Home

Search

Collections

Journals

About

Contact us

My IOPscience

Properties of Nd-substituted SrBi4Ti4O15 ferroelectric ceramics

This article has been downloaded from IOPscience. Please scroll down to see the full text article.
2006 J. Phys. D: Appl. Phys. 39 370
(http://iopscience.iop.org/0022-3727/39/2/019)
View the table of contents for this issue, or go to the journal homepage for more

Download details:
IP Address: 147.47.241.104
The article was downloaded on 28/06/2013 at 09:40

Please note that terms and conditions apply.

INSTITUTE OF PHYSICS PUBLISHING

JOURNAL OF PHYSICS D: APPLIED PHYSICS

J. Phys. D: Appl. Phys. 39 (2006) 370374

doi:10.1088/0022-3727/39/2/019

Properties of Nd-substituted SrBi4Ti4O15

ferroelectric ceramics
Wei Wang1 , Jun Zhu1 , Xiang-yu Mao1 and Xiao-bing Chen1,2,3
1
College of Physics Science and Technology, Yangzhou University, Yangzhou 225002,
Peoples Republic of China
2
National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210008,
Peoples Republic of China

E-mail: xbchen@yzu.edu.cn

Received 29 May 2005, in final form 13 October 2005

Published 6 January 2006
Online at stacks.iop.org/JPhysD/39/370
Abstract
Ceramic samples of SrBi4x Ndx Ti4 O15 (SBNT-x, x = 0.001.00) have
been prepared by the conventional solid-state reaction method. As the Nd
doping content increases from 0.00 to 0.18, the remnant polarization (2Pr )
increases steadily and reaches a maximum value of 25.8 C cm2 , which is
almost 56% higher than that of the non-doped sample. However, 2Pr
decreases with further substitution. The variation of 2Pr is dominated by the
restraint of space charge and the relief of structural distortion. The coercive
field (Ec ) remains almost unchanged at a value of 80 kV cm1 in the case
of x = 0.000.18, then decreases with further Nd-doping, which is probably
due to the formation of anti-phase boundaries induced by the modification.
As doping content exceeds 0.75, the specimens exhibit relaxor behaviour
due to a ferroelectric microdomain state caused by the random fields.

1. Introduction
Lead-free bismuth layer-structured ferroelectrics (BLSFs)
have been widely expected to be a promising candidate
for ferroelectric random access memories (FeRAMs)
which exhibit the advantage of nonvolatility, low power
consumption, and high operation speed compared with
conventional memories [1]. The general formula for this
kind of Aurivillius phase material can be expressed as
(Bi2 O2 )2+ (Am1 Bm O3m+1 )2 where A denotes mono-, di- or
trivalent ions or a mixture of them, B represents Ti4+ , Nb5+
and Ta5+ , etc. The integer, m, represents the number of sheets
of corner-sharing BO6 octahedra forming the ABO3 -type
perovskite-like blocks which are interleaved with (Bi2 O2 )2+
slabs [2]. In this BLSF family, SrBi2 Ta2 O9 (SBT) and
SrBi2 Nb2 O9 (SBN) thin films exhibit an excellent fatiguefree nature even with the Pt electrode, but their relative
small remnant polarization (2Pr = 8 C cm2 ) as well
as high processing temperature (800 C) are unfavourable
for practical applications [3]. Bismuth titanate Bi4 Ti3 O12
(BIT), another intensively studied BLSF, has large spontaneous
polarization, low switching field and high Curie temperature,
but its high leakage electric current and poor fatigue resistance
quality fail to satisfy industrial demands [4]. Recently,
3

Author to whom any correspondence should be addressed.

