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Perovskite ferroelectric nanomaterials†

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Cite this: Nanoscale, 2013, 5, 8752

Nurxat Nuraje*a and Kai Su*b

Received 16th May 2013
Accepted 20th June 2013
DOI: 10.1039/c3nr02543h
www.rsc.org/nanoscale
In this review, the main concept of ferroelectricity of perovskite oxides and related materials at nanometer
scale and existing difficulties in the synthesis of those nanocrystals are discussed. Important effects, such as
depolarization field and size effect, on the existence of ferroelectricity in perovskite nanocrystals are
deliberated. In the discussion of modeling works, different theoretical calculations are pinpointed
focusing on their studies of lattice dynamics, phase transitions, new origin of ferroelectricity in
nanostructures, etc. As the major part of this review, recent research progress in the facile synthesis,
characterization and various applications of perovskite ferroelectric nanomaterials, such as BaTiO3,
PbTiO3, PbZrO3, and BiFeO3, are also scrutinized. Perspectives concerning the future direction of
ferroelectric nanomaterials research and its potential applications in renewable energy, etc., are
presented. This review provides an overview in this area and guidance for further studies in perovskite
ferroelectric nanomaterials and their applications.

1 Introduction uncertain in the scientic community, even though many

1.1 Ferroelectricity
As one of the important topics in modern physics, ferroelec-
tricity has attracted much attention since around 100 years ago.1
Pioneering studies on ferroelectricity in perovskite oxides
occurred in the period of 1940s to 1960s, mainly on barium
titanate, strontium titanate, lead titanate, etc.2–7 In those early
times, scientists did very interesting studies io perovskite-type
ferroelectrics. For example, in von Hippel's research, phase
transitions at Curie temperatures for different perovskite-type
ferroelectrics were clearly observed and an extremely high
dielectric constant, more than 11 000, was also observed in a
material of “71% BaTiO3 and 29% SrTiO3”.2 Other materials
were also thoroughly studied in the reference. Since then,
ferroelectrics and their physics have been studied systematically
through experimental physics, computer modeling, material
synthesis, wet-chemical synthesis, etc. Since the early 1990s, the
origin of ferroelectricity in macroscopic scale has been funda-
mentally understood.8 The industrial applications of ferroelec-
trics at that time include Multi-Layer Ceramic Capacitors
(MLCCs), transducers and actuators, catalysts, etc.9,10 On the
other hand, demanding advances in nano-science and tech-
nology revealed a so-called size effect in perovskite-type
oxides.11–30 The size effect indicates the disappearance of
ferroelectricity in perovskite-type oxides with dimensions
smaller than a critical value. The reason why it happens is still
a
Department of Materials Science & Engineering, Massachusetts Institute of
Technology, Cambridge, MA 02139, USA. E-mail: nurxat@mit.edu
b
BASF Corporation, 500 White Plains Road, Tarrytown, NY 10591, USA. E-mail: kai.
su@basf.com
† The authors declare no competing nancial interests.
hypotheses have been proposed. In this review, different
hypotheses are discussed and readers can refer to original
research studies for details. In addition, the inuence of
depolarization on the formation of ferroelectric perovskite
oxides is explored. Some computational modeling progress in
this area is also discussed. The second important part of the
progress is the advancement of the synthesis and applications
of ferroelectric perovskite oxide in nanometer scale. Important
progress in this area, mainly from 1990s to now, is reviewed
thoroughly.
In the rst part of this review, we introduce important topics
in the perovskite-type ferroelectrics at nanometer scale,
including “Fundamentals of ferroelectricity” in Section 1.2,
“Barium titanate, strontium titanate and their solid solutions in
nanometer scale” in Section 1.3, “Size effects of ferroelectric
nanomaterials properties” in Section 1.4 and “Computation
and modeling works in perovskite-type ferroelectrics” in Section
1.5. The discussion of the fundamentals gives the readers a brief
overview of ferroelectric physics, which can further guide the
process design of the synthesis of ferroelectric perovskite oxides
in both macroscopic and nanometer scales. Perovskite oxides
are the major topic in ferroelectricity. Although extensive
research works have been done on other types of ferroelectric
materials, for example polymeric/organic ferroelectrics, they are
not the major interest for this review. Readers can refer to other
studies in this eld.31–48
In the second part of this review, we present a detailed
discussion on the synthesis, fabrication, characterization and
applications of ferroelectric perovskite oxides. As a whole
account, this review summarizes the major progress in the eld
of ferroelectric perovskite-type oxides in nanometer scale and
provides guidance for further research in this area.

