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Ferroelectrics
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Structural and Electrical

Characterization of Ferroelectric
SrBi2Nb2O9 Single Crystals Grown by
High-Temperature Self-Flux Solution
a

H. AmorN , R. S. Martins

a b

, A. L. Kholkin & M. E. V. Costa

Department of Ceramics and Glass Engineering & Center for

Research in Ceramic and Composite Materials (CICECO), University
of Aveiro, Aveiro, 3810-193, Portugal
b

Also at Department of Mechanical Engineering, Federal University

of Santa Catarina, Florianopolis, Brazil
Published online: 09 Mar 2011.

To cite this article: H. AmorN , R. S. Martins , A. L. Kholkin & M. E. V. Costa (2005): Structural and
Electrical Characterization of Ferroelectric SrBi2Nb2O9 Single Crystals Grown by High-Temperature
Self-Flux Solution, Ferroelectrics, 320:1, 43-50
To link to this article: http://dx.doi.org/10.1080/00150190590966775

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Ferroelectrics, 320:4350, 2005

Copyright Taylor & Francis Inc.
ISSN: 0015-0193 print / 1563-5112 online
DOI: 10.1080/00150190590966775

Structural and Electrical Characterization of

Ferroelectric SrBi2 Nb2 O9 Single Crystals Grown by
High-Temperature Self-Flux Solution

Downloaded by [Seoul National University] at 01:40 28 June 2013

H. AMORIN, R. S. MARTINS, A. L. KHOLKIN,

AND M. E. V. COSTA
Department of Ceramics and Glass Engineering & Center for Research in
Ceramic and Composite Materials (CICECO), University of Aveiro, 3810-193
Aveiro, Portugal
High-quality SrBi2 Nb2 O9 (SBN) single crystals were grown from a melt using a hightemperature self-flux solution method and Bi2 O3 added with B2 O3 as a flux. A suitable
thermal profile involving slow cooling rates allowed growing large and translucent SBN
crystals exhibiting platelet morphology with typical size 5 5 mm2 and thickness
approximately 400 m. X-ray diffraction revealed a dominant (001)-orientation of the
major face of the platelet crystals and edges oriented parallel to the [110] directions.
The dielectric properties were evaluated along the ab-plane and in the c-axis direction.
The ferro-paraelectric phase transition was observed at TC = 440 C with Curie-Weiss
relationship above TC . The anisotropy of dielectric permittivity, i.e., the ratio between
permittivity in the ab-plane and along c-axis was about 10 at TC . The obtained results are
used to discuss the observed correlations between anisotropy, crystalline orientation,
and electrical properties.
Keywords Bi-layer structured ferroelectrics; SrBi2 Nb2 O9 single crystals; hightemperature self-flux solution growth; dielectric anisotropy
PACS: 81.10.Dn; 77.84.Dy; 77.22.Ch; 77.80.Bh

Introduction
Ferroelectric materials belonging to the Aurivillius family [1] such as SrBi2 Ta2 O9 (SBT)
and its Nb counterpart SrBi2 Nb2 O9 (SBN) are potential candidates for applications in
nonvolatile ferroelectric random access memories (FeRAMs) [2, 3] and high-temperature
piezoelectric sensors [4]. For FeRAMs device applications, in addition to the fatigue endurance property, high switching polarization, sufficiently low coercive field and high ferroelectric Curie temperature (TC ) are required properties for high performance and reliable
operation. The spontaneous polarization and TC of SBN are higher than those of SBT,
but the coercive field is higher [5, 6]. That is why the SBN films are much less favorable
Received September 6, 2004; In revised form January 4, 2005.

Also at Department of Mechanical Engineering, Federal University of Santa Catarina,

Florianopolis, Brazil.

Corresponding author. E-mail: hamorin@cv.ua.pt

[511]/43

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H. Amorn et al.

for FeRAMs applications, even though the fatigue endurance of SBN is as high as that of
SBT.
The Aurivillius phases are described by the general formula (Bi2 O2 )2+
(Am1 Bm O3m+1 )2 , where m is an integer number, A can be mono-, di-, or trivalent ions
and B represents Ti4+ , Nb5+ , Ta5+ or the combination of them [1]. Among the Aurivillius
phases, SBN system (m = 2) is described by an orthorhombic distortion in the ferroelectric
phase (space group A21 am), where the spontaneous polarization is directed along the orthorhombic a-axis and originates mainly from the polar displacements of the A cation and
co-operative tilting of the BO6 octahedral units [710].
From the very beginning it was understood that the layered structure of the Aurivillius
phases, where perovskite blocks are interleaved with Bi2 O2 layers, should lead to a high
dielectric, ferro-, and piezoelectric anisotropy due to the predominantly 2D character of
the ferroelectric switching [11]. Thus, the improved performance should be achieved in
suitably oriented single crystals to optimize ferro- and piezoelectric properties and, as such,
should be investigated in detail in single crystals. Besides, from the fundamental science
point of view, single crystal data are also required for the thermodynamic analysis of the
phase transitions in these technologically important materials.
In the last years, the efforts were mainly focused on obtaining single crystals of the
Aurivillius family by high-temperature self-flux solution method using a Bi2 O3 flux [12
16]. Recently, the authors reported the ferroelectric and dielectric anisotropy in high-quality
SBT single crystals [17]. However, the synthesis of SBN crystals is generally difficult, and
thus, to the best of our knowledge, the study of the SBN intrinsic properties has not been
reported so far, due mainly to the lack of large SBN single crystals. The main objective of this
work was to grow large and high-quality SrBi2 Nb2 O9 single crystals using an optimized
process. The structural and dielectric properties were evaluated and used to confirm the
quality of the grown crystals.

