Extrinsic effects on dielectric response of

ultrafine grain ceramics

Cite as: Appl. Phys. Lett. 97, 162913 (2010); https://doi.org/10.1063/1.3505924
Submitted: 13 April 2010 . Accepted: 04 October 2010 . Published Online: 22 October 2010

Haitao Zhang, Xiangyun Deng, Ting Li, Wen Zhang, Rike Chen, Wenwei Tian, Jianbao Li, Xiaohui Wang,
and Longtu Li

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Appl. Phys. Lett. 97, 162913 (2010); https://doi.org/10.1063/1.3505924 97, 162913

© 2010 American Institute of Physics.

 APPLIED PHYSICS LETTERS 97, 162913 共2010兲

Extrinsic effects on dielectric response of ultrafine grain BaTiO3 ceramics

Haitao Zhang,1 Xiangyun Deng,1,2,a兲 Ting Li,1 Wen Zhang,1 Rike Chen,1 Wenwei Tian,1
Jianbao Li,1,3 Xiaohui Wang,3 and Longtu Li3
1
Key Laboratory of Ministry of Education for Application Technology of Chemical Materials
in Hainan Superior Resources, Hainan Provincial Key Laboratory of Research on Utilization of Si–Zr–Ti
Resources, Materials and Chemical Engineering Institute, Hainan University, Haikou 570228,
People’s Republic of China
2
College of Physics and Electronic Information, Tianjin Normal University, Tianjin 300387,
People’s Republic of China
3
Department of Materials Science and Engineering, Tsinghua University, Beijing 100084,
People’s Republic of China
共Received 13 April 2010; accepted 4 October 2010; published online 22 October 2010兲
The complex dielectric response of ultrafine grain barium titanate ceramics is investigated using
broadband dielectric spectrometer. Extrinsic effects like conduction, space charge associating with
grain boundaries are discussed. One dielectric relaxation ascribes to the interaction of defects with
grain boundaries, for which the activation energy fitted by Arrhenius equation is equivalent to 0.26
eV and the value shifts to 0.41 eV after annealing treatment. Another relaxation phenomenon
locating at elevated temperature can be attributed to interfacial polarization due to space charge
accumulation effect. The study of complex impedance spectra suggests that grain boundary effects
support extrinsic mechanism. © 2010 American Institute of Physics. 关doi:10.1063/1.3505924兴

Barium titanate 共BTO兲-based ceramics is one of the
most attractive ferroelectric material for the use of multilayer
capacitors.1 However, the BTO-based ceramics show un-
usual dielectric characteristics when its grain size down to
nanoscale.
Comparing with coarse BTO ceramics, the conductivity
of 35 nm nanocrystalline enhances one to two orders of mag-
nitude due to a greatly reduced oxidation enthalpy.2 Colossal
permittivity present in ultrafine grain nonstoichiometric BTO
ceramics, which is ascribed to small polarons based on elec-
tronic hopping of Ti3+ / Ti4+.3 And the dielectric properties
are more susceptible to grain boundary for nanocrystalline
BTO ceramics, so called “dilute the effects of grain size.”4,5
Dielectric response mechanism, effectively deduced by
dielectric relaxation investigation, is closely to dielectric
like fluctuation of dipolar,6 ferroelectric domain,7 interfacial
polarization,8,9 and structural defect in ferroelectric
ceramics,10,11 etc. For nanocrystalline BTO ceramics, the ef-
fective permittivity will be controlled by the combination of
the intrinsic size effect and of the “dilution” effect due to the
nonferroelectric grain boundaries,5 at which an interfacial
polarization could be induced,12 thus, the electrical proper-
ties were susceptible to the space charge and chemical de-
fects.
Here we investigated the dielectric properties of 15 nm
BTO ceramics. Dielectric relaxation and its dominant extrin-
sic effects like conductions, space charge between grains
were discussed. BTO ceramics with an average grain size of
15 nm were prepared as reported elsewhere.13 The relative
density determined by Archimedes’ method is 98.6%. X-ray
diffraction 共XRD兲, atomic force microscopy 共AFM兲, x-ray
photoelectron spectroscopy 共XPS兲, and transmission electron
microscopy 共TEM兲 were used to characterize the microstruc-
a兲
Author to whom correspondence should be addressed. Electronic mail:
xiangyundtj@126.com.
ture of the samples. Dielectric properties were studied on a
broadband dielectric spectrometer.
Figure 1共a兲 demonstrates that the crystal structure is
BTO and the average grain size calculated by Scherrer for-
mula in 共200兲 diffractive plane is 16.7 nm, the value shifts to
19.3 nm deduced from the inner of Fig. 1共a兲 after thermal
treatment. Thus, the thermal treatment does not induce ap-
parent growth of ceramics grain. The grain size determined
by AFM topography of the surface is about 15 nm illustrated
in Fig. 1共b兲. Binding energy of Ti 2p3/2 marked in Line 1 is
derived 457.43 eV from XPS analysis, which is smaller than
that reported for standard BTO ceramics spectrum, demon-
strating that the valence of Ti in BTO ceramics shifts from
Ti4+ to Ti3+ in order to balance the oxygen vacancies. How-
ever, the oxygen vacancies cannot be efficiently compen-
sated after thermal treatment in air atmosphere because bind-
ing energy of Ti 2p3/2 marked in Line 2 is derived 457.13
eV in Fig. 1共c兲. The grain boundary and ferroelectric domain
detected by TEM present in the samples 共figures are not
shown here兲.
Dielectric response of 15 nm BTO ceramics, examined
in terms of dielectric constant, dependence of temperature is
showed in Fig. 2. Some interesting features can be observed
as follows: 共1兲 at approximately megahertz frequency, one
dielectric response peak corresponding to phase transition
from ferroelectric to paraelectric displays disperse behavior,
which consists with our previous works.14,15 共2兲 With the
measured frequency decline to tens to hundreds of kilohertz,
dielectric constant increases with further increasing tempera-
ture after Curie phase transition, the same results were re-
ported for 50 nm dense nanocrystalline BTO ceramics.16
What’s more, relaxation phenomenon locates in the paraelec-
tric phase. 共3兲 With further decreasing frequencies to 1 kHz
or even lower, the dielectric constant present two pronounced
relaxation processes.
The ferroelectric to paraelectric phase transition can be
attributed to the relaxation process associated with the do-

