J. Am. Ceram. Soc.
, ]] []]] 1–3 (2009)
Journal
Effect of Donor, Acceptor, and Donor–Acceptor Codoping on
the Electrical Properties of Ba0.6Sr0.4TiO3 Thin Films for Tunable
Device Applications
Yuanyuan Zhang, Genshui Wang, Ying Chen, Fei Cao, Lihui Yang, and Xianlin Dongw
Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
We have investigated the effects of donor, acceptor, and donor–
acceptor codoping on both the dielectric properties and the leak-
age current behavior of Ba0.6Sr0.4TiO3 thin films prepared by
the metalorganic solution deposition technique. La and Co were
selected as donor and acceptor dopants, respectively. The elec-
trical properties depend strongly on the type of dopants. Com-
pared with others, codoped BST films have a much lower loss
tangent, higher figure of merit, and lower leakage current. The
electronic conduction mechanisms of the three types of dopants
are reported.
I. Introduction
I N recent years, much attention has been paid to the develop-
ment of tunable dielectric materials for tunable microwave
device applications such as phase shifters, filters, delay lines, and
so on.1–4 Barium strontium titanate (Ba1xSrxTiO3, BST) is the
leading candidate for such applications due to its highly non-
linear dielectric response to an applied electric field.5–7 For BST
to be used in tunable device applications, the dielectric and in-
sulating properties must satisfy the following requirements: high
tunability, low leakage current, moderate dielectric constant,
and low dielectric loss.6 To date, a BST thin film that simulta-
neously possesses all of these electrical properties as required for
many microwave device applications has not been realized. It is
well-known that dopants could significantly modify the electri-
cal properties and that processing conditions also exert strong
effects on these modifications. Lower and higher valent substit-
uents (which are conventionally referred to as dopants, if the
concentrations are not too high) can be accommodated on the A
or B sites of the ABO3 perovskite lattice and act as acceptors
and donors, respectively. It is well documented that small con-
centrations of acceptor dopants, such as Mg21, Co21, Co31,
Fe21, Fe31, Sc31, Mn21, Al31, Cr31, and Ni31, which can oc-
cupy the B site of the (ABO3) perovskite structure, have been
known to lower the dielectric loss.7–11 The mechanism for this
behavior centers on the thesis that ions with a charge of less than
41 substituting for Ti41 can behave as electron acceptors and
prevent the reduction of Ti41 to Ti31. Meanwhile, Lanthanum
(La) cationic is recognized as a donor dopant of the A site in the
BST system, which can also improve the dielectric proper-
ties.6,12–14 However, there is lack of investigations on the dielec-
tric properties of acceptor and donor codoped BST, especially
M. W. Cole—contributing editor
Manuscript No. 26155. Received April 17, 2009; approved May 27, 2009.
This work was supported partly by One Hundred Talent Project of Chinese Academy of
Sciences, National Basic Research Project (No. 61363ZA09.1), Shanghai Qimingxing
Project (06QA14055), and Knowledge Innovation Project of Chinese Academy of Sciences
(SCX200702).
w
Author to whom correspondence should be addressed. e-mail: xldong@sunm.shcnc.
ac.cn
1
DOI: 10.1111/j.1551-2916.2009.03237.x
r 2009 The American Ceramic Society
on the tunability and leakage current properties.15,16 Here we
chose La and Co as donor and acceptor dopants, respectively,
and focused on the effects of acceptor, donor, and donor–
acceptor codoping on the structural and electrical properties
of BST thin films.
II. Experimental Procedure
In this letter, we studied the properties of BST thin films with the
compositions of Ba0.6Sr0.4TiO3 (BST), 0.5 mol% La-doped
Ba0.6Sr0.4TiO3 (LBST), 0.5 mol% Co-doped Ba0.6Sr0.4TiO3
(CBST), and 0.25 mol% La plus 0.25 mol% Co codoped
Ba0.6Sr0.4TiO3 (LCBST). Lanthanum acetate and cobalt acetate
were used as the dopant precursors. All the films were fabricated
by the metalorganic solution deposition technique, followed by
deposition on LaNiO3/SiO2/Si substrates by spin coating at
5000 rpm for 30 s. The LaNiO3 films were prepared by a sol–
gel method, and the thickness is about 150 nm. Many more de-
tails about LNO electrodes were reported elsewhere.17 The
thickness of the films was about 400 nm, measured by FE-scan-
ning electron microscopy (SEM) of the cross-section. The Pt top
electrodes with a 0.2 mm diameter were deposited onto the films
through a shadow mask by direct current sputtering for electri-
cal testing. The samples were annealed at 4501C for 5 min in O2
in order to improve the interface between the top Pt electrode
and the BST film, after the top electrode deposition.
The structures of BST thin films were characterized by X-ray
diffraction (XRD) and SEM. The dielectric properties were
measured with an Agilent 4294A precision impedance analyzer
(Englewood, CO). The tunability is defined in terms of the fol-
lowing equation, [Cr(0)Cr(V)]/Cr(0)  100%, where Cr(0) and
Cr(V) denote the capacitance without and with a direct current
(dc) bias field, respectively. Leakage current was measured at
room temperature (B151C) with a Keithley 6517A electrometer
(Cleveland, OH) as the voltage source and a picoammeter. For
measuring the true leakage current, the polarization current and
the field-induced degradation components can be effectively
avoided by this technique.
III. Results and Discussion
Figure 1 shows the XRD patterns of BST thin films. All the films
had a typical cubic perovskite structure and were (100) oriented.