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1.2 Fundamentals of ferroelectricity in perovskite oxides
Ferroelectric materials exhibit a spontaneous dipole moment;
their orientations can be switched by the application of an
external electrical eld, i.e., the coercive eld. In a typical
ferroelectric perovskite oxide, a phase transition from a cubic
phase at a higher temperature to a tetragonal phase at a lower
temperature is usually observed. This transition point is called
the Curie temperature, Tc. Scheme 1 shows the lattice units of
barium titanate, one of the most widely studied ferroelectric
perovskite oxides, in both cubic (paraelectric) and tetragonal
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(ferroelectric) phases. The cubic phase, Scheme 1(a), exhibits an
induced polarization, which returns to zero when the external
eld is removed; while the tetragonal phases retain a sponta-
neous polarization, the two variants, Scheme 1(b) and (c), have a
180
difference in direction due to the off-center position of the
titanium ion. Because of the distinctive physics of ferroelectric
perovskite oxides, they have been attracting extensive research
interest in the elds of high-K materials, electromechanical
transducers, and ferroelectric random access memories, or
FeRAM.9,49–52 The rst observation of ferroelectricity in perov-
skite oxides occurred in the 1940s.2 The perovskite oxides have
the chemical formula ABO3. In the case of BaTiO3, as shown in
Scheme 1(a), “A” atoms or barium are located at the corner
positions, “B” atom or titanium is located at the body center
position and oxygen atoms are located at the face-centered
position. With the application of the coercive eld, the “B” atom
moves off-center according to the direction of the external eld.
Because of the relatively small atom size and high charge of Ti4+,
Scheme 1 Lattice units of barium titanate in both cubic, paraelectric (a), and
tetragonal, ferroelectric (b and c), phases. The two polarization variants (b) and (c)
have 180
difference in polarization direction due to the off-center position of the
Ti4+. In (b) the polarization is down and in (c) it is up.
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the atom off-center effect can store a large amount of potential
energy. This is a microscopic view of a capacitor in a lattice.
According to electronic physics, the capacitance of the bulk
cubic barium titanate is given by
A
C ¼ 3r 30
d
where C is the capacitance; A is the area of the face of the
barium titanate cube, 3r is the relative static permittivity, or
dielectric constant, of barium titanate; 30 is the dielectric
constant of the air (30 z 8.854  1012 F m1); and d is the edge
length of the barium titanate cube. Therefore, barium titanate
usually has a very large dielectric constant.2,9,30
In addition to the high dielectric constant, phase transitions
in ferroelectric perovskite oxide materials are also interesting.
Using barium titanate and strontium titanate as examples, the
phase transitions are listed in Table 1.
Table 1 summarizes the cubic–tetragonal phase transitions
of perovskite oxides barium titanate and strontium titanate.26,53
The Curie temperatures for barium titanate and strontium
titanate are 130
C and 168
C, respectively. Since the
tetragonal phase is ferroelectric below the Curie temperature,
barium titanate is ferroelectric at room temperature, while
strontium titanate is paraelectric at room temperature.
Another interesting phenomenon of ferroelectricity in
perovskite oxides is the giant dielectric constant at its Curie
temperature. As early as 1940s, von Hippel discovered the giant
dielectric constant effect in barium titanate, strontium titanate,
75% BaTiO3-25% SrTiO3 and 71% BaTiO3–29% SrTiO3 at their
Curie temperatures. Furthermore, by tuning the ratio between
barium titanate and strontium titanate, the Curie temperature
can be changed to room temperature, which makes the material
a high-K material at room temperature.54–59 Su et al. recently
published a synthesis process for solid solutions of barium
titanate and strontium titanate with different Ba/Sr molar
ratios. The characteristics of this material will be further dis-
cussed in Section 1.3.