0003-6951/2010/97共16兲/162913/3/$30.00 97, 162913-1 © 2010 American Institute of Physics

162913-2 Zhang et al. Appl. Phys. Lett. 97, 162913 共2010兲

FIG. 2. Dielectric constant depends on temperature at selected frequency for

15 nm BTO ceramics.

lower than 104 Hz, accompanying with a wide and promi-

nent dielectric loss peak in Fig. 3共b兲. The peak shifts to
higher frequency with increasing temperature, indicating a
thermally activated relaxation process,18,19 which probably
relates to the motion of oxygen vacancies.11 The results of
XPS measurements support this assumption. Furthermore,
activated energy was confirmed through Arrhenius law fit-
ting, written as follow:

␶ = ␶0 exp共− Ea/kBT兲, 共1兲

where ␶ is relaxation time, Ea represents the activated energy,
kB is Boltzmann constant, and T corresponds to the absolute
temperature. Our excellent fit yields activation energy of re-

FIG. 1. 共Color online兲 The microstructure of ultrafine nanocrystalline BTO

ceramics, 共a兲 XRD analysis; 共b兲 topography of the surface characterized by
AFM; and 共c兲 binding energy of Ti 2p measured by XPS.

main reorientation, domain wall emotion, and the dipolar

behavior.17 However, the dielectric abnormal of paraelectric
phase indicates that the extrinsic mechanisms like space
charge polarization and/or nonignorable ionic conductivity
dominate dielectric behaviors. The breadth of dielectric con-
stant in the paraelectric phase propose existing the composi-
tional fluctuations of Ti4+ / Ti3+, which indicates the existence
of oxygen vacancies and released electron.
Figures 3共a兲 and 3共b兲 illustrated dielectric relaxation and FIG. 3. Dielectric properties vs frequency at selected temperatures for 15
accompanied activation energy, respectively. A sharp incre- nm BTO ceramics, 共a兲 the real dielectric constant and dielectric loss; and 共b兲
ment of the real dielectric constant appears at the frequency the imaginary modulus.
162913-3 Zhang et al. Appl. Phys. Lett. 97, 162913 共2010兲

laxation process to be 0.26 eV, the value increases to 0.41 eV

共the relaxation process locates at lower temperature and fre-
quency兲 with the samples annealed at 873 K for 30 h. Lewis
and co-workers20 reported that the experimental diffusion en-
ergy for vacancies of oxygen is 0.4–0.68 eV. So it is reason-
able to believe that the dielectric relaxation induced by the
oxygen defects. Because grain boundary facilitates the defect
reaction, the activation energy was remarkably lower in
nanocrystalline BTO ceramics.2 Thus, the activation energy
in the present study is lower than the previous work may be
ascribed to the accumulation of electron released by the for-
mation of oxygen vacancies at grain boundaries.
Another interesting characterization is that the real di-
electric constant increases sharply with decreasing frequency FIG. 4. The impedance spectra for the samples measured at selected
and reaches maximum ⬃70 000 at higher temperature dis- temperatures.
played in Fig. 3共a兲. However, the colossal permittivity is not predominant for the ultrafine grain size BTO ceramics, even
originated from the intrinsic mechanism but probably results they are highly-dense and possess of ferroelectric domains.
from interfacial polarization model, also called Maxwell–
Wagner effect, which was usually adopted to explain the di- This work was supported by the 863-project under Grant
electric relaxation with extremely high dielectric constant No. 2007AA03Z524, and the National Natural Science
and found to be intensively reported for BTO-based thin Foundation of China 共NSFC兲 under Grant No. 50872094,
films ceramics capacitor21,22 and deficient BTO-based and Hainan University Research Fund.
ceramics.3 When an electric current passes through interfaces
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