 but also KF-BT/0.12 demon-
strates a dramatic change in TC, as shown in Figure
1b: KF-BT/0.12 (a.g.) has its TC at 298 K, while the
TC increases to 314 K in KF-BT/0.12 (1273 K), to
382 K in KF-BT/0.12 (1373 K) and to 373 K in KF-
BT/0.12 (1473 K). The TC becomes identical for both
compositions after annealing above 1373 K. In addition,
the increase in e0 and e00 are also observed at higher tem-
peratures in the annealed KF-BT/0.12. These annealing
effects on TC must be general to all KF-BT/x. As far as
we know, this is the first report that annealing raises the
TC of ferroelectrics by 120 K.
To observe the differences in the annealing effects on
the ferroelectric materials, dielectric measurements were
carried out on KF-BT/0.10 single crystals at higher tem-
peratures (see Fig. 2a) in addition to the lower tempera-
tures (represented in Figure 1). The e 0 of KF-BT/0.10
(a.g.) does not show any increase on heating up to
gle crystal grows with heating above 500 K, which is
attributed to the electrical conductivity due to vacancies
inside the crystals [12,19]. K+ acts as an acceptor while
substitution improves the dielectric property by hybrid
(a) x= 0.10
a.g. 1273 K 1373 K 1473 K
100000
100 Hz
ε'
10000
1000
10 kHz
400 600 400 600 400 600 400 600
(b) 10 -1 1373 K
10 -2
m−1)
−1
1473 K
σ (Ω
10 -5 a.g.
10 -6
1.5 2.0 2.5
1 / T 10-3(K-1)
Figure 2. (a) e0 of KF-BT/0.10 (Ta) as a function of temperature above
300 K at four annealing conditions. (b) Temperature dependence of
conductivity calculated from e00 using Eq. (1). The r of KF-BT/0.10
(1373 K) overlaps with that of KF-BT/0.10 (1473 K).
270 S. Tsukada, Y. Akishige / Scripta Materialia 64 (2011) 268–271

doping. On the other hand, the e0 values of the annealed 1600 1473 K

T (K)
samples are dispersive: e0 becomes larger and its order of 1200
800 1373 K 1273 K
400
magnitude changes as the measurement frequency is in- 0
creased. In addition, the peak around 550 K is apparent 100.0
BT Ta=1473 K
in the annealed samples. This peak is observed in many 99.6
KF-BT/0.10

Weight (%)
perovskite oxides, and our result can be explained by the 99.2 Ta=1273 K
“relaxation of defect dipoles” [20]. So, the enhancement
98.8 1373 K
of the dielectric constant by annealing in Figure 2a is
attributed to the increase in the number of vacancies. 98.4
1473 K
Because the origin of the increase in e0 at high temper- 98.0
10000 20000 30000 40000
atures is induced by the electrical conductivity, it is valu-
Time (min.)
able to estimate that conductivity. We determine the
conductivity r by using e00 (not shown) through Figure 3. TGA curves of the KF-BT/0.10 and BaTiO3 (BT) powders.
00 The measurement was carried out in an N2 gas flow.
r ¼ 2pf e ð1Þ
where f denotes the measurement frequency. The r of
KF-BT/0.10 is demonstrated in Figure 2b as a function In the following, we discuss the microscopic origins
of reciprocal temperature. The higher the annealing tem- for every phenomenon observed in Figures 1 and 2.
perature is set, the greater the enhancement of r, which First, the composition unit of defect dipoles in KF-
supports our idea that annealing generates the vacan- BT/0.10 (a.g.) is discussed. Here, K+ substitutes for
cies. Change in the inclination is also found in the an- Ba2+ (denoted as K0Ba [23]) and F substitutes for O2
nealed samples at T1  0.0016 K1 (T  625 K). On (FO ), respectively. K0Ba and FO have opposite charges
the basis of the thermally activated Arrhenius law repre- and attract one other; as a result, the defect dipole
sented by Eq. (2), we determine the activation energy Ea: K0Ba  FO is easily formed. The K0Ba  FO is static and
r ¼ r0 expðEa =k B T Þ ð2Þ does not rotate at all temperatures because there is no
space for the rotation (the absence of oxygen vacancies
where r0 is the conductivity at the high-temperature lim- blocks the rotation). As a consequence, no enhancement
it and kB denotes the Boltzmann constant. Ea is deter- in e0 is found even at high temperatures (Fig. 2a). In con-
mined to be 0.88 eV at all temperatures for KF-BT/ trast, O2 vacancies (V O ) should be created in the an-
0.10 (a.g.); on the other hand, it is 0.95 eV at higher tem- nealed samples to keep the charge neutral throughout
peratures (above 625 K) and 0.62 eV at lower tempera- the reaction (schematically illustrated in Figure 4b):
tures (below 625 K) for three annealed KF-BT/0.10 s.
These two values are also obtained in Mg-doped and 1
2FO þ O2 ! V O þ O
O þ F2 ðgasÞ ð3Þ
Bi-doped BaTiO3 at almost the same temperature range 2
[20–22]. The r can be attributed to the free ionic carriers,
which appear across the whole temperature range with
Ea = 0.95 eV. In addition, the relaxation of defect di-
poles contributes to r below 625 K. As a result, the incli- (a)
nation of r changes.
The contrasting dielectric behaviors as well as TC be-
ε

tween KF-BT/0.10 (a.g.) and the annealed KF-BT/0.10

indicate the inherent differences inside them. According
to Bao et al. [23], KF-flux-grown BaTiO3 crystals that
have been annealed well at 1273 K in air show a marked
TC

