This article was downloaded by: [Seoul National University]

On: 25 June 2013, At: 23:42

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK

Integrated Ferroelectrics: An
International Journal
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/ginf20

FERROELECTRIC PROPERTIES
OF SrBi4Ti4O15 THIN FILMS
PREPARED BY SOL-GEL METHOD
a

HUI SUN , HONG FANG , WEI-DONG ZHOU &

XIAO-BING CHEN

College of Physics Science and Technology,

Yangzhou University, Yangzhou, 225002, China
b

Testing Center of Yangzhou University, Yangzhou,

225002, China
Published online: 12 Oct 2011.

To cite this article: HUI SUN , HONG FANG , WEI-DONG ZHOU & XIAO-BING CHEN
(2006): FERROELECTRIC PROPERTIES OF SrBi4Ti4O15 THIN FILMS PREPARED BY SOL-GEL
METHOD, Integrated Ferroelectrics: An International Journal, 79:1, 203-210
To link to this article: http://dx.doi.org/10.1080/10584580600659571

PLEASE SCROLL DOWN FOR ARTICLE

Full terms and conditions of use: http://www.tandfonline.com/page/termsand-conditions
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden.
The publisher does not give any warranty express or implied or make any
representation that the contents will be complete or accurate or up to
date. The accuracy of any instructions, formulae, and drug doses should be

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

independently verified with primary sources. The publisher shall not be liable
for any loss, actions, claims, proceedings, demand, or costs or damages
whatsoever or howsoever caused arising directly or indirectly in connection
with or arising out of the use of this material.

Integrated Ferroelectrics, 79: 203210, 2006

Copyright Taylor & Francis Group, LLC
ISSN 1058-4587 print / 1607-8489 online
DOI: 10.1080/10584580600659571

Ferroelectric Properties of SrBi4 Ti4 O15 Thin Films

Prepared by Sol-Gel Method

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

Hui Sun,1 Hong Fang,1 Wei-Dong Zhou,2 and Xiao-Bing Chen1,

1

College of Physics Science and Technology, Yangzhou University,

Yangzhou 225002, China
2
Testing Center of Yangzhou University, Yangzhou 225002, China

ABSTRACT
Bismuth-based layered ferroelectric thin films of SrBi4 Ti4 O15 (SBTi) have been successfully prepared on Pt/Ti/SiO2 /Si by the sol-gel method. The films with smooth and uniform
surface are of single phase of SBTi and randomly oriented. The well-saturated ferroelectric hysteresis loops and the good fatigue properties of SBTi films were obtained
by using a metal-ferroelectric-metal structure. The remnant polarization (2Pr ) reached
a large value of 22.3 C/cm2 at the electric field of about 160 kV/cm. The SBTi film
showed little change of Pnv and Pnv up to 3 109 switching cycles, which suggests
the excellent fatigue-endurance characteristics of the SBTi films.
Keywords: SrBi4 Ti4 O15 thin film; sol-gel; ferroelectric properties; fatigue

INTRODUCTION
Recently, bismuth layer-structured ferroelectric (BLSFs) thin films have been
extensively developed as the memory media in ferroelectric random access memories (FeRAMs) due to their fatigue-free properties even with
Pt electrode [1]. BLSF belongs to the Aurivillius structure, described as
(Bi2 O2 )2+ (Am1 Bm O3m+1 )2 , where A represents Bi, Ba, Pb, Sr, Ca, K, Na
and rare earth elements, B represents Ti, Ta, Nb, W, Mo, and Fe, and m = 1,
2, 3, 4, . . . , represents the number of BO6 octahedra between two Bi2 O2 layers. Bi4 Ti3 O12 (BIT) and SrBiTa2 O9 (SBT) are both typical members of this
family, which have been the most promising materials for ferroelectric memories. However, both of them have some drawbacks. BIT suffers its low 2Pr

Received April 17, 2005; in final form January 23, 2006.