0022-3727/06/020370+05$30.00

2006 IOP Publishing Ltd

lanthanide substitution for BIT has attracted great attention

since Parks pioneering work, which reported a significant
enhancement of 2Pr up to 24 C cm2 and a pronounced
improvement of fatigue-free property in Bi3.25 La0.75 Ti3 O12
films [5]. It has been reported as well that the randomly
oriented Bi3.15 Nd0.85 Ti3 O12 thin films deposited by the sol
gel process show excellent ferroelectric response with 2Pr
and the coercive field (Ec ) in the range of 8286 C cm2
and 7084 kV cm1 , respectively [6].
On the other
hand, preferentially-oriented epitaxial Bi3.15 Nd0.85 Ti3 O12
films fabricated by pulsed laser ablation also possess a high
2Pr of 40 C cm2 at a low Ec of 50 kV cm1 [7]. Besides,
negligible imprint shifts and excellent fatigue-free properties
were also found in Bi3.15 Nd0.85 Ti3 O12 films deposited by the
chemical solution deposition method [8]. All these reports
indicate that neodymium modification plays a significant role
in the improvement of ferroelectric properties of BLSFs.
SrBi4 Ti4 O15 (SBTi), another Aurivillius family compound with four perovskite units, has been intensively investigated due to its better fatigue-endurance property and high
Curie temperature [9]. Irie et al have grown SBTi single crystal and reported 2Pr as high as 58 C cm2 along the a(b)-axis
under an electric field of 59 kV cm1 [10]. However, SBTi still
has several drawbacks such as small 2Pr (6.213 C cm2 ) and
high Ec in the thin film forms. The fatigue-free performance

Printed in the UK

370

Properties of Nd-substituted ferroelectric ceramics

deteriorates with the increase of the switching pulse width and

the decrease of operation frequency [9]. Zhu et al reported
that the ferroelectric properties of SBTi were improved by
La-doping. 2Pr reaches a value of 24.2 C cm2 when the
La content is 0.25, while the coercive field decreases from
80 to 60 kV cm1 [11]. Considering the remarkable influence
of neodymium doping on BIT and lanthanum substitution for
SBTi together with their structural similarity, it can be deduced
that neodymium-substitution should improve the ferroelectric
properties of SBTi. This paper reports that the ferroelectric
properties of SBTi ceramics are significantly improved by
Nd-doping, and the possible mechanism responsible for such
improvement is discussed in detail.

2. Experimental
The SrBi4x Ndx Ti4 O15 (SBNT-x) (x = 0.00, 0.05, 0.10, 0.18,
0.25, 0.50, 0.75, 1.00) ceramic samples were prepared by the
solid-state reaction method. Stoichiometric amounts of metal
oxide SrCO3 , Bi2 O3 , TiO2 and Nd2 O3 with high purity were
used as starting materials. A 10 wt% excess bismuth oxide was
added to compensate for the possible loss of bismuth during
the high temperature process. The constituent oxides were
mixed and ball-milled for 24 h, then precalcined at 800 C
for 8 h. The calcined powders were finely ground and then
uniaxially pressed into pellets. The obtained pellets are of
12 mm diameter and 1.5 mm thickness, respectively. These
pellets were finally sintered at 11801220 C for 4 h, then
naturally cooled down in the furnace.
Phase identification of the sintered pellets was performed
by x-ray diffraction using the M03XHF22 diffractometer with
Cu K radiation at an accelerating voltage of 40 kV and
a current of 40 mA. These pellets were filed and polished
to a thickness of 0.2 mm and 0.5 mm and then coated with
silver electrodes for the measurements of ferroelectric and
dielectric properties, respectively. Ferroelectric hysteresis
loops were obtained by a standard ferroelectric analyser
(Radiant Technologies, Precision LC). Dielectric permittivity
() dependence on temperature and frequency was investigated
by an HP-4192A low frequency impedance analyser.

3. Results and discussion

3.1. Crystal structure
Figure 1 shows the XRD patterns of the SBNT-x (x = 01.00)
ceramic samples. The diffraction peaks are identified and
indexed using the standard XRD data of SrBi4 Ti4 O15 [12]. All
the ceramic samples are of random orientation and consist of a
single phase without a secondary pyrochlore or fluorite phase.
The positions of the peaks (020) and (0018) shift slightly
toward larger Bragg angle, implying that the lattice parameters
b and c decrease when the Nd doping content increases. The
slight decrease of this lattice spacing suggests that the Nd3+
ion has been solid soluted in SBTi because the comparative
ionic radius for eight-fold coordination of Nd3+ is close to that
of Bi3+ (Nd3+ : 1.109 , Bi3+ : 1.170 ) [13].

Figure 1. X-ray diffraction patterns of SBNT-x.

