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Grain Size Effect on the Nonlinear Dielectric Properties of Barium Titanate

Ceramics

Article in Applied Physics Letters · January 2011

DOI: 10.1063/1.3526375 · Source: IEEE Xplore

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 APPLIED PHYSICS LETTERS 97, 242909 共2010兲

Grain size effect on the nonlinear dielectric properties of barium

titanate ceramics
Lavinia Curecheriu,1,a兲 Maria Teresa Buscaglia,2 Vincenzo Buscaglia,2 Zhe Zhao,3 and
Liliana Mitoseriu1
1
Department of Physics, Alexandru Ioan Cuza University, Bv. Carol I No. 11, Iasi 700506, Romania
2
Institute of Energetics and Interphases (IENI)-CNR, Via De Marini No. 6, I-16149 Genoa, Italy
3
Department of Materials and Environmental Chemistry, University of Stockholm, SE-10691 Stockholm,
Sweden
共Received 31 October 2010; accepted 20 November 2010; published online 16 December 2010兲
The nonlinear dielectric properties of dense BaTiO3 ceramics with grain size of 1 ␮m – 90 nm were
investigated. In the finest ceramics, the permittivity reduces below 1000 and a remarkable
nonhysteretic linear dc-tunability 关␧共E兲兴 is obtained at high field, above 40 kV/cm. The observed
behavior was explained by considering the nanostructured ceramic as a composite formed by
ferroelectric grains, whose nonlinearity is reducing, and by low-permittivity nonferroelectric grain
boundaries, whose volume fraction increases when decreasing the grain size. Reducing the grain
size in ferroelectric dense materials is an alternative route to accomplish the application
requirements: nonhysteretic tunability and permittivity below 1000. © 2010 American Institute of
Physics. 关doi:10.1063/1.3526375兴

In the past years, intensive efforts have been spent in
developing nonlinear dielectric materials due to their poten-
tial for substantial miniaturization of microwave components
and integration in microelectronic circuits.1–4 Such applica-
tions demand nonhysteretic materials possessing relatively
high tunability, moderate dielectric constant of ⬃1000, and
tan ␦ below 3%.5 Since these requirements are, to some ex-
tent, conflicting, new solutions to realize a compromise of
these parameters are still searched. One largely adopted
solution to reduce losses and permittivity while preserving
a high tunability was to realize composites formed by
ferroelectric solid solutions, e.g. 共Ba, Sr兲TiO3 with low-
permittivity nonferroelectrics such as MgO, MgTiO3, or
Al2O3.6,7 However, the reproducibility and stability of their
properties need to be improved and, in any case, the explo-
ration of other materials and the design of new structures are
still desirable for tunable devices, together with fundamental
studies related to the origin of dielectric nonlinearity.
A ferroelectric ceramic can be regarded as a composite
formed by grain cores and low-permittivity grain boundary
layers with different structural, compositional, and defect-
related properties.8 The influence of grain boundary layers on
the functional properties became major when ceramics have
ultrafine grains below 200 nm. For example, in dense
BaTiO3 nanostructured ceramics with average grain size of
⬃50 nm, the volume fraction of the grain boundary layer
was estimated to represent ⬃20% – 30% of the whole sample
volume.9 The peculiar properties of nanostructured dense
BaTiO3 ceramics with grains in the range of tenths of
nanometers10,11 were described within the model of compos-
ite ceramic grains. A systematic investigation of the crystal
structure, phase transitions, switching, and permittivity of
BT dense ceramics with grain sizes from 1200 down to 30
nm show that the decrease of the effective permittivity, and
the suppression of the polarization-field P共E兲 hysteresis are
determined by a combination of intrinsic size effect and the
a兲
Electronic mail: lavinia_curecheriu@stoner.phys.uaic.ro.
“dilution” effect due to the low-permittivity grain
boundaries.9,10,12 The boundary layer is very sensitive to the
processing parameters and to the quality of the starting nan-
opowders. Even in pure BaTiO3 nanoceramics, the Ba/Ti sto-
ichiometry, atomic bonding, charge defects, and dipolar
ferroelectric interaction at the grain boundaries are com-
pletely different than the grain cores. It is largely accepted
that grain boundary layer is a highly atomic disordered re-
gion, even amorphous, or with relaxed tetragonality, charac-
terized by low polarization 共nonferroelectric兲 and low
permittivity.8–11
Following these considerations, it seems that an alterna-
tive method to reduce the permittivity and hysteretic behav-
ior while preserving high tunability can be achieved by re-
ducing the grain size in the ferroelectric nanoceramics. Being
ferroelectric at room temperature, pure BaTiO3 was previ-
ously considered less interesting for tunability applications
due to its hysteretic P共E兲 dependence and domain wall re-
laxation at 104 – 106 Hz.13 Only few communications re-
ported permittivity-field dependences in BaTiO3 single crys-
tal, films, and ceramics.14–16 Therefore, based on the model
of composite, a study of the grain size influence on the non-
linear permittivity in pure BaTiO3 ceramics with grain size
共GS兲 in the range of 1 ␮m – 90 nm was realized.
Ultrafine BaTiO3 powders 共particle size about 15 nm兲
obtained by solution precipitation17 were sintered by spark
plasma sintering 共SPS兲,18 at different temperatures 共1250
− 1050 ° C兲 for 3 min, in order to result in dense ceramics
with various grain sizes. The ceramics were annealed in air
at 800 ° C / 24h after sintering to reduce the oxygen vacancies
caused by the reducing atmosphere characteristic in the SPS
process. The final samples were characterized by high den-
sity 共 ⬎ 95% 兲 and low dielectric losses 共tan ␦ ⬍ 1% at 20–
150 °C and 104 − 106 Hz兲. The sample morphology was ob-
served on fracture surfaces by a scanning electron
microscopy 共SEM兲 共LEO 1450VP兲 equipped with an energy
dispersive x-ray microprobe 共Oxford Instruments Inca 300兲.
Gold electrodes were applied by rf-sputtering on the polished

