J Nanopart Res (2013) 15:1787
DOI 10.1007/s11051-013-1787-y
RESEARCH PAPER
Nanotubes of piezoelectric BNT–BT0.08 obtained
from sol–gel precursor
Marin Cernea • Lucian Trupina •
Bogdan S. Vasile • Roxana Trusca •
Cristina Chirila
Received: 13 March 2013 / Accepted: 8 June 2013
Ó Springer Science+Business Media Dordrecht 2013
Abstract Barium titanate-substituted bismuth tita-
nate ((Bi0.5Na0.5)0.92Ba0.08TiO3, BNT–BT0.08) nano-
tubes were fabricated using sol–gel chemistry, spin
casting, and a porous polycarbonate membrane tem-
plate. The structure and morphology of the tubes have
been investigated by scanning electron microscopy
and transmission electron microscopy. The diameter
and length of these tubes were about 650 nm and
20 lm, respectively, and their wall thickness was
about 50 nm. The tubes were polycrystalline with
average grain size of *40 nm. The BNT–BT0.08
nanotubes exhibited ferroelectric behavior as evi-
denced by saturated piezoresponse hysteresis loops
and phase switching. BNT–BT0.08 piezoelectric nano-
tubes promise novel device architectures and
enhanced electric properties.
Keywords Lead-free ferroelectrics

(Bi0.5Na0.5)0.92Ba0.08TiO3 nanotubes
Sol–gel
processes
Piezoelectric properties
M. Cernea (&)
L. Trupina
C. Chirila
National Institute of Materials Physics, P.O. Box MG-7,
077125 Bucharest-Magurele, Romania
e-mail: mcernea@infim.ro
B. S. Vasile
University Politehnica of Bucharest, 060042 Bucharest,
Romania
R. Trusca
METAV-R&D S. A., P.O. 22, Bucharest, Romania
Introduction
Sodium bismuth titanate (Na1/2Bi1/2)TiO3 (BNT) is
studied as a viable alternative lead-free material to
lead zirconate titanate (PZT) perovskite materials
(Takenaka et al. 1991). BNT bulk ceramics show
excellent piezoelectric properties but it is difficult to
achieve successful poling due to its electrical conduc-
tivity (Takenaka and Sakata 1989; Nagata and Take-
naka 2001; Wang et al. 2004; Bousquet et al. 2010).
Doping of the BNT compound with alkaline earth
oxides (barium, strontium, or potassium oxides) is a
common way to improve the poling process of BNT
ceramics and its piezoelectric properties (Zhang et al.
2010a, b; Chen et al. 2011; Sung et al. 2010).
(Na0.5Bi0.5)1-xBaxTiO3 (BNT–BTx) solid solutions
(0 B x B 0.15) were prepared as bulk ceramics (Jo
et al. 2011; Zhang et al. 2008; Wang et al. 2010) and
thin films (Cernea et al. 2011; Zhang et al. 2010a, b;
Guo et al. 2008). However, the authors are not aware
of any published works on BNT–BTx tubes prepared
by sol–gel method. Nanorods and nanotubes are
usually defined as 1D rod-like nanostructures with a
large aspect ratio (length divided by width) in a range
of 3–5, which are the most studied examples of
anisotropic nanocrystals (Luo et al. 2003; Yilmaz et al.
2003; Chen et al. 2008; Jones and Thomas 2002;
Carbone et al. 2007; Glotzer and Solomon 2007;
Persano et al. 2010; Rizzo et al. 2009; Ryan et al. 2006;
Stebe et al. 2009; Sun et al. 2007; Wang and Li 2006).
The nanotubes and nanowires of many materials have
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attracted great interest because they exhibit different
physical properties than their bulk and thin films
(Yilmaz et al. 2003). The ferroelectric nanowires and
nanotubes are promising candidates for use in minia-
turized devices like detectors for biological and
chemical species (Cui et al. 2001). Wetting of the
porous templates is an usual technique for fabricating
ferroelectric nanostructures like nanotubes (or more
correctly, nanoshell tubes, as their diameter is typi-
cally of the order of several hundred nanometers or
several micrometers while the wall thickness is just
tens of nanometers) (Gruverman and Kholkin 2006).
In this paper, we report on the preparation, micro-
structure, and piezoelectric investigations of BNT–
BT0.08 nanotubes by a sol–gel route. We chose the
composition BNT–BT0.08 to fabricate piezoelectric
tubes because there is an interval x = 0.06–0.10,
named morphotropic phase boundary (MPB), where
the solid solutions BNT–BTx show enhanced dielec-
tric properties, ferroelectric and piezoelectric activi-
ties (Wang et al. 2009).