Experimental Procedure
SBN single crystals were grown using a modified high-temperature self-flux solution method
described elsewhere [1518]. Polycrystalline SBN powder was firstly synthesized via solidstate reaction using high-purity (>99.5%) SrCO3 , Bi2 O3 and Nb2 O5 reagents. Pure SBN
powder was obtained by heating up to 950 C and soaking at this temperature for 2 h in air.
After calcinations the powder was ball milled in ethanol for 8 h and then mixed with the
flux using a molar ratio of 60/40 of SBN to flux. The flux used was a mixture of 35 wt% of
Bi2 O3 (melting point: 825 C) and of 5 wt% of B2 O3 (melting point: 450 C).
An amount of 40 g of the ground SBN/flux mixture was put inside a 15 ml Pt crucible
covered with a Pt lid. Figure 1 shows the setup used for the growth of SBN single crystals.
The Pt/Al2 O3 double crucible was used to prevent the evaporation of the flux at high
temperature. First, a premelting was done at 950 C for 2 h, followed by the melting and
cooling stages using the thermal profile illustrated in Fig. 2. The profile includes heating up
to 1350 C and soaking at this temperature for 10 h. After this, a gradually accelerated slow
cooling process similar to the previously optimized one for growing SBT single crystals
[18] was introduced in order to create the required supersaturation for crystals nucleation
and growth. The profile included a slow cooling at 2 C/h down to 1300 C, an accelerated
cooling at 5 C/h down to 1200 C, fallowed by faster cooling at 10 C/h down to 1000 C,
then at 20 C/h down to 800 C, and a final cooling at 100 C/h down to room temperature.
The grown SBN crystals were separated from the flux using a two-step process. First,
the crystals and solidified flux were taken out from the Pt crucible by inverting it on a

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Ferroelectric SrBi2 Nb2 O9 Single Crystals

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Figure 1. Setup for the growth of SrBi2 Nb2 O9 single crystals. The assembly of Pt and Al2 O3 crucibles
is used to prevent the evaporation of the flux at high temperature, due to its high volatility.

porous ceramics at 1000 C, and then the crystals were separated by leaching in hot nitric
acid to dissolve the flux. This process is slow and takes a few days to completely remove
the existing flux between the platelet single crystals. Finally, SBN crystals were leached in
hot water for several hours to dissolve the nitric salt and then annealed at 750 C for 10 h.
The crystallographic orientation of the plate-like SBN single crystals was examined by
X-ray diffraction analysis (XRD) using a Rikagu/New diffractometer (CuK radiation and
0.05 /step) and x-ray angular 2 and -scanning topography methods [19]. The crystals
were polished in two directions: parallel to the ab-plane (measurements along c-axis), and
perpendicular to the [110] direction [measurements in ab-plane] for dielectric measurements. In the latter case, because of the small transverse size of the samples, a correction
for the stray capacitance of the sample holder and connecting wires was necessary to precise
the capacitance of the sample. Gold electrodes were sputtered onto the polished parallel

Figure 2. Illustration of the furnace thermal profile used for the growth of SrBi2 Nb2 O9 single crystals.

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H. Amorn et al.

Figure 3. Micrographs showing (a) the solidified flux and crystals inside the Pt crucible and (b) the
as-grown and cleaned SrBi2 Nb2 O9 single crystal platelets (1 division = 1 mm).

facets of the samples. Dielectric properties were measured using a HP4284A LCR Meter
in the frequency range from 1 kHz to 1 MHz.

Results and Discussion

It has been already reported that high-quality SBT single crystals could be obtained by
self-flux solution method adding a low amount of B2 O3 to the Bi2 O3 flux [1518]. The
addition of a small amount of B2 O3 (5 wt%) to the flux improves the crystallization results
by promoting melting of the powder and leading to a more viscous and stable medium,
where SBT crystals nucleate [15]. In the same manner, large and translucent SBN single
crystals with rectangle shape, dimensions of approximately 5 5 0.4 mm3 and smooth
surfaces have been grown for the first time in this work by using the boron-modified flux. The

Figure 4. X-ray diffraction pattern for the major face of a perfect c-axis oriented SrBi2 Nb2 O9 single
crystal platelet showing the (00l) plane reflections.