3.2. Ferroelectric properties

Figure 2 shows the P E hysteresis loops of SBNT-x (x =
0.001.00) under an applied electric field of 180 kV cm1 . It
can be seen that all the hysteresis loops approach saturation
under such a driven field. The dependence of 2Pr and Ec on the
neodymium content at an applied electric field of 180 kV cm1
is given in figure 3. As the Nd content increases from x = 0.00
to 0.18, 2Pr increases steadily and reaches a maximum value
of 25.8 C cm2 , which is roughly 56% higher than that of
the undoped SBTi, then decreases with further substitution.
Ec remains almost unchanged at 80 kV cm1 when x =
0.000.18, then decreases monotonously. Therefore, the
comprehensive ferroelectric property is obviously improved
by Nd-doping with appropriate content.
In Pb(Zr,Ti)O3 and BLSFs, oxygen vacancies act as
space charge which assemble into extended structures near
the domain boundaries and make these domains pinned and
hard to switch, leading to a decrease of the switchable
polarizations.
Theoretical calculations also suggest an
increase of polarization when the oxygen vacancies are
effectively suppressed [14].
On the other hand, the
investigations on the neutron powder diffraction of La-doped
BIT have suggested that the substitution of La3+ for Bi3+ causes
less structural distortion, which is responsible for a smaller
spontaneous polarization and a lower Curie temperature [15].
The Raman spectrum investigations on La-doped BIT and
SBTi indicated that the La ions substitute for the Bi ions only
at the A site of the perovskite slabs when x < 1.00 and
x < 0.1, respectively. With further La-doping, La ions tend to
get incorporated into the (Bi2 O2 )2+ layers [15, 16]. In BLSFs,
(Bi2 O2 )2+ slabs usually serve as space charge storage, and the
self-regulating ability of (Bi2 O2 )2+ slabs can prevent defects
such as oxygen vacancies from assembling at domain walls,
thus alleviating the domain pinning. The resistivity along the
c-axis is two to three orders of magnitude higher than that
in the ab plane due to the existence of insulating (Bi2 O2 )2+
layers [17, 18]. In our case, due to the more stable chemical
371

W Wang et al

Figure 3. Dependence of 2Pr and Ec of SBNT-x on Nd content.

Table 1. Doping content of M (La, Nd) in BLSFs (m = 3, 4, 5)
corresponding to the maximum 2Pr .

Figure 2. Ferroelectric hysteresis loops of SBNT-x under a driven

electric field of 180 kV cm1 .

property of Nd3+ , the substitution of Nd3+ for volatile Bi3+

brings about the restraint of Bi3+ vacancies and consequently
lowers the concentration of oxygen vacancies. Since SBTi has
a crystal structure similar to BIT and Nd is also a member
of the lanthanides, it is reasonable to consider that the Nd
modification in SBTi could have site selectivity and results in
the relief of structural distortion. When the doping content is
lower than 0.18, the Nd ions may only substitute for Bi ions
in the perovskite layer. Within this doping range, the effect
of the restraint of oxygen vacancies is greater than that of the
relief of lattice distortion, which causes the enhancement of
polarization. With further doping, part of the Nd ions begin
to be incorporated into the (Bi2 O2 )2+ layers, which makes
the restraint of oxygen vacancies in the perovskite layer less
evident than before. On the other hand, the entry of Nd ions
into the (Bi2 O2 )2+ layers may destroy their original effects and
372

BLSFs

M = La

M = Nd

Bi4x Mx Ti3 O12 (m = 3)

SrBi4x Mx Ti4 O15 (m = 4)
Sr2 Bi4x Mx Ti5 O18 (m = 5)