Experimental procedure
Precursor sol of 0.92[(Bi0.5Na0.5)TiO3]–0.08[BaTiO3]
was prepared by sol–gel technique starting from anhy-
drous sodium acetate (CH3COONa, 99.995 %, Aldrich),
barium acetate ((CH3COO)2Ba, 99 %, Aldrich), bismuth
(III) acetate ((CH3COO)3Bi, 99.99?%, Aldrich), and
titanium(IV) isopropoxide, 97 % solution in 2-propanol
(Ti{OCH(CH3)2}4, Aldrich). Acetic acid (C99.7 %,
Aldrich) was used as solvent for the acetates. The
mixture of sodium, bismuth, and barium acetic solutions
was added drop-wise, to the titanium isopropoxide
solution to produce a Na–Bi–Ba–Ti complex solution
(sol). The sol used in our experiments was homogeneous,
and stable colloidal sols. The sol was stabilized by adding
dimethylformamide and acetylacetone. To prepare
BNT–BT0.08 tubes, this sol precursor was poured on the
surface of polycarbonate membrane with thickness of
20 lm, pore diameter of about 0.8 lm, respectively, and
108 cm-2 pore density) at room temperature. The sol was
uniformly distributed on the membrane surface by spin
casting at 3,000 rpm for 20 s. The polymeric sol wets the
pore walls of porous membrane and fills the pores. The
prevention of surface film formation on one side of the
membrane was achieved by washing the surface of
membrane with propanol. Then, the membrane with sol
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J Nanopart Res (2013) 15:1787
was kept for 2 days in air to complete transformation of
the sol to a gel. Finally, the membrane was dissolved in
dichloromethane (CH2Cl2). The tubes were separated
from the solution by repeated centrifugation and washing
with dichloromethane. NBT–BT0.08 crystallized tubes
were obtained after heating the tubes-gel at 700 °C, 2 h in
air. The tubes made by sol–gel were investigated by
scanning electronic microscopy (SEM), transmission
electron microscopy (TEM), and selected area electron
diffraction (SAED). The microstructure of the samples
was investigated using a FEI Quanta Inspect F scanning
electron microscope and a TecnaiTM G2 F30 S-TWIN
transmission electron microscope with a line resolution of
1 Å, in high-resolution transmission electron microscopy
(HR-TEM) mode and selected area electron diffraction
(SAED). The local piezoelectric properties were inves-
tigated by piezoresponse force microscopy (PFM) using
an Asylum Research MFP-3D atomic force microscope
(AFM).
Results and discussion
Microstructure
The SEM micrographs of BNT–BT0.08 tubes depos-
ited on Si/Pt substrate and calcined at temperature of
700 °C, 2 h in air, are presented in Fig. 1.
Figure 1a is a top view of the tubes showing that the
tubes are open-ended; the average outer diameter and
wall thickness of tubes are about 650 nm (Fig. 1b) and
50 nm (Fig. 1a), respectively. During the heating
stage, the templated sol–gels underwent densification
and shrinkage to produce tubes with diameter smaller
than the diameter of membrane channel (0.8 lm). The
nanotubes length does not vary significantly from that
of template (20 lm) (Fig. 1c).
Nanostructure morphology of BNT–BT0.08 tubes
resulting from our sol–gel template method was
analyzed by TEM and HR-TEM. The TEM image of
a single tube shows that these structures comprise
grains of *50 nm (Fig. 2a, b). The tube shown was
calcined at 700 °C, 2 h in air.
The HR-TEM image (Fig. 2c) shows the lattice
fringes of polycrystalline nanoparticles with d =
2.74 Å, corresponding to the (110) crystallographic
planes of Na0.5Bi0.5TiO3 rhombohedral phase (Jones
and Thomas 2002). The regular succession of the
atomic planes indicates that the nanocrystallites are
J Nanopart Res (2013) 15:1787 Page 3 of 7

Fig. 1 SEM images of BNT–BT0.08 tubes; a top view, b close Fig. 2 TEM images of the BNT–BT0.08 tubes (a, b) corre-
side view, and c side view of the tubes sponding HR-TEM of nanocrystals (c) and SAED pattern (d)

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structurally uniform. Both HR-TEM image and the
SAED ring patterns (Fig. 2d) indicate a rhombohedral
Na0.5Bi0.5TiO3 phase for BNT–BT0.08 tube.