decrease in the amount of F and only a slight decrease in

ε

the amount of K. Therefore, we consider that the change

in the dielectric behavior after annealing at 1273 K can 1273 1373 1473
be attributed mainly to the evaporation of F from Temperature (K) Annealing Temperature (K)
KF-BT/0.10 (a.g.). Figure 3 shows the TGA results for (b)
BaTiO3 and KF-BT/0.10 (Ta). Here, weight fractions
of F and K in KF-BT/0.10 (a.g.) are calculated to be
0.85% and 1.75%, respectively. The weight of BaTiO3
is almost constant at all temperatures up to 1473 K,
indicating that Ba, Ti and O do not evaporate notably.
Weight losses of 0.7, 1.1 and 1.6 wt.%, respectively, oc-
cur in KF-BT/0.10 (1273 K), KF-BT/0.10 (1373 K),
and KF-BT/0.10 (1473 K) above 1000 K. If we consider
the results by Bao et al. together with the TGA on Ba-
TiO3, the TGA on KF-BT/0.10 (1273 K) represents Figure 4. (a) Left: temperature dependence of the dielectric constants
the evaporation of F; that on KF-BT/0.10 (1373 K) rep- of KF-BT/0.10 and KF-BT/0.12 under different annealing conditions.
resents the evaporation of almost all of F as well as a The probe frequency is set to 10 kHz. Right: TC vs. Ta. (b) Schematic
small amount of K; and that on KF-BT/0.10 (1473 K) perovskite structure of KF-BT/x before (left) and after (right)
represents the evaporation of both F and K. annealing. It represents Eq. (3).
 S. Tsukada, Y. Akishige / Scripta Materialia 64 (2011) 268–271
The defect dipole K0Ba  V O is thus formed. In this
case, rotation of the defect dipole is possible through
the hopping V O when it is thermally activated. The rota-
tion must correspond to the peak in e0 around 625 K.
The defect dipoles are disassociated at higher tempera-
ture than 625 K; consequently, ionic conduction is in-
duced due to the V O . The activation energy for the
diffusion of V O must be 0.95 eV, corresponding to the
conductivity in Figure 2b. The higher the annealing tem-
perature, the more V O the sample contains. Therefore, it
is natural that the r of KF-BT/0.10 (1273 K) is lower
than that of KF-BT/0.10 (1473 K). Ba2+ vacancies
(V 0Ba ) are also created in KF-BT/0.10 (1373 K) and
KF-BT/0.10 (1473 K) through
K0Ba ! V 0Ba þ K ðgasÞ ð4Þ
2+
However, Ba is too large to move freely. Actually,
as shown in Figure 2b, the r of KF-BT/0.10 (1373 K)
coincides with that of KF-BT/0.10 (1473 K), where the
difference between the two samples is the amount of
V 0Ba . Thus, we regard the contribution of V 0Ba to r as
being small.
Next, the annealing effect on TC is discussed. The TC,
which is related to the strength of the Ti–O (F) covalen-
cy, is decreased by the KF substitution. We attribute
this decrease to the substitution of O2 by F rather
than that of Ba2+ by K+ due to the reduction in the cov-
alency between Ti and O (F), because F has the greatest
electronegativity. Here, the ionic radii of Ba2+ and K+
are almost the same and those of O2 and F are rela-
tively close, thus the effect of chemical pressure is
excluded as a dominant factor in this case. When the
samples are annealed, FO is replaced by V O and O O , as
described in Eq. (3), which stiffens the covalency and,
as a result, TC increases. The e0 of each sample is summa-
rized in Figure 4a. TC of KF-BT/0.10 is identical to that
of KF-BT/0.12 after annealing above 1373 K, indicating
that TC does not increase after the evaporation of all FO .
The samples with the highest TC (KF-BT/0.10 (1373 K)
and KF-BT/0.12 (1373 K)) still have a TC (384 K) that
is different from the TC of BaTiO3 (=396 K). This gap
could be due to the V O (i.e., a decrease in the covalent
electrons), as observed in other acceptor-doped BaTiO3
[20–22,24]. One of the authors (Y.A.) has already re-
ported the annealing effect on the tand of BaTiO3 grown
by the KF-flux method, and the effect was attributed to
the conducting electrons generated by the acceptor (K)
doping [12]. However, the current study gives a clear
solution for it.
We have observed remarkable changes in dielectric
properties induced by annealing in KF-BT/x single crys-
tals. We have succeeded in controlling the TC between
262 and 384 K by the combination of annealing (which
raises TC) and KF substitution (which suppresses TC).
The remarkable changes originate from the change in
the amount of F. Because F is the largest electronegativ-
ity of all elements, we attribute the phenomenon to the
change in the covalency between Ti and O (F). This
intriguing phenomenon, induced by annealing, has
important technical implications for tuning ferroelectric
271
properties through controlling the amount of F in the
crystal. It is not usual to substitute the O-site in the fer-
roelectric perovskite ABO3, even though the ferroelec-
tricity is closely connected with the O-site. It would be
interesting to investigate the O substitution from various
viewpoints.
The authors would like to express their cordial
gratitude to Natsui and Hidaka (TDK Corp.) for fruit-
ful discussions. We also appreciate Hada and Matsum-
oto (Shimane University) for their help with the TGA
and XGT measurements, respectively. The KF powders
used in this study were provided by Honeywell Interna-
tional Inc.
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