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DOPING EFFECT OF LA AND V

IN SrBi4Ti4O15 THIN FILMS
a

HUI SUN , YA-FENG QIAN , HONG FANG , JUN

a

ZHU & XIAO-BING CHEN

College of Physics Science and Technology,

Yangzhou University, Yangzhou, 225002, China
Published online: 10 Mar 2011.

To cite this article: HUI SUN , YA-FENG QIAN , HONG FANG , JUN ZHU & XIAO-BING
CHEN (2006): DOPING EFFECT OF LA AND V IN SrBi4Ti4O15 THIN FILMS, Integrated
Ferroelectrics: An International Journal, 84:1, 83-89
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Integrated Ferroelectrics, 84: 8389, 2006

Copyright Taylor & Francis Group, LLC
ISSN 1058-4587 print / 1607-8489 online
DOI: 10.1080/10584580601085289

Doping Effect of La and V in SrBi4 Ti4 O15

Thin Films

Downloaded by [Seoul National University] at 23:42 25 June 2013

Hui Sun, Ya-feng Qian, Hong Fang, Jun Zhu, and Xiao-bing Chen
College of Physics Science and Technology, Yangzhou University,
Yangzhou 225002, China

ABSTRACT
SrBi4 Ti4 O15
(SBTi),
SrBi4x Lax Ti4 O15
(x = 0.10,
0.25:
SBLT),
and
SrBi4y/3 Ti4y V y O15 (y = 0.03: SBTV) thin films have been prepared by the
sol-gel method. The ferroelectric properties of the SBTi thin films have been improved
by La and V substitution. The SBLT-0.10 and SBTV-0.03 films exhibit large remnant
polarization (2Pr ) of 45.9 C/cm2 and 34.0 C/cm2 respectively. V doping brings
about the more significant improvement of the fatigue resistance of the SBTi. After
being subject to 2.2 109 switching cycles at the low frequency of 50 kHz, the Pnv of
SBTV-0.03 change little.
Keywords: Ferroelectric thin films; sol-gel method; La, V substitution; ferroelectric
properties

INTRODUCTION
The non-volatile ferroelectric materials, which are used in ferroelectric random
access memories (FeRAMs), should at least meet the four following criteria: large remnant polarization (2Pr ), low coercive field (E c ), fatigue-free with
metallic electrodes and a low processing temperature [1]. Due to their promising fatigue-free nature, bismuth layer-structured ferroelectrics (BLSFs) have
attracted considerable attention [2]. Among the prototype BLSFs, thin films
of SrBi2 Ta2 O9 (SBT) show excellent endurance against polarization switching
over 1012 cycles. However, its small 2Pr (typically 416 C/cm2 ) and its high
processing temperature (800850 C) hinder its further application in FeRAMs
[1, 3]. Another category of BLSF films, namely Bi4 Ti3 O12 (BIT), fails to meet
Received May 31, 2006.
Corresponding author. E-mail: xbchen@yzu.edu.cn

83

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Hui Sun et al.