Corresponding author. E-mail: xbchen@yzu.edu.cn

[1613]/203

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

204/[1614]

Hui Sun et al.

and poor fatigue property, whereas, SBT requires high processing temperature
(>800 C) and its small 2Pr (typically 416 C/cm2 ) hinders its further application in FeRAMs [2, 3]. SrBi4 Ti4 O15 (SBTi), another typical member of that
family in which A = Sr, Bi, B = Ti, m = 4, and whose structure is similar to BIT
and SBT, has higher Curie temperature (520 C) [4]. The remnant polarization
(2Pr ) of the SBTi single crystals is 58 C/cm2 along a(b) axis under an applied
electric field of 60 kV/cm [4]. However, the 2Pr of the SBTi thin films prepared
by pulse laser deposition (PLD) or metal organic deposition (MOD) is low (6.2
14.4 C/cm2 ) [57], and their fatigue properties are poor at the low frequency
[6]. It is known that the film growth technique and subsequent processing steps
play an important role in the film quality. The sol-gel processing have some potential profits of good homogeneity, ease of chemical composition control, high
purity, low temperature processing, and large area and versatile shaping without
the requirement of vacuum condition. In the present work, SBTi thin films with
large remnant polarization were prepared by the sol-gel method with layer by
layer annealing process, and a good fatigue-endurance property was obtained.

EXPERIMENTS
The SBTi films were synthesized on Pt (258 nm)/Ti (16 nm)/SiO2 /Si(100)
substrate using a repeated coating-drying cycle method. Bismuth acetate and
strontium acetate were dissolved in the mixed solutions of acetic acid and water,
then tetra-n-butyl titanate stabilized in n-propanol was added. Excess bismuth
acetate (5 mol %) was added in order to compensate the Bi loss during processing. A certain amount of acetylacetone and ethanolamine were dripped into the
solutions and adjust the pH value of the solution to 34. The resultant solutions
were stirred for several hours. The concentration of the precursor solutions
was 0.1 mol/L. The precursors were spin-coated at 3000 rpm for 30 s, and the
coated films were baked at 250400 C in air for several minutes, followed by
annealing at 650750 C for 10 minutes in flowing oxygen atmosphere. The
spinning-baking-annealing process was repeated for several times till the film
reached a thickness of 400 nm.
The crystal structure of the films was identified by X-ray diffraction (XRD)
analysis using M03XHF22 diffractometer with Cu K radiation at a tube voltage
of 40 kV and a tube current of 40 mA. The surface and cross-section images of
the films were obtained by a scanning electron microscopy (XL-30ESEM). And
the surface morphology was observed by an atomic force microscope (AFM,
Model NAN04). To examine the electric properties of the films, Pt was deposited
on the films with a shadow mask as top electrode (area = 3.14 104 cm2 )
using RF sputtering to form Pt/SBTi/Pt/Ti/SiO2 /Si (Pt/SBTi/Pt) configuration.
The ferroelectric hysteresis loops were measured using a standard ferroelectric
analyzer (Radiant Technologies, RT66), and the fatigue measurements were
carried out by RT6000 ferroelectric test system (Radiant Technologies).

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

Ferroelectric Properties of SrBi4 Ti4 O15 Thin Films

[1615]/205

Figure 1. The X-ray diffraction patterns of SBTi thin films annealed at 650, 700, 750 C.

RESULTS AND DISCUSSION

Figure 1 shows the XRD patterns of the SrBi4 Ti4 O15 thin films annealed at
650, 700 and 750 C, respectively. The peaks are indexed according to standard
powder diffraction data of SBTi. No pyrochlore phase was observed. The appearance of almost all the XRD peaks suggests that the SBTi films are well
crystallized when annealed above 650 C. Peaks of the XRD patterns become
sharper and their intensity increases as annealing temperatures increases, indicating the growing of the grain sizes. It also can be seen from the XRD patterns
that the SBTi thin films are randomly orientated. According to Lijima et al. [8],
the c-axis ratio of the films is defined as follows:
= I (0010)/[I (0010) + I (119)],