Besides barium titanate and strontium titanate, other
perovskite oxides include BaZrO3, PbTiO3, PbZrO3, Pb(ZrxTi1x)
O3, LiNbO3, CaTiO3, etc.54,60–71
Table 1 Phase transitions in ferroelectric barium titanate and strontium
titanate26,53
Ferroelectricity Ferroelectric Paraelectric
Phase transformation
BaTiO3 <130
C (Curie temperature) 130–1432
C
SrTiO3 <168
C (Curie temperature) >168
C
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1.3 Barium titanate, strontium titanate and their solid
solutions in nanometer scale
Barium titanate (BaTiO3, BTO) and strontium titanate (SrTiO3,
STO) are among the most widely studied ferroelectric perovskite
oxides. The Tc of BTO is 400 K; and 105 K for STO. Thus, at
room temperature, BTO is ferroelectric and STO is paraelectric.
Barium–strontium titanate (BaxSr1xTiO3, BST) refers to a series
of solid solutions of BTO and STO. The ferroelectric properties
of BSTs can be optimized by adjusting the molar ratio, x. With
the current rapid advances in nanoscience, BTO, STO and BST
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crystals in nanometer scale with high quality and low defects
are highly desirable systems for fundamental as well as tech-
nological investigations.
In the past, most synthetic procedures for the preparation
of perovskite crystals included high temperature (1000
C)
sintering followed by annealing. Recently, extensive efforts
have been focused on the establishment of moderate reaction
conditions, especially lowering the synthesis temperature for
high-quality nanocrystals.21,28,61,72–81 Various methods for the
synthesis of perovskite nanocrystals have been developed,
including co-precipitation,22,82 sintering of organometallic
precursors,83 hydrothermal and solvothermal
methods,14,61,76,77,84,85 sol–gel process,72,86 and procedures
mediated by molten composite-hydroxide, etc.81 Recent
interest in nanoscience led to extensive efforts focusing on
obtaining BTO and STO nanocrystals based on the under-
standing gained from bulk crystals.49,87 The synthesis of BST
nanocrystals with systematic composition variation has not
been reported.
There are special issues in preparing ferroelectric nano-
crystals due to their very high surface to volume ratio. The
impurity ions on the surface of the nanostructures may form a
depolarization eld preventing the growth of the tetragonal
phase.28,49,88,89 The tetragonal polymorph was usually obtained
upon cooling the products to room temperature aer sintering at
1000
C. Although approaches with the trend towards low-
temperature synthesis of perovskite nanocrystals have been
developed, most of the synthetic temperatures were higher than
the Curie temperature (130
C) of BTO.61,77,81 One recent room
temperature synthesis of ferroelectric nanocrystals with diame-
ters from 6 to 12 nm using a bolaamphiphilic peptide ring as the
template was discussed.28 The peptide ring at the equatorial
position prevented the approach of impurity ions to the particle
surface from the lateral directions providing an asymmetric
environment conducive for the growth of the tetragonal poly-
morph. A fungus-mediated biological route toward the synthesis
of tetragonal barium titanate nanoparticles of sub-10 nm
dimensions under ambient conditions was also reported.79 Most
recently, a bio-inspired process has been applied for the room-
temperature synthesis of BTO from a bimetallic alkoxide
precursor.80 Nonaqueous approaches have also been developed
to synthesize nanocrystalline BTO, STO, and Ba0.5Sr0.5TiO3
mixed-metal oxide using elemental alkaline earth metals as
starting materials.61,77 The resulting BTO and BST nanocrystals
were found to be cubic.58 Based on a reaction between a metallic
salt and a metallic oxide, nanometer-sized BTO and
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Ba0.5Sr0.5TiO3 have also been synthesized in a solution of
composite-hydroxide eutectic at 200
C.81 One reverse micelle
route performed on a bench top at 80
C gives high-quality
nanocrystalline BSTs with variable compositions leading directly
to nanocrystals with giant dielectric constant.30 This nding is
signicant in providing, through a readily accessible synthesis
route, novel particles with sizes down to the 10 nm level for
nanoelectronics.
BTO/STO articial superlattices in thin lms have been
fabricated by pulsed laser deposition (PLD) on many
substrates.90 The PLD method can be used to fabricate BTO/STO
superlattices with stacking periodicity varying from 1 : 1 to
125 : 125. In X-ray diffraction (XRD), the BTO/STO superlattices
showed both BTO and STO characteristic peaks, while BST solid
solutions from the solvothermal method77 and our present
system only showed characteristic peaks for the BST nano-
crystals, indicating the atomically mixed nature of the Ba2+ and
Sr2+ sites.