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Ferroelectric SrBi2 Nb2 O9 Single Crystals

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obtained crystal dimensions are similar to those reported for SBT [1618] when using the
same temperature profile, but the thickness of the grown SBN crystals (400 m) is twice the
value obtained for SBT single crystals. Figure 3 shows the micrographs of the solidified
flux with crystals inside the Pt crucible and of the as-grown and cleaned SBN single crystal
platelets.
The crystalline structure of the grown SBN single crystals was studied by XRD technique at room temperature. Figure 4 shows the XRD spectra for a rectangular SBN single
crystal platelet where only (00l) plane reflections were obtained along the direction perpendicular to the major face of the crystal. On the other hand, from x-ray topography
measurements it was observed that the narrow sides of the rectangular shaped crystals are
oriented along the orthorhombic [110] direction [45 to both a- and b-axes] with the [001]
direction (c-axis) lying perpendicular to the major face.
Figure 5 shows the temperature dependence of the relative permittivity at different
frequencies measured on cooling on the ab-plane (along the [110] direction) and along
c-axis of the SBN single crystal. In both cases, the ferro-paraelectric phase transition is
clearly observed at TC = 440 C (Curie temperature), confirming the results of previous reports on SBN ceramics [6]. The maximum permittivity of SBN in the ab-plane (3000
at 1 kHz) was about an order of magnitude greater than that along c-axis ( 200 at
1 kHz) in a good agreement with the results obtained in other bismuth layer structured
ferroelectrics single crystals [12, 17]. The permittivity value measured in the ab-plane exceeds significantly that of bulk ceramics [6]. It should be noted that our measurements in
the ab-plane were performed in the [110] direction, which is oriented 45 with respect
to the polarization direction (a-axis). As such, the obtained value should correspond

Figure 5. Temperature dependence of the dielectric permittivity at different frequencies along the
[110] (ab-plane) and the [001] (c-axis) directions in the SrBi2 Nb2 O9 single crystal.

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H. Amorn et al.

Figure 6. Temperature dependence of the dielectric losses at different frequencies along the [110]
(ab-plane) and the [001] (c-axis) directions in the SrBi2 Nb2 O9 single crystal.

to an averaging of both a- (polarization direction) and b-axes permittivity values, i.e.,

[110] = (a +b )/2.
Figure 6 shows the temperature dependence of the dielectric losses (tan ) at different frequencies in the ab-plane and along c-axis, where a similar behavior was obtained
in both cases. The loss factor could be measured both below and above TC thus suggesting that the dc conductivity that typically prevents high-temperature dielectric measurements in BLSF is not a problem in our crystals. The low value of tan (< 0.04
both above and below TC ) confirms low defect concentration and high quality of the
crystals.
In ferroelectric materials, the temperature dependence of the permittivity typically
obeys the Curie-Weiss law: = C/(T TCW ), originated from the temperature dependence of the first coefficient in the phenomenological Landau theory. Here, C is the Curie
constant and TCW is the Curie-Weiss temperature, which is generally somewhat lower
than TC . Figure 7 shows the linear relationship between reciprocal permittivity and (T-TC )
in the ab-plane above and below TC for the curve obtained at 1 MHz. The Curie constant was determined from the slope of the straight line above TC (C = 4.7 104 C)
and TCW was 422 C. The obtained value of Curie constant is of the same order of magnitude than that previously obtained for SBT single crystals [17]. From the theoretical
point of view there should be no coupling between the order parameter lying in the abplane and the out-of-plane (along c-axis) dielectric displacement. The dielectric behavior along c-axis should be mainly determined by the paraelectric bismuth oxide layers
and thus it is suggested that the small peak around TC is of the extrinsic character and
could be attributed to a slight deviation of the crystal from the [001] direction during
preparation.

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Figure 7. Temperature dependence of the reciprocal dielectric permittivity at 1 MHz along the [110]
(ab-plane) direction showing the Curie-Weiss behavior.

Conclusions
In summary, high-quality SrBi2 Nb2 O9 single crystals with typical sizes of 5 5 0.04 mm2
were grown for the first time by the self-flux method, and their dielectric properties were
investigated independently in the ab-plane and along c-axis. The narrow sides of the rectangular shaped crystals are oriented along the orthorhombic [110] direction [45 to both
a- and b-axes] with the [001] direction (c-axis) lying perpendicular to the major face. The
ferro-paraelectric phase transition was observed at TC = 440 C, while the maximum permittivity along the ab-plane (3000) was an order of magnitude greater than that along
the c-axis direction (200). The Curie-Weiss law is obeyed in the ab-plane and displays a
value of Curie constant 4.7 104 C.

Acknowledgments
H. Amorn acknowledges the Foundation for Science and Technology (FCT, Portugal) for
the financial support through a PhD grant. The authors also thank Dr. Igor K. Bdikin for his
technical support and helpful discussion of the x-ray topography measurements.

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