(1)

where I (119) and I (0010) are the XRD intensities of (119) and (0010) respectively. The calculated c-axis ratio for the films annealed at 750 C, = 0.17,
which is a very low value.
The surface morphology of the SBTi films annealed at 750 C was shown in
Fig. 2. The film surface is homogeneous, dense and smooth without any cracks,
and composed of closely stacked column grains of 300400 nm in size. And the
grains piled randomly on the substrate, which suggests the random orientation
as well. The cross-section scanning electron microscopy (SEM) images of the
SBTi film annealed at 750 C, presented in Fig. 3, revealed a clear and sharp
boundary between the film and Pt electrodes. The thickness of the SBTi film is
determined to be about 400 nm. The surface morphology of the SBTi thin films
was recorded by the AFM over an area of 2 m 2 m as shown in Fig. 4. It
is clear that the smooth surface of the SBTi films is advantageous to integration
with silicon devices.
Hysteresis loops of the SBTi film annealed at 750 C were obtained at
different electric field, as indicated in Fig 5. The loops are well saturated as

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

206/[1616]

Hui Sun et al.

Figure 2. Surface morphology of SBTi films annealed at 750 C.

the applied electric is larger than 160 kV/cm. Figure 6 shows the dependence
of the remnant polarization on the electric field with the applied electric field
ranging from 67 kV/cm to 253 kV/cm. When the applied electric field is lower
than 147 kV/cm, the 2Pr increases dramatically with the electric field. With
the further increasing of the electric field, the increase rate of 2Pr slows down.
As the applied electric field is 160 kV/cm, the 2Pr becomes saturated, and
reaches a large value of 22.3 C/cm2 , while the coercive field (E c ) is about
50 kV/cm.
Compared with the SBTi ceramics, the 2Pr of the present film is larger
and the E c is lower [9]. It may be contributed to the lower defect concentration
and the higher density of the films. The 2Pr of the present film is much larger than
that of PLD-grown and MOD-grown SBTi films [5, 6]. And in comparison with
the SBT (SrBi2 Ta2 O9 ) and La doped BIT (Bi3.25 La0.75 Ti3 O12 ) thin films, the
present film appears very good ferroelectric properties, which are suitable for
the application of the high density and low electric consumption FeRAMs. The
ferroelectric properties of the above materials are presented in Table 1 in detail.
The 2Pr of the present film is as twice as that of SBT thin films under higher
electric field, whereas the E c is comparable with the SBTs [10]. And the 2Pr

Figure 3. Cross-section SEM micrograph of the SBTi/Pt/Ti/SiO2 /Si structure.

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

Ferroelectric Properties of SrBi4 Ti4 O15 Thin Films

[1617]/207

Figure 4. AFM image showing the surface morphology of the SBTi film.

of the present film is very close to that of the BLT [3], though the present films
do not take any advantage of doping modification. It is more important for the
present films that these values, i.e., 2Pr and E c are almost constant throughout
the whole area of the present SBTi thin film, which presumably results from
the homogeneity of the grain orientation in the present sol-gel derived films.
Those features in the ferroelectric properties may possibly remove the problems
associated with the bit-to-bit variability in film capacitors.
The 2Pr of the present SBTi films is very large in comparison with that of the
SBTi thin films prepared by other methods [57]. This may originate from the
following aspects: On one hand, the grain size is closely related to ferroelectric
properties in both simple ABO3 type materials and bismuth layered perovskite
materials. Better properties can be expected in films with larger grains [11]. On
the other hand, the spontaneous polarization of SBTi was along a(b) axis, and
the polarization along c axis is zero [4]. So the large remnant polarization of the
SBTi thin film derived by our sol-gel method may attribute to the large grain
size and the mixed orientation.

Figure 5. P-E hysteresis loops for the SBTi film at different applied voltages.

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

208/[1618]

Hui Sun et al.

Figure 6. Remnant polarization as a function of electric field.

Figure 7 illustrates the decay of non-volatile polarization as a function of

the switching cycles. The applied electric field is 107 kV/cm. The pulse width
is 5 106 s and the frequency is 100 kHz. The Pt/SBTi/Pt capacitors exhibit
excellent fatigue characteristics even after 3 109 cycles. The Pnv remains at
the value of about 11.5 C/cm2 . Furthermore, no significant change in the shape
of the hysteresis loops is observed after being subjected to 3 109 read/write
cycles.
The present SBTi thin films have better fatigue-endurance property than
those reported by others [5, 6]. According to the Zhang et al. [6], the fatigue
rate (K ) was defined as:
(P P ) = K lgN + b,

