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Integrated Ferroelectrics: An
International Journal
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INTRODUCTION
Bi-layered structured ferroelectrics (BLSF), especially SrBi2 Ta2 O9 (SBT),
have been recently recognized as promising materials for nonvolatile ferroelectric random access memories (NvFRAM), mainly due to their excellent
fatigue endurance and low leakage current [1]. To date, most of the work on
SBT has been focused on thin films for NvFRAMs. To accelerate the development of SBT-based devices and to improve the functionality of ferroelectric
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EXPERIMENTAL PROCEDURE
Highly oriented SBT single crystal platelets with layered habit and translucent appearance were grown by the high-temperature self-flux method described elsewhere [68], using a boron-modified Bi2 O3 flux. The largest
crystals with sizes around 7 5 mm2 and thickness of 50 m were obtained
by an optimized thermal profile that included an accelerated slow cooling
process. After separating the crystals from the flux by leaching in hot nitric
acid, both facets of the crystals was polished using a colloidal-silica aqueous solution and then annealed at 750 C for 10 hours for dielectric and PFM
measurements.
The structural quality of the SBT single crystals was investigated by
x-ray angular -2 and -scanning topography methods [9]. In these methods, the platelet sample is rotated at an angular rate , and a photographic
film placed directly in front of the x-ray detector and perpendicular to the
diffracted beam, is either rotated at an angular rate 2 (for -2 -scanning
topography) or is fixed (for -scanning topography). The standard DRON-2
diffractometer was used. The -2 -scanning topography method is sensitive
to the misorientation between adjacent blocks of the crystal, and the misorientation angles are related to the angular interval of rotation. The samples
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FIGURE 1 (a,b) X-ray diffraction spectra for a rectangular perfect c-oriented SBT
crystal platelet along [100] and [001] directions, respectively. (c) Rocking curve of
the (0 0 18) reflection.
FIGURE 2 X-ray (a) -scanning and (b) -2 -angular scanning topographies, using
the (110) and (0 0 18) reflection, respectively, for a small, rectangular and perfect
SBT single crystal.
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scanning topographs using the (0 0 18) reflection. For an ideal crystal, this
image should also give a uniform contrast with the size of the image depending linearly on the geometry of the experimental setup [9]. In our case,
the deviation of the diffraction image in Fig. 2(b) from the rectangular form
[-angular scanning topographs in Fig. 2(a)] comes from the small bending
of the crystal leading to the misorientation from c-direction. It was estimated
that this deviation is due to the misorientation less than 1 for this crystal.
The crystal quality is better demonstrated through the rocking curves [see
Fig. 1(c) for (0 0 18) reflection], where the half width of the rocking curve
is 0.04 .
X-ray topography also gives information about crystallographic orientation of the SBT single crystal facets. Figure 2(a) also presents the directions
of the main crystallographic axes, where the narrow sides of the rectangular
shaped crystals are oriented along [110] and [1 1 0] directions with the [001]
direction (c-axis) lying perpendicular to the major face.
To investigate and to confirm the anisotropic properties of the SBT crystals, the D-E hysteresis loop was measured at room temperature along the
direction normal to the major face of the crystals (along c-axis) in the ferroelectric state. Figure 3 shows the linear behavior of the D-E relation for the
perfectly oriented SBT crystal, where no remanent polarization is observed
FIGURE 3 D-E hysteresis measurements for the perfect c-axis oriented SBT single
crystal.
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along the c-axis for a maximum electric field of 100 kV/cm. This finding is
consistent with that expected for BLSF materials with even number (m) of
BO6 octahedra, where the dipole moments caused by ionic displacements
along the c-axis are cancelled out due to the presence of a mirror plane perpendicular to the axis [5]. Thus, spontaneous polarization vector in the SBT
structure lies entirely along the crystallographic a-axis (in a-b plane) and no
polarization is obtained in the direction perpendicular to the bismuth layer
(c-axis) [12]. Furthermore, the applied high electric field also demonstrates
good insulating properties of our crystals. Low conductivity and high breakdown field are indicative of a low concentration of defects. High resistivity
along c-axis direction could be achieved due to the insulating Bi2 O3 layers
blocking charge transport as explained in other BLSF crystals [4]. The direct
determination of the spontaneous polarization in a-b plane is difficult since
the thickness of the crystals is too small, 50100 m at best.