Piezoelectric characterization
We used PFM to explore the domain morphology and
polarization phenomena at nanoscale level because
PFM is useful for investigating the polarization
behavior in complex multidomain structures (Rogers
et al. 2012). The PFM investigations require a good
electrical contact between tip and surface of the tube
which often leads to the displacement of tube from its
initial position or to the tip damage. An atomic force
microscope (MFP 3D SA, Asylum Research) was
Fig. 3 AFM height (a), PFM amplitude (b), and PFM phase image (c) of a BNT–BT0.08 microtube. The PFM data are overlaid onto
height image
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J Nanopart Res (2013) 15:1787
employed to obtain high-resolution images of the
surface. Olympus AC240-TM cantilevers (Pt coated)
were used for simultaneous topography and domain
imaging. Dual AC Resonance Tracking (DART)
method was used because it allows the cantilever to
be operated at or near resonance thus achieving the
highest signal to noise ratio.
Figure 3 shows the atomic force microscopy
(AFM) image (a), piezoresponse amplitude image
(b), and piezoresponse phase image (c) of a BNT–
BT0.08 nanotube.
As can be seen from Fig. 3b, the amplitude
piezoresponse signal obtained on the upper part of
the tube is smaller than in the lateral parts. The
possible explanation attributed to this result may be
J Nanopart Res (2013) 15:1787
that the electric field applied on tube is not uniform, as
a consequence of the particular geometry of the tip as
top electrode and the investigated surface of the tube
with a semicircular shape. The upper part of the tube is
not in direct electrical contact with the platinum
bottom electrode which makes the applied electric
field on the tube wall to be very small. The PFM phase
Fig. 4 Morphology (a), amplitude (b), and phase (c) images of
piezoresponse signal for BNT–BT0.08 thin film
Page 5 of 7
image (Fig. 3c) shows strong and clear contrasts
indicating the presence of polarized nanoregions with
different polarization orientations in the BNT–BT0.08
nanotube. The maximum displacement values were
obtained at the end of the tube, as can be seen in
Fig. 3b (bright region). Due to favorable tip-tube
geometry we assume that the tip was in direct contact
with the inner surface of the tube. In this case the
electric field strength maxima occur because the
driving voltage was directly applied between the inner
wall of the tube and the platinum bottom electrode.
Due to this geometry, quantitative results are difficult
to obtain on BNT–BT0.8 tube.
In order to compare the piezoelectric characteristics
of BNT–BT0.08 nanotube and thin film, we prepared a
Fig. 5 Switching spectroscopy piezoresponse force micros-
copy (SSPFM) of BNT–BT0.08 thin film: a amplitude-voltage
butterfly loop and b phase-voltage hysteresis loop
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BNT–BT0.08 thin film from the same sol precursor. The
PFM results obtained on a BNT–BT0.8 thin film (shown
in Figs. 4 and 5) support our assumption. The value of
amplitude piezoresponse signal, obtained in the same
scanning conditions, on thin film has the same order of
magnitude with the value obtained at the end of tube.
As can be seen in Fig. 4c, the piezoactive regions
form a complex labyrinth structure, which reflects
spatial inhomogeneities determined by both random
fields and random strains introduced with BaTiO3
doping. The characteristic butterfly loops between
PFM amplitude and DC bias (Fig. 5a) and the
hysteresis loops between the PFM phase and DC bias
(Fig. 5b) indicate the ferroelectric and piezoelectric
behavior of BNT–BT0.08 thin film with the same
chemical composition as the nanotubes.
Conclusions
BNT–BT0.08 nanotubes with outer diameters of about
650 nm and a wall thickness of *50 nm were
successfully fabricated using a sol–gel process com-
bining porous polycarbonate membrane templates
with pore diameters of 0.8 lm. This paper reports on
the optimum processing conditions used to prepare the
piezoelectric BNT–BT0.08 tubes. The room-tempera-
ture crystalline symmetry of the BNT–BT0.08 nano-
tubes, calcined at 700 °C, for 2 h in air, analyzed by
HR-TEM and SAED indicated a polycrystalline
structure corresponding to the rhombohedral
(Bi0.5Na0.5)TiO3 perovskite phase. The PFM investi-
gations on the as-prepared BNT–BT0.08 nanotubes and
thin films, derived from the same sol precursor,
indicated a ferroelectric and piezoelectric behavior.
Acknowledgments The authors gratefully acknowledge the
Romanian Research Ministry ‘‘NUCLEU 45N’’-project, from
the National plan for RDI, funded by the Romanian Ministry of
Education and Research, and the National Authority for
Scientific Research for financial support.
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