industrial requirements due to its low 2Pr and poor fatigue property [1, 4].
Recent researches have found that doping BIT by lanthanide series not only
improves the fatigue-free property of BIT, but also increases 2Pr . And Noguchi
et al. reported that the incorporation of a small amount of higher-valent cations
(such as V5+ , W6+ ) into BIT can improve the electric properties [5, 6]. The 2Pr
was increased remarkably, and the leakage current was lowered as well.
Compared with BIT, SrBi4 Ti4 O15 (SBTi) processes a more perovskite unit
sandwiched between the two Bi-O layers and exhibit typical ferroelectric behavior with 2Pr of 58 C/cm2 in a/b axis orientations under an applied electric
field of 60 kV/cm [7]. It is considered that similar substitution can improve its
properties as well. In this article, we report the fabrication and properties of the
La3+ and V5+ doped SBTi thin films prepared by the sol-gel method.
EXPERIMENTS
The SrBi4x Lax Ti4 O15 (SBLT) (x = 0.00, 0.10, and 0.25) and
SrBi4y/3 Ti4y V y O15 (y = 0.03: SBTV) thin films were grown on
Pt/Ti/SiO2 /Si(100) substrates by the sol-gel method. The precursor solutions for the coating were prepared as follows. Stoichiometric bismuth acetate,
lanthanum acetate and strontium acetate were dissolved in the mixed solutions
of acetic acid and water. Excess bismuth acetate (5 mol%) was added in order to
compensate the Bi loss during heat treatment. Separately, titanium n-butoxide
and vanadium oxytripropoxide were added to the vessel with n-propanol
solvent, and acetylacetone was used as a stable agent. The titanium-vanadium
solutions were dripped into the strontium-bismuth solutions with continuous
stirring. Then the resultant solutions were stirred for several hours. The final
concentration of the precursor solutions was 0.1 mol/L. The precursors were
spin coated at 3500 rpm, and a two-step baking procedure was employed with
baking temperatures at 250 C and 400 C for several minutes, respectively. The
deposited films were then annealed in flowing oxygen atmosphere at 750 C.
The time for each annealing was 10 minutes except for the last one, which
was 30 minutes. This process was repeated several times to reach the ultimate
thickness of the films.
The structures of the films were characterized by X-ray diffraction (XRD)
analysis using an M03XHF22 diffractometry with CuK radiation. The surface
morphologies were observed by an atomic force microscope (AFM: NAN04).
And cross-sectional scanning electron microscopy images of the films multilayered structures were obtained by a scanning electron microscopy (SEM: XL30ESEM). To examine ferroelectric properties of the films, Pt were deposited
onto the films with a shadow mask as top electrodes (area = 3.14 104 cm2 ) at
room temperature to form a Pt/SBTV/Pt/Ti/SiO2 /Si (Pt /SBTi/Pt) configuration.
The ferroelectric hysteresis loops were measured by a standard ferroelectric
analyzer (Radiant Technologies, RT66), and the fatigue measurements were
carried out by RT6000 ferroelectric test system.

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Doping Effect of La and V in SrBi4 Ti4 O15 Thin Films

85

Figure 1. X-ray diffraction patterns of SBTi, SBLT-0.10, SBLT-0.25, and SBTV-0.03

thin films.

RESULTS AND DISCUSSION

From the XRD patterns shown in Fig. 1, it is observed that all of the films are
well crystallized and there is no evidence of a second phase. The coincidence of
the diffraction peaks for all of the films implies that La3+ or V5+ doping does
not change the crystal structure of SBTi. It is worthy noticed that the c-axis
orientation is improved substantially with La-substitution and V5+ substitution
decreases the c-axis orientation.
Figure 2(a), (b), (c), and (d) show the surface topographic images of the
SBLT-0.00, 0.10, 0.25, and SBTV-0.03 thin films examined by AFM, respectively. All of the samples exhibit smooth surface with few cracks. The grain
size of the SBLT-0.10, 0.25 and SBTV is smaller than that of SBTi. Crosssectional SEM images were recorded to determine the thickness of the films.
Figure 3 presents the SEM image of the SBLT-0.10 film. It displays a clear and
sharp boundary between the film and the Pt electrode, suggesting no obvious
inter-diffusion across the capacitor structure. The thickness of the film is quite
uniform, which is about 600 nm.
Figure 4 shows the hysteresis loops of thin films of SBTi, SBLT-0.01,
SBLT-0.25, and SBTV-0.03 under a maximum electric field of 300 kV/cm. Well
saturated hysteresis loops of all of the samples are observed, and the ferroelectric
properties of SBTi are improved by La or V doping. The 2Pr of SBTi, SBLT0.10, SBLT-0.25, and SBTV-0.03 films is 23.4, 45.9, 29.6, and 34.0 C/cm2 ,
respectively. Meanwhile, the E c of SBTi is decreased. The SBLT-0.10 appears
the most excellent ferroelectric properties, the largest 2Pr and the lowest E c ,
which are increased by 96% and decreased by 37% in comparison with those
of SBTi respectively. The further La-addition decreases the 2Pr , which may be
attributed to the higher c-orientation and the smaller grain size. As for SBTV
film, the enlargement of 2Pr is not as significant as that in V-doped SBTi bulk,
which may be due to the grain size decrease of SBTV thin film [8]. Nowadays

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Hui Sun et al.

