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J. Am. Ceram. Soc.

, ]] []]] 1–3 (2009)
DOI: 10.1111/j.1551-2916.2009.03237.x
r 2009 The American Ceramic Society

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– on the tunability and leakage current properties.15,16 Here we
acceptor codoping on both the dielectric properties and the leak- chose La and Co as donor and acceptor dopants, respectively,
age current behavior of Ba0.6Sr0.4TiO3 thin films prepared by and focused on the effects of acceptor, donor, and donor–
the metalorganic solution deposition technique. La and Co were acceptor codoping on the structural and electrical properties
selected as donor and acceptor dopants, respectively. The elec- of BST thin films.
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 II. Experimental Procedure
electronic conduction mechanisms of the three types of dopants In this letter, we studied the properties of BST thin films with the
are reported. 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
I. Introduction Ba0.6Sr0.4TiO3 (LCBST). Lanthanum acetate and cobalt acetate
were used as the dopant precursors. All the films were fabricated
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
by the metalorganic solution deposition technique, followed by
deposition on LaNiO3/SiO2/Si substrates by spin coating at
so on.1–4 Barium strontium titanate (Ba1xSrxTiO3, BST) is the 5000 rpm for 30 s. The LaNiO3 films were prepared by a sol–
leading candidate for such applications due to its highly non- gel method, and the thickness is about 150 nm. Many more de-
linear dielectric response to an applied electric field.5–7 For BST tails about LNO electrodes were reported elsewhere.17 The
to be used in tunable device applications, the dielectric and in- thickness of the films was about 400 nm, measured by FE-scan-
sulating properties must satisfy the following requirements: high ning electron microscopy (SEM) of the cross-section. The Pt top
tunability, low leakage current, moderate dielectric constant, electrodes with a 0.2 mm diameter were deposited onto the films
and low dielectric loss.6 To date, a BST thin film that simulta- through a shadow mask by direct current sputtering for electri-
neously possesses all of these electrical properties as required for cal testing. The samples were annealed at 4501C for 5 min in O2
many microwave device applications has not been realized. It is in order to improve the interface between the top Pt electrode
well-known that dopants could significantly modify the electri- and the BST film, after the top electrode deposition.
cal properties and that processing conditions also exert strong The structures of BST thin films were characterized by X-ray
effects on these modifications. Lower and higher valent substit- diffraction (XRD) and SEM. The dielectric properties were
uents (which are conventionally referred to as dopants, if the measured with an Agilent 4294A precision impedance analyzer
concentrations are not too high) can be accommodated on the A (Englewood, CO). The tunability is defined in terms of the fol-
or B sites of the ABO3 perovskite lattice and act as acceptors lowing equation, [Cr(0)Cr(V)]/Cr(0)  100%, where Cr(0) and
and donors, respectively. It is well documented that small con- Cr(V) denote the capacitance without and with a direct current
centrations of acceptor dopants, such as Mg21, Co21, Co31, (dc) bias field, respectively. Leakage current was measured at
Fe21, Fe31, Sc31, Mn21, Al31, Cr31, and Ni31, which can oc- room temperature (B151C) with a Keithley 6517A electrometer
cupy the B site of the (ABO3) perovskite structure, have been (Cleveland, OH) as the voltage source and a picoammeter. For
known to lower the dielectric loss.7–11 The mechanism for this measuring the true leakage current, the polarization current and
behavior centers on the thesis that ions with a charge of less than the field-induced degradation components can be effectively
41 substituting for Ti41 can behave as electron acceptors and avoided by this technique.
prevent the reduction of Ti41 to Ti31. Meanwhile, Lanthanum
(La) cationic is recognized as a donor dopant of the A site in the
III. Results and Discussion
BST system, which can also improve the dielectric proper-
ties.6,12–14 However, there is lack of investigations on the dielec- Figure 1 shows the XRD patterns of BST thin films. All the films
tric properties of acceptor and donor codoped BST, especially had a typical cubic perovskite structure and were (100) oriented.
The (100)-orientation parameter, a100, was calculated from the
M. W. Cole—contributing editor 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-
Manuscript No. 26155. Received April 17, 2009; approved May 27, 2009. nity, and the codopant is beneficial for the (100) orientation.
This work was supported partly by One Hundred Talent Project of Chinese Academy of
Sciences, National Basic Research Project (No. 61363ZA09.1), Shanghai Qimingxing The surface and the cross-section microstructure of the thin
Project (06QA14055), and Knowledge Innovation Project of Chinese Academy of Sciences films were investigated using SEM. The surface images indicated
(SCX200702).
w
Author to whom correspondence should be addressed. e-mail: xldong@sunm.shcnc. that all the films have dense and crack-free surfaces with a
ac.cn fine grain structure. Among all the films, LCBST thin films show
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2 Communications of the American Ceramic Society Vol. ]], No. ]]