The (100)-orientation parameter, a100, was calculated from the
relative heights of the (100), (110), and (111) diffraction peaks,
i.e., a100 5 I100/(I1001I1101I111).18 For BST, LBST, CBST, and
LCBST, a100 was 0.25, 0.27, 0.34, and 0.53, respectively. It can
be seen that the dopant can dramatically influence the crystalli-
nity, and the codopant is beneficial for the (100) orientation.
The surface and the cross-section microstructure of the thin
films were investigated using SEM. The surface images indicated
that all the films have dense and crack-free surfaces with a
fine grain structure. Among all the films, LCBST thin films show
2 Communications of the American Ceramic Society
Fig. 1. X-ray diffraction pattern of the films (a) BST, (b) LBST,
(c) CBST, (d) LCBST.
a much more uniform surface morphology. No significant
morphological differences could be found between the four
sets of BST films.
The dielectric properties of all the BST films were shown in
Table I. It shows that dopants had a strong influence on the
dielectric properties of the BST thin films. The dielectric con-
stants of all the doped BST thin films have a slight increase,
while the loss tangents were lower. LCBST thin films (tan
d 5 0.025) have the largest figure of merit (tunability/tan d,
FOM). It is well demonstrated that the samples’ composition,
grain size, and crystallinity have a strong influence on the di-
electric properties of the BST-based thin films. Furthermore, the
influence of the codoping effect on the structure, microstructure,
surface morphology, and dielectric properties should be fully
studied and analyzed.
The doping effect on the leakage current characteristics for
the BST thin films is shown in Fig. 2. The figure shows an ap-
preciable decrease in the leakage current for the doped BST thin
films, especially the La and Co codoped BST thin films. This
type of I–V curve clearly exhibits the different slope region. In
the low bias region, the slope is close to 1.0, which means that an
ohmic behavior is obtained. At the high bias region, the slope
becomes higher, up to 4.0–7.0, which corresponds to the ac-
complishment of a trap-filling process, leading to a sharp in-
crease of the leakage current. The conduction mechanism is
likely to be a space-charge limited conduction, with the grain
boundaries as distributed traps.19–21 According to other works,
the net conductivity in BST thin films is n-type, and the follow-
ing is the defect equation22:
0 cancy. These all will cause the reduction of the intrinsic oxygen
OO 2VO þ1=2O2 þ2e (1)
We signed this is the intrinsic oxygen vacancy, and its con-
centration is half of the electron concentration. La is regarded as
a donor doping in the system, and the donors are compensated
by cation vacancies.23–25 The incorporation reaction induced the
cation vacancy, as in the following equation:
00
La2 O3 þ3TiO2 ! 2LaBa ðor SrÞ þ 3TiTi þ 9OO þ VBa ðor SrÞ
(2)
Based on the Schottky equilibrium, the cation vacancy can
suppress the intrinsic oxygen vacancy concentration, which can
Table I. Summary of Dielectric Properties for Undoped and Doped Ba0.6Sr0.4TiO3 Thin Films as a Frequency of 10 kHz
Samples er
Ba0.6Sr0.4TiO3 610
Ba0.6Sr0.4TiO310.5 mol% La 636
Ba0.6Sr0.4TiO310.5 mol% Co 616
Ba0.6Sr0.4TiO310.25 mol% La10.25 mol% Co 630
Vol. ]], No. ]]
Fig. 2. Leakage current density of the films as a function of the applied
electric fields (a) BST, (b) LBST, (c) CBST, (d) LCBST.
lead to a reduction in the electron concentration through Eq. (1)
and then to a decrease of the leakage current. At the same time,
the smaller grain size of the films, leading to an increase in the
grain boundary that can be seen as distributed traps, also has a
contribution to the low leakage current.21 On the other hand,
cobalt doping is believed to be a form of acceptor doping. The
valence state of Co (21 or 31) is not certain, but for the sake of
simplicity we adopt 21, and the incorporation is described by
00 
BaO ðor SrOÞ þ CoO ! BaBa ðor SrSr Þ þ CoTi þ 2OO þ VO
(3)
It means the cobalt doping can remarkably increase the in-
duced oxygen vacancy concentration and eventually cause a re-
duction in the intrinsic oxygen vacancy, which is half of the
electron concentration through Eq. (1). Kim and Park22 sug-
gested that this can increase the width of the depletion layer or
the barrier height, which will make it more difficult for an elec-
tron to pass the potential barrier, finally resulting in a reduction
of the leakage current. Obviously, La and Co doping can de-
crease the leakage current, and there are two kinds of different
mechanisms. The LCBST thin films have both donor and ac-
ceptor doping. La donor doping can induce the cation vacancy,
and Co acceptor doping can increase the induced oxygen va-
vacancy, which is half of the electron concentration, and then
decrease the leakage current. It means that codoping can com-
bine the different mechanisms together and lower the leakage
current. At present, it is not clear yet as to which mechanism is
dominant and how to accommodate those two mechanisms.
Further studies will be carried out to clarify this.
IV. Conclusions
In summary, the dielectric and electrical properties of the BST
thin films strongly depend on the dopants. All the dopants can
enhance the tunable properties, and the donor–acceptor co-
doped BST films have a much higher FOM. The codoped BST
Tan d Tunability (%) (at 12.5 kV/mm) FOM
0.043 25.9 6.0
0.034 32.7 9.6
0.028 39.3 14.0
0.025 38.4 15.4
2009 Communications of the American Ceramic Society
also has a much lower leakage current, because both La (donor)
and Co (acceptor) contribute to the reduction of the electron
concentration. There are two different mechanisms working
together to diminish the leakage current.
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