0.75
0.25

0.60
0.18
0.10

cause greater relaxation of lattice distortion. These joint effects

lead to the decrease of 2Pr when x > 0.18.
It was reported that 2Pr of La-doped BIT ceramics
increases at first and reaches its maximum value at the critical
doping content of x = 0.75, then decreases with further
substitution [19]. In our previous work, a similar tendency of
2Pr was also found in BIT, SBTi and Sr2 Bi4 Ti5 O18 ceramics
doped by La or Nd [11, 20, 21]. Table 1 shows the different
doping content of La and Nd corresponding to the maximum
value of 2Pr in BLSFs with different TiO6 octahedral layers.
It is found that the doping contents of both La and Nd decrease
with the increase of TiO6 octahedral blocks, which could be
attributed to the inhomogeneous existence of A site ions in
perovskite layers for BIT, SBTi and Sr2 Bi4 Ti5 O18 . In BIT,
only two Bi3+ occupy the A site, while one Sr2+ and two Bi3+
occupy the A site in SBTi. As for Sr2 Bi4 Ti5 O18 , there are two
Sr2+ and two Bi3+ at the A site. Because Sr2+ is more stable than
Bi3+ and is more metal-like than the Bi3+ and lanthanide ions,
its existence in the A site favours the suppression of the oxygen
vacancies just as the doping lanthanide ions do. In a unit cell,
the Sr2+ increases from 0 to 2 and the Bi3+ stays constant, so
the acceptability for lanthanide ions decreases from BIT to
Sr2 Bi4 Ti5 O18 . As shown in table 1, the doping content of Nd
for the maximum value of 2Pr is lower than that of La when
doped in the same BLSFs. This behaviour can be attributed
to the difference in the effective ion charge between La3+ and
Nd3+ , which causes a structural distortion to a different extent.
As the atomic number increases in lanthanide, the effective
ion charge increases rapidly. The effective ion charge of
La3+ and Nd3+ are 11.00 and 11.45, respectively [22], and
the radius of Nd3+ (1.109 ) is smaller than that of La3+
(1.160 ), so the Coulomb interaction between Nd3+ and O2 is

Properties of Nd-substituted ferroelectric ceramics

Figure 4. Dependence of dielectric constant on temperature of

SBNT-x at a frequency of 50 kHz.

stronger than that between La3+ and O2 , which suggests that

Nd-doping causes less relief of the lattice distortion than does
the La-doping under identical doping conditions. Because
Nd-doping causes less negative influence on 2Pr , the 2Pr can
reach the maximum value at a smaller doping content than that
of La-doping, as found in table 1.
As shown in figure 3, the coercive field (Ec ) remains
almost unchanged as Nd content ranges from x = 0.00 to
x = 0.18 and then decreases with higher doping content.
Chen et al attributed the unchanging of Ec in La-doped SBTi to
the anti-phase boundaries (APBs) [23, 24]. The investigations
into the APBs in BLT grains indicate that APBs can absorb
the stress in the crystal and serve as new sites for nucleation
of new domains. In this way, the energy for domain reversal is
reduced, and the number of reversible domains increases. So
with increasing Nd content in SBTi, some pinned domains take
part in the reversal process and enhance Pr . Meanwhile, the
Ec that represents the highest reversal energy of the reversible
domain remains unchanged, as SBNT-0.18 does. With a
further increase of Nd content, no more pinned domains can
take part in the reversal process, which leads to the decreasing
of Ec as the reversal energy decreases continuously.
3.3. Dielectric and relaxor properties
The real part of the dielectric permittivity () of SBNT-x
samples as a function of the temperature is shown in figure 4.
reaches a maximum value at the Curie temperature (Tc ). The
peak value of at Tc decreases with Nd doping, which is similar
to that in La-doped SBTi. The dielectric peak broadens with
Nd-doping, indicating the diffusing of the ferro-paraelectric
phase transition, which is attributed to the occurrence of
ferroelectric microdomains induced at high doping content.
The Tc values of these microdomains are slightly different,
which induce the dispersion of the phase transition. The Nd
modification in the SBTi brings about a decrease of Tc , as
shown in figure 5. This implies that Nd doping leads to

Figure 5. Tc for SBNT and SBLT as a function of doping content.

Figure 6. Dependence of on the temperature of SBNT-0.75 near

Tc with different frequencies.

the relaxation of the lattice distortion, thus decreasing the

spontaneous polarization. Because the Nd3+ has no 6s electron,
the covalent bonding force between O2 and Nd3+ is less than
that between O2 and Bi3+ , which has lone-pair 6s electrons.
So the Nd-doping results in the relief of lattice distortion. The
Tc of SBLT decreases more drastically than that of SBNT,
indicating that the La-doping causes more drastic relief of
lattice distortion than the Nd-doping does. The Tc of SBNT0.18 is 475 C, higher than that of SBT (300 C) and BLT-0.75
(420 C), which confirms its better thermal stability.
The dependence on the frequency for SBNT-0.75 in
the vicinity of Tc is presented in figure 6. A typical relaxor
behaviour is observed with the peak position shifting towards
high temperature and the height of the peak decreasing with
the increasing of frequencies. The relaxor characteristics
373

W Wang et al

disappear when the doping content is below 0.75, which

suggests its close relationship with the doping content. Raman
studies on the La-doped BIT and SBTi suggest that substitution
with high La content leads to the ferro-paraelectric phase
transition which could also be induced by increasing the
temperature. So it is expected that doping will induce the
randomly distributed paraelectric states. But there must
be some small ferroelectric states (microdomains) induced
by the random strain fields as well as the local electric
fields. However, the dipoledipole interaction cannot be
completely prohibited, and it leads to the appearance of
macrodomains [25]. The competition between these two kinds
of domains results in the relaxor-like phase transition.