Fig. 1. X-ray diffraction pattern of the films (a) BST, (b) LBST,
(c) CBST, (d) LCBST.
Fig. 2. Leakage current density of the films as a function of the applied
a much more uniform surface morphology. No significant electric fields (a) BST, (b) LBST, (c) CBST, (d) LCBST.
morphological differences could be found between the four
sets of BST films.
The dielectric properties of all the BST films were shown in lead to a reduction in the electron concentration through Eq. (1)
Table I. It shows that dopants had a strong influence on the and then to a decrease of the leakage current. At the same time,
dielectric properties of the BST thin films. The dielectric con- the smaller grain size of the films, leading to an increase in the
stants of all the doped BST thin films have a slight increase, grain boundary that can be seen as distributed traps, also has a
while the loss tangents were lower. LCBST thin films (tan contribution to the low leakage current.21 On the other hand,
d 5 0.025) have the largest figure of merit (tunability/tan d, cobalt doping is believed to be a form of acceptor doping. The
FOM). It is well demonstrated that the samples’ composition, valence state of Co (21 or 31) is not certain, but for the sake of
grain size, and crystallinity have a strong influence on the di- simplicity we adopt 21, and the incorporation is described by
electric properties of the BST-based thin films. Furthermore, the
influence of the codoping effect on the structure, microstructure, 00 
BaO ðor SrOÞ þ CoO ! BaBa ðor SrSr Þ þ CoTi þ 2OO þ VO
surface morphology, and dielectric properties should be fully
studied and analyzed. (3)
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 It means the cobalt doping can remarkably increase the in-
films, especially the La and Co codoped BST thin films. This duced oxygen vacancy concentration and eventually cause a re-
type of I–V curve clearly exhibits the different slope region. In duction in the intrinsic oxygen vacancy, which is half of the
the low bias region, the slope is close to 1.0, which means that an electron concentration through Eq. (1). Kim and Park22 sug-
ohmic behavior is obtained. At the high bias region, the slope gested that this can increase the width of the depletion layer or
becomes higher, up to 4.0–7.0, which corresponds to the ac- the barrier height, which will make it more difficult for an elec-
complishment of a trap-filling process, leading to a sharp in- tron to pass the potential barrier, finally resulting in a reduction
crease of the leakage current. The conduction mechanism is of the leakage current. Obviously, La and Co doping can de-
likely to be a space-charge limited conduction, with the grain crease the leakage current, and there are two kinds of different
boundaries as distributed traps.19–21 According to other works, mechanisms. The LCBST thin films have both donor and ac-
the net conductivity in BST thin films is n-type, and the follow- ceptor doping. La donor doping can induce the cation vacancy,
ing is the defect equation22: and Co acceptor doping can increase the induced oxygen va-
0 cancy. These all will cause the reduction of the intrinsic oxygen
OO 2VO þ1=2O2 þ2e (1) vacancy, which is half of the electron concentration, and then
decrease the leakage current. It means that codoping can com-
We signed this is the intrinsic oxygen vacancy, and its con- bine the different mechanisms together and lower the leakage
centration is half of the electron concentration. La is regarded as current. At present, it is not clear yet as to which mechanism is
a donor doping in the system, and the donors are compensated dominant and how to accommodate those two mechanisms.
by cation vacancies.23–25 The incorporation reaction induced the Further studies will be carried out to clarify this.
cation vacancy, as in the following equation:
00
La2 O3 þ3TiO2 ! 2LaBa ðor SrÞ þ 3TiTi þ 9OO þ VBa ðor SrÞ IV. Conclusions
(2) In summary, the dielectric and electrical properties of the BST
thin films strongly depend on the dopants. All the dopants can
Based on the Schottky equilibrium, the cation vacancy can enhance the tunable properties, and the donor–acceptor co-
suppress the intrinsic oxygen vacancy concentration, which can doped BST films have a much higher FOM. The codoped BST

Table I. Summary of Dielectric Properties for Undoped and Doped Ba0.6Sr0.4TiO3 Thin Films as a Frequency of 10 kHz
Samples er Tan d Tunability (%) (at 12.5 kV/mm) FOM

Ba0.6Sr0.4TiO3 610 0.043 25.9 6.0
Ba0.6Sr0.4TiO310.5 mol% La 636 0.034 32.7 9.6
Ba0.6Sr0.4TiO310.5 mol% Co 616 0.028 39.3 14.0
Ba0.6Sr0.4TiO310.25 mol% La10.25 mol% Co 630 0.025 38.4 15.4
2009 Communications of the American Ceramic Society 3
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