Figure 2. Surface morphology AFM images of the (a) SBTi, (b) SBLT-0.10, (c) SBLT0.25, and (d) SBTV-0.03 thin films.

the acknowledged cause for the improvement of the ferroelectric property is

the restraint of the defect due to the substitution at A or B site, which has been
verified by the X-ray photoelectron scattering and the dielectric loss test [810].
The decays of non-volatile polarization Pnv of SBTi, SBLT-0.10, and SBTV0.03 thin films as a function of switching cycles are tested at the frequency of

Figure 3. Cross-sectional SEM micrograph of the SBLT-0.10 thin film.

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87

Figure 4. Hysteresis loops for the SBLT-x (x = 0.00, 0.10, 0.25) and SBTV-0.03 films
at maximum applied electric field of 300 kV/cm.

1.0 MHz and the electric field of 200 kV/cm, as depicted in Fig. 5. After
4.4 1010 reading/writing cycles, the Pnv show little change. The drop of the
Pnv is about 4.7%, 3.5%, and 1.7%, respectively. This implies that all of the films
exhibit excellent fatigue characteristics, and La3+ and V5+ -substitution favors
to the improvement of fatigue-endurance properties. To exam the doping effect

Figure 5. Nonvolatile polarization as a function of switching cycles of the SBTi,

SBLT-0.10, and SBTV-0.03 capacitors measured at frequency of 1 MHz.

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Hui Sun et al.

Figure 6. Variation of nonvolatile polarization of the SBTi, SBLT-0.10, and SBTV-0.03

capacitors with number of read/write cycles measured at a frequency of 50 kHz.

on fatigue characteristics at low frequency, the fatigue measurement was performed at the frequency of 50 kHz, as illustrated in Fig. 6. La or V-substitution
improves the fatigue resistance property of SBTi, and the effect of V-doping is
more significant. After being subject to 2.2 109 switching cycles, the Pnv of
the SBTi and SBLT-0.10 decrease by 49.3% and 32.6% respectively, while the
value of SBTV-0.03 change little. The more excellent fatigue resistance property
of SBTV-0.03 at low frequency suggests that higher-valent-cation substitution
is a very effective method to improve the fatigue resistance property of BLSFs.
It is accepted that the oxygen vacancy play a very important role in the fatigue
property. Yao et al.s [11] investigations on the dielectric properties of La and
Nb doped BIT ceramics revealed that higher-valent-cation doping at B site reduce the oxygen vacancies more significantly. Similarly, the oxygen vacancy
concentration in SBTV will be lower than that in other films in our case, so the
SBTV film presents the excellent fatigue resistance properties. In the future,
La and V co-substituted SBTi films should be fabricated to further improve the
ferroelectric and fatigue properties.

CONCLUSIONS
In summary, SBTi films with La3+ substitution at the A site and V5+ substitution at B site have been fabricated using sol-gel method. La and V substitution
at A and B site not only improve the ferroelectric but also improve the fatigue properties of SBTi. The substitution at the A site enhance the remnant

Doping Effect of La and V in SrBi4 Ti4 O15 Thin Films

89

polarization significantly, while the modification at B site leads to an more

obvious improvement of the fatigue resistance characteristics.

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ACKNOWLEDGMENT
This work was supported by the financial support from the National Natural Science Foundation of China (Grant No. 10274066) and the Natural Science Foundation of Education Bureau of Jiangsu Province, China (Grant No.
GK0410181). Partial support was also provided by the Natural Science Foundation of Jiangsu Province, China (Grant No. BK2005052).

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