4. Conclusions
The SrBi4 Ti4 O15 ceramics are of single phase after the Nd
modification. 2Pr of SBNT-x increases at first, and then
decreases with the increase of Nd doping content. As
Nd content is 0.18, 2Pr reaches its maximum value of
25.8 C cm2 , roughly 56% higher than that of pure SBTi.
The variation of 2Pr is dominated by the restraint of the space
charge and the relief of structural distortion. The coercive field
remains almost unchanged from x = 0.00 to x = 0.18 and then
decreases monotonously with further Nd doping. Nd-doping
brings about the decrease of the Curie temperature due to
the relief of the lattice distortion. The relaxor characteristics
appear in the samples when the Nd content exceeds 0.75, which
is attributed to the competition between macrodomains and the
microdomains. Appropriate Nd-doping is found to improve
the ferroelectric property of SBTi considerably.

Acknowledgments
The authors would like to acknowledge the financial support
by 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).

374

References
[1] Auciello O, Scott J F and Ramesh R 1998 Phys. Today
July 1998, p 22
[2] Watanabe H, Mihara T, Yoshimori H and A-Paz de Araujo C
1995 Japan. J. Appl. Phys. 34 5240
[3] Dat R, Lee J K, Auciello O and Kingon A I 1995 Appl. Phys.
Lett. 67 572
[4] Joshi P C and Krupanidhi S B 1993 Appl. Phys. Lett. 62
1928
[5] Park B H, Kang B S, Bu S D, Noh T W, Lee J and Jo W 1999
Nature 401 682
[6] Li J H, Qiao Y, Liu X L, Nie C J and Lu C J 2004 Appl. Phys.
Lett. 85 3193
[7] Garg A, Snedden A, Lightfoot P, Scott J F, Hu X and
Barber Z H 2004 J. Appl. Phys. 96 3408
[8] Wu D, Li A D and Ming N B 2004 J. Appl. Phys. 95
4275
[9] Zhang S-T, Yang B, Chen Y-F and Liu Z-G 2002 J. Appl. Phys.
91 3160
[10] Irie H and Miyayama M 2001 Appl. Phys. Lett. 79 251
[11] Zhu J, Lu W P, Mao X Y, Hui R and Chen X B 2003 Japan. J.
Appl. Phys. 42 5165
[12] Lu C-H and Wu C-H 2002 J. Eur. Ceram. Soc. 22 707
[13] Shannon R D 1976 Acta Crystallogr. A 32 751
[14] Noguchi Y, Miwa I, Goshima Y and Miyayama M 2000 Japan.
J. Appl. Phys. 39 L1259
[15] Osada M, Tada M, Kakihana M, Watanabe T and Funakubo H
2001 Japan. J. Appl. Phys. 40 5572
[16] Zhu J, Chen X-B, Zhang Z-P and Shen J-C 2005 Acta Mater.
53 3155
[17] Kim S K, Miyayama M and Yanagida H 1996 Mater. Res. Bull.
31 121
[18] A-Paz de Araujo C, Cuchiaro J D, McMillan L D, Scott M C
and Scott J F 1995 Nature 374 627
[19] Takenaka T and Sakata K 1981 Ferroelectrics 38 769
[20] Mao X and Chen X 2004 J. Rare Earths 22 117
[21] Feng Q, He J-h, Zhu J and Chen X-b 2005 J. Solid. State
Chem. submitted
[22] Miessler G L and Tarr D A 2004 Inorganic Chemistry 3rd edn
(Englewood Cliffs, NJ: Prentice Hall) p 38
[23] Ding Y, Liu J S, Qin H X, Zhu J S and Wang Y N 2001 Appl.
Phys. Lett. 78 4175
[24] Chen Y P, Yao Y Y, Bao Z H, Zhu J S and Wang Y N 2003
Mater. Lett. 57 3623
[25] Chen X B, Hui R, Zhu J, Lu W P and Mao X Y 2004 J. Appl.
Phys. 96 5697