0003-6951/2010/97共24兲/242909/3/$30.00 97, 242909-1 © 2010 American Institute of Physics

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 242909-2 Curecheriu et al.
FIG. 1. 共Color online兲 Computed permittivity vs field dependence of
BaTiO3 ceramics with different grain sizes in the range 共90 nm, 1 ␮m兲
within the effective field model and Johnson approach. Inset: grain size
dependence of the filling factor f.
surfaces of ceramics for the electrical characterization. High-
voltage dc-tunability measurements were performed at room
temperature on the electroded ceramic disks immersed in
transformer oil, under high voltages produced by a function
generator coupled with a TREK 30/20A-H-CE amplifier.19
A simplified approach based on the Bruggeman effective
medium theory20 coupled with a nonlinear field-dependence
permittivity approximation was first used to estimate the size
dependent tunability in BaTiO3 nanoceramics in a manner
similar to that proposed for ferroelectric-dielectric
composites.21 A spherical dielectric inclusion with high per-
mittivity coated by a low-permittivity layer embedded into
an infinite homogeneous medium was considered in the
analysis. The effective permittivity ␧eff of the mixture is a
macroscopic quantity describing the average permittivity
over a large sample of such composite material. Among the
several theories describing the effective permittivity,20 the
Bruggeman theory was chosen for which,
␧ f − ␧eff ␧d − ␧eff
f + 共1 − f兲 = 0,
␧ f + 2␧eff ␧d + 2␧eff
where ␧eff is the effective field permittivity, f is the volume
filling ratio of the ferroelectric material in the matrix, and ␧d
and ␧ f are the permittivities of the dielectric and ferroelectric
phases, respectively. This formula predicts a reducing per-
mittivity to less than a half, when grain size ranges from
1 ␮m down to 50 nm, as a “dilution effect,” similar to the
experimental features reported for nanostructured dense
ceramics.8,9
The grain size dependence of tunability was first esti-
mated by considering that only the ferroelectric grain core
exhibits a nonlinear behavior, while the grain boundary layer
remains linear with a constant permittivity of ␧d ⬃ 100,8 and
it does not contribute to the dc-tunability. The field variation
of permittivity of the ferroelectric grain core is commonly
described by Johnson’s relationship,22 which is derived
from the Landau–Ginzburg–Devonshire 共LGD兲 theory of
ferroelectricity,23
Downloaded 17 Dec 2010 to 85.122.26.116. Redistribution subject to AIP license or copyright; see http://apl.aip.org/about/rights_and_permissions
Appl. Phys. Lett. 97, 242909 共2010兲
FIG. 2. SEM image on the fractured surface of BaTiO3 ceramics with ex-
treme grain sizes investigated in the present study: 共a兲 GS= 1000 nm; 共b兲
GS= 90 nm.
␧ f 共0兲
␧ f 共E兲 = , 共2兲
关1 + 3␤␧ f 共0兲3␧30E2兴1/3
in which ␧ f 共0兲 is the ferroelectric permittivity at zero field
and ␤ is a LGD parameter directly related to the permittivity
nonlinearity.
The calculated field dependence of the effective
permittivity of the composite material with filling factors
in the range of 0.97–0.67 共see inset in Fig. 1兲, corresponding
to GSs between 1 ␮m and 70 nm, is shown in Fig. 1, where
the parameters used in the simulations were considered
from the experimental data of barium titanate-based
ceramics:11,24,25 ␧ f 共0兲 = 900– 3500 and ␤ in the range of
共1.3– 6兲 ⫻ 1010 V m5 / C3.
The computed permittivity has a strong field variation
共high tunability兲 and zero-field permittivity ␧eff共0兲 of 1000–
3500 for ceramics with large grains 共GS⬎ 400 nm兲, while
for fine grained ceramics 共GS⬍ 100 nm兲, ␧共0兲 is below
1000 and tunability is also lower 共Fig. 1兲. For the finest grain
sizes, two different field regions were identified: one below
20 kV/cm, for which the permittivity has a small variation
共below 4%兲, and one for high fields, above 30 kV/cm, where
the field decreasing permittivity is almost linear 共Fig. 1兲. The
model predicts the possibility to induce an almost linear de-
pendence ␧共E兲 together with a reduction of permittivity be-
low 1000 as a “dilution” effect due to the nonferroelectric
grain boundaries in nanostructured BaTiO3 ceramics with
GS below 100 nm.
共1兲
In order to experimentally check this possibility, the dc-
field ␧共E兲 dependence was determined at room temperature
in dense BaTiO3 ceramics 共densities above 98%兲, with grain
sizes ranging from 1 ␮m to 90 nm 共Fig. 2兲. The permittivity
versus temperature for BaTiO3 dense ceramics with different
grain sizes of 1000, 600, 150, 100, and 90 nm is presented in
Fig. 3 at a frequency of 750 kHz. The data qualitatively show
the system’s tendency toward a diffuse phase transition and a
shift of the Curie temperature from 120 to 104 ° C as the
grain size is reduced from 1 ␮m to 90 nm. A reduction of
the dielectric constant to ⬃1000 with decreasing grain size is
noticed, as predicted by effective field calculations and also
in agreement with the data reported elsewhere.8–11,26
The dc-tunability at room temperature is comparatively
presented in Fig. 4. The coarse BaTiO3 ceramic shows a
strong nonlinear decrease of the ␧共E兲 dependence, without a
tendency to saturation, even at fields as high as ⬃35 kV/ cm.
The finest grained ceramics 共GS= 90 and 100 nm兲 show non-
hysteretic ␧共E兲 variations at the increasing/decreasing dc
field, very similar to each other. In the field range E
 242909-3 Curecheriu et al. Appl. Phys. Lett. 97, 242909 共2010兲