(2)

where N is the switching time and b is a constant. The smaller is the value of
K , the better the fatigue property is [6]. In our experiment, the K is about 0.01,
which is much lower than the PLD-grown SBTi (about 0.025) [6].
The fatigue property of ferroelectric materials is related to the competition
of the pinning and unpinning of the domain walls. The oxygen vacancies could
stabilize the charge trapped at domain boundaries [12], which would make the
Table 1
Ferroelectric properties of some materials

Materials
Present film
SBTi thin film [5, 6]
SBTi ceramic [9]
SBT [10]
BLT(0.75) [3]

Applied electric field

(kV/cm)

2Pr
(C/cm2 )

2E c
(kV/cm)

160
275
150
286
170

22.3
6.22
16.4
11
24

100
136
162
95
100

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

Ferroelectric Properties of SrBi4 Ti4 O15 Thin Films

[1619]/209

Figure 7. Fatigue characteristics of the SBTi capacitors measured at a frequency of

100 kHz.

unpinning of domain wall difficult. So, the less the oxygen vacancy, the better
the fatigue property is. There is an Sr ion resided at the A-site of SBTi. The Sr
ion is more stable than Bi, and is comparable with the La ions in La-doped BTO.
Thus, the SBTi should have better fatigue property intrinsically. Meanwhile, the
fatigue property is related to the processing of the films as well. As mentioned
above, the films prepared by the sol-gel method have better ferroelectric properties and fatigue characteristic than those obtained using the other methods.
These may attribute to the precise control of the stroichiometric proportion of
the precursors in the preparation of the precursor solutions. Besides, the layer
by layer annealing of the SBTi thin films may introduce fewer defects and make
the grains well-crystallized, leading to an excellent fatigue property.
CONCLUSION
SBTi thin films with random orientation were fabricated by sol-gel method.
Well-saturated rectangular hysteresis loops of the SBTi films were obtained
through a Pt/SBTi/Pt MFM structure. The 2Pr reaches a large value of
22.3 C/cm2 at an applied electric field about 160 kV/cm. And the SBTi capacitors show excellent fatigue-endurance property with the electric field of
107 kV/cm and the frequency of 100 kHz.
ACKNOWLEDGMENTS
The authors acknowledge 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).

210/[1620]

Hui Sun et al.

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

REFERENCES
1. J. K. Lee, C. H. Kim, H. S. Suh, and K. S. Hong, Appl. Phys. Lett. 80, 3593
(2002).
2. C. A. Paz de Araujo, J. D. Cuchiaro, L. D. McMillan, M. C. Scott, and J. F.
Scott, Nature (London) 374, 12 (1995).
3. B. H. Park, B. S. Kang, S. D. Bu, T. W. Noh, J. Lee, and W. Jo, Nature
(London) 401, 682 (1999).
4. H. Irie and M. Miyayama, Appl. Phys. Lett. 79, 251 (2001).
5. S. T. Zhang, B. Sun, B. Yang, Y. F. Chen, Z. G.. Liu, and N. B. Ming,
Mater. Lett. 47, 334 (2001).
6. S. T. Zhang, B. Yang, Y. F. Chen, Z. G. Liu, X. B. Yin, Y. Wang, M. Wang,
and N. B. Ming, J. Appl. Phys. 91, 3160 (2002).
7. H. Watanabe, T. Mihara, H. Yoshimori, and C. A. Paz de Araujo, Jpn. J.
Appl. Phys. 34, 5240 (1995).
8. K. Lijima, Y. Tomita, R. Takayama, and I. Ueda, J. Appl. Phys. 60, 361
(1986).
9. J. Zhu, X. Y. Mao, and X. B. Chen, Solid State Commu. 129, 707 (2004).
10. K. Aizawa, E. Tokumitsu, K. Okamoto, and H. Ishiwara, Appl. Phys. Lett.
76, 2609 (2000).
11. J. Zhu, X. Zhang, Y. Zhu, and S. B. Desu, J. Appl. Phys. 83, 1610 (1998).
12. W. L. Warren, B. A. Tuttle, and D. Dimos, Appl. Phys. Lett. 67, 1426
(1995).