Small high-quality crystals were also tested via dielectric measurements
along c-axis (nonpolar direction). Figure 4 shows the temperature dependence of the relative permittivity at various frequencies for SBT crystal
upon cooling. A ferro-paraelectric phase transition with a sharp maximum
in permittivity is clearly observed at Tc = 350 C (Curie temperature), in
a good agreement with previous reports on SBT crystals from XRD and
FIGURE 4 Temperature dependence of the relative permittivity at several frequencies for the perfect c-axis oriented SBT crystal. (inset) Reciprocal permittivity displaying a linear relationship (Curie-Weiss behavior).
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specific heat measurements [13, 14]. Here, the phase transition can be observed along nonpolar direction, similarly to other BLFS systems with even
number of BO6 octahedra [2]. It should be noted that the Tc s reported for
SBT ceramics [15] are somewhat lower than the transition temperature found
in our SBT crystals.
The Curie-Weiss behavior displays a linear relationship between the inverse permittivity and (T-Tc ) for temperatures above Tc , from which the
Curie-Weiss constant (C) can be determined (see the inset to Fig. 4). From
our measurements, the value of the Curie constant was evaluated C = 4.1
104 C. This is one order of magnitude lower than that expected for displacive
phase transitions. This including data on SBT ceramics [15].
The low permittivity values, with small frequency dispersion, recorded
in the entire temperature range (max
135 at the Curie point, significantly
smaller than the values reported for SBT ceramics, max
600) are attributed
to the perfect orientation of the crystal, with c-axis perpendicular to the major
face. On the other hand, low dielectric losses values were obtained in the
entire temperature range (tan 0.04) confirming that the crystals have low
conductivity and thus low concentration of defects.
For PFM measurements the cantilever was positioned parallel to one of the
crystal edge 110 and the tip was scanned at the small rate of 1 m/s. Figure 5
(a, b) shows simultaneously acquired topography and domain images. On the
domain image the regions of bright and dark contrast correspond to domains
with polarization oriented up and down in the Figure plane, respectively. To
ascertain the complete orientation of polarization inside domains the sample
was rotated at 90 degree. The images of similar domains for initial position
of the sample [Fig. 5(c)] and after its rotation [Fig. 5(d)] are complementary
and the domains appear well faceted.
The observed domain pattern is typical of twinning structure. Twins
boundaries are visible as straight forward lines oriented in 110-direction
(on the image they looks slightly inclined due to imperfect orientation of
cantilever relative single crystal) and separate the regions with orthogonal
[(100) or (010)] polar axis directions. Generally the observed twin widths are
in the range of 0.71.5 m. Alternating bright and dark stripes inside twins
correspond to 180 domains with domain walls oriented parallel to polar
axis as previously reported by the authors [16]. The size of these domains
varies in the range of 250500 nm. The peculiarities of domain structure
observed directly by PFM prove that paraelectric-ferroelectric phase transition in the studied SBT single crystals is accompanied by formation of
developed banded twin structure, consisting mainly on oppositely oriented
domains. The comparison of the obtained data with previous observation
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of a-c (b-c) plane of the SBT crystals [16], allows as concluding that 180
degree domain walls have rod-like shape parallel to a-axis.
CONCLUSIONS
Highly oriented SBT single crystal platelets with layered habitus and translucent appearance were grown by self-flux method using a boron-modified
Bi2 O3 flux. The narrow sides of the rectangular shaped crystals are oriented
along [110] and [1 1 0] directions with the [001] direction (c-axis) lying
perpendicular to the major face. The absence of hysteresis, [expected for
BLSF materials with even number (m) of BO6 octahedra], and the sharp
phase transition from permittivity curve have confirm the high quality of
the grown SBT crystals. The domain pattern observed by PFM measurements is typical of twinning structure with twin boundaries oriented along
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the 110-direction. 180 domains were also observed with domain walls
oriented parallel to polar axis.
ACKNOWLEDGMENTS
H. Amorn, I. K. Bdikin and V. V. Shvartsman acknowledge the Foundation
for Science and Technology (FCT, Portugal) for the financial support through
a Ph.D. and Postdoctoral grants, respectively.
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