accessible. In any case, reducing the grain size at nanoscale

in BaTiO3 seems to be an alternative route to the traditional
ones to accomplish the requirements of high tunability, non-
hysteretic ␧共E兲 dependence, and permittivity in the range of
⬃1000, necessary for tunable applications.
This work was supported by CNCSIS-UEFISCSU-PNII-
RU-TE code 187/2010.
1
O. G. Vendik, E. Kollberg, S. S. Gevorgian, A. B. Kozyrev, and O. I.
Soldatenkov, Electron. Lett. 31, 654 共1995兲.
2
A. B. Kozyrev, T. B. Samoilova, A. A. Golovkov, E. K. Hollmann, D. A.
Kalinikos, V. E. Loginov, A. M. Prudan, O. I. Soldatenkov, D. Galt, C. H.
Mueller, T. V. Rivkin, and G. A. Koepf, J. Appl. Phys. 84, 3326 共1998兲.
3
FIG. 3. 共Color online兲 Temperature dependence of the dielectric constant of C. Ang, A. S. Bhalla, R. Guo, and L. E. Cross, Appl. Phys. Lett. 76, 1929
BaTiO3 dense ceramics with various grain sizes 共indicated in figure, in nm兲 共2000兲.
4
at the frequency of 750 kHz. Z. Yu, C. Ang, R. Guo, and A. S. Bhalla, Appl. Phys. Lett. 81, 1285
共2002兲.
5
A. K. Tagantsev, V. O. Sherman, K. F. Astafiev, J. Venkatesh, and N.
⬍ 40 kV/ cm, their permittivity has a small field variation of Setter, J. Electroceram. 11, 5 共2003兲.
only 5%–10% 共Fig. 4兲. For higher fields 共up to 6
U.-C. Chung, C. Elissalde, M. Maglione, C. Estournes, M. Pate, and J. P.
80– 120 kV/ cm, limited by breakdown field兲, an almost lin- Ganne, Appl. Phys. Lett. 92, 042902 共2008兲.
7
ear decrease of permittivity is observed, as reported in the M. W. Cole, P. C. Joshi, M. H. Ervin, M. C. Wood, and R. L. Pfeffer, Thin
Solid Films 374, 34 共2000兲.
inset of Fig. 4. The grain size effect of the ␧共E兲 dependence 8
A. Y. Emelyanov, N. A. Pertsev, S. Hoffman-Eifert, U. Böttger, and R.
in BaTiO3 ceramics is similar to that predicted by combining Waser, J. Electroceram. 9, 5 共2002兲.
9
the effective field model and Johnson approach. Z. Zhao, V. Buscaglia, M. Viviani, M. T. Buscaglia, L. Mitoseriu, A.
In summary, the present study shows that ␧共E兲 depen- Testino, M. Nygren, M. Johnsson, and P. Nanni, Phys. Rev. B 70, 024107
dence in fine BaTiO3 structures is driven by a combined 共2004兲.
10
M. H. Frey and D. A. Payne, Phys. Rev. B 54, 3158 共1996兲.
effect of the ferroelectric core whose nonlinearity is gradu- 11
M. T. Buscaglia, M. Viviani, V. Buscaglia, L. Mitoseriu, A. Testino, P.
ally reducing, together with the increasing amount of the Nanni, Z. Zhao, M. Nygren, C. Harnagea, D. Piazza, and C. Galassi, Phys.
nonferroelectric “dead-layer” grain boundaries, when reduc- Rev. B 73, 064114 共2006兲.
12
ing the grain size down to tenths of nanometers. The remark- T. Hoshina, S. Wada, Y. Kuroiwa, and T. Tsurumi, Appl. Phys. Lett. 93,
able linear decrease of ␧共E兲, combined with the reduced 192914 共2008兲.
13
M. Maglione, R. Bohmer, A. Loidl, and U. T. Hochli, Phys. Rev. B 40,
permittivity below 1000, makes BaTiO3 nanostructured ce- 11441 共1989兲.
ramics interesting for tunability applications. However, this 14
I. N. Leont’ev, A. Leiderman, V. Yu. Topolov, and O. E. Fesenko, Phys.
␧共E兲 linear feature is typical to very high fields. Further stud- Solid State 45, 1128 共2003兲.
15
ies to check this opportunity should be performed in thin J. Xu, J. Zhai, and X. Yao, J. Alloys Compd. 467, 567 共2009兲.
16
BaTiO3 nanostructures, for which lower voltage is easily I. Fujii, M. Ugorek, and S. Trolier-McKinstry, J. Appl. Phys. 107, 104116
共2010兲.
17
A. Testino, M. T. Buscaglia, M. Viviani, V. Buscaglia, and P. Nanni, J.
Am. Ceram. Soc. 87, 79 共2004兲; A. Testino, M. T. Buscaglia, V. Busca-
glia, M. Viviani, C. Bottino, and P. Nanni, Chem. Mater. 16, 1536 共2004兲.
18
Z. Shen, Z. Zhao, H. Peng, and M. Nygren, Nature 共London兲 417, 266
共2002兲.
19
F. M. Tufescu, L. Curecheriu, A. Ianculescu, C. E. Ciomaga, and L. Mi-
toseriu, J. Optoelectron. Adv. Mater. 10, 1894 共2008兲.
20
D. A. G. Bruggeman, Ann. Phys. 416, 636 共1935兲; K. K. Kärkkäinen, A.
H. Sihvola, and K. I. Nikoskinen, IEEE Trans. Geosci. Remote Sens. 38,
1303 共2000兲.
21
L. Jylha and A. H. Sihvola, Progr. in Electromag. Res., PIER 78, 189
共2008兲.
22
K. Johnson, J. Appl. Phys. 33, 2826 共1962兲.
23
V. L. Ginzburg and A. P. Levanyuk, J. Phys. Chem. Solids 6, 51 共1958兲;
Phys. Lett. A 47, 345 共1974兲.
24
FIG. 4. 共Color online兲 Experimental permittivity vs field dependence of C. Ang and Z. Yu, Phys. Rev. B 69, 174109 共2004兲.
BaTiO3 ceramics with grain sizes between 1 ␮m and 90 nm. Inset: linear 25
L. P. Curecheriu, F. M. Tufescu, A. Ianculescu, C. E. Ciomaga, L. Mito-
variation of permittivity with dc field for fields higher than 40 kV/cm for the seriu, and A. Stancu, J. Optoelectron. Adv. Mater. 10, 1792 共2008兲.
26
finest grain size ceramics: GS= 100 nm and GS= 90 nm. D. V. Taylor and D. Damjanovic, Appl. Phys. Lett. 73, 14 共1998兲.

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