1.4 Size effects of ferroelectric nanomaterials properties
As we discussed previously, perovskite oxides, barium titanate,
strontium titanate and their solid solutions, are of critical
importance for both fundamental and technical studies in the
subject of high-K materials. Extensive efforts have been made to
develop efficient methods for the synthesis of high-quality
ferroelectric perovskite nanocrystals (Section 2). These devel-
opments were primarily based on early works in the late 1940s
and early 1950s. The landmark reports include a treatise in 1946
by von Hippel and coworkers illustrating the origin of a
remarkable dielectric behavior and higher values of polariza-
tion than those of titanium dioxide observed in bulk titanates.2
The then “new” mechanism, “In the ionic crystal lattices dipole
moments are created by the displacing of ions from their equilib-
rium positions”, is now widely accepted as the origin of the high
values of dielectric constant. In 1951, Matthias discussed, in his
review paper, the relationship between the ferroelectricity and
the phase transitions in perovskite type titanates.3 In barium
titanate, for example, a paraelectric cubic structure form is
stable above its Curie temperature, 130
C, whereas a tetragonal
ferroelectric structure form takes over at the temperature range
of 0 to 130
C. The tetragonal polymorph is decisively important
for the spontaneous polarization by a distortion of titanium
ions from the centrosymmetric to an asymmetric position
within the TiO6 octahedra.8–10,49,91 Although a wide variety of
synthetic methods have been reported for titanates, there are
two crucial issues with regard to the development of their
fabrication: (1) the size effect of titanates in the nanometer
scale; and (2) synthesis conditions, especially the synthesis
temperature.14,20–22,27,57,61,72–86,92–118
The rst crucial issue is the size effect of titanates in nano-
meter regime. High-quality titanate nanocrystals are required
for the next generation of electronics and semiconducting
industry. The paraelectric cubic barium titanate crystal lattice
belongs to the centrosymmetric Pm3m space group, whereas the
ferroelectric tetragonal one belongs to the non-centrosymmetric
P4mm space group (lattice units c > a: c ¼ 4.036 Å; a ¼ 3.992 Å).72
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The ratio of “c/a” is dened as “tetragonality”. For bulk ferro-
electric barium titanate crystals, the tetragonality is usually
measured by techniques including X-ray diffraction (XRD),
neutron powder diffraction or Raman spectroscopy.58,119,120 For
example, in XRD, the peaks for lattice indices 200 and 002 are
usually distinct with observable splitting. With the decrease in
the particle size, a diminishing of ferroelectricity or tetragon-
ality has been observed in previously synthesized barium tita-
nate nanoparticles. As shown in Fig. 1, the critical size for the
disappearance of ferroelectricity was around 30 nm. The origin
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for the size effect is still not established, although two main
reasons were suggested: (1) it is the intrinsic nature of the
nanoparticles smaller than the critical size; (2) the impurity
surface ions form a local depolarization eld preventing the
formation of the tetragonal phase. Recently, we observed the
ferroelectric tetragonal phase in barium titanate nanocrystals
with particle size as small as 6 nm.28 This nding provided the
evidence that the diminishing of ferroelectricity in previous
reported studies may not be inherent to the system. Special
techniques, including ultraviolet Raman spectroscopy and the
atomic pair distribution function (PDF) technique, have been
Fig. 1 Size effects in barium titanate nanoparticles. The change of particle size of
barium titanate with its lattice axial ratio (a) and with lattice constant (b).26
Reproduced with permission from American Institute of Physics, copyright ª
American Institute of Physics.
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developed; they could be very useful as methods to further
substantiate the ferroelectricity observed in our barium titanate
nanocrystals.120
Additional important issues include the synthesis tempera-
ture. Lower synthesis temperature is preferred and the nal
titanate product should be the tetragonal polymorph. For
barium titanate, the tetragonal polymorph is thermodynami-
cally stable at room temperature. However, the synthesis
approaches at low temperature usually result in the formation
of the cubic polymorph. A sintering process, at around 1000
C,
followed by annealing through the Curie temperature, was
requisite for obtaining the tetragonal polymorph. The high-
temperature sintering process not only is energy-consuming but
results in agglomerations, which deteriorate the size distribu-
tion of the nal products. For crystals in nanometer scale, the
agglomeration is a more serious concern with regard to the
particle distribution and size level. Previously, various synthesis
methods have been developed, including co-precipitation,22,82
sintering of coordinate precursors,83 hydrothermal and sol-
vothermal methods,14,61,76,77,84,85 sol–gel process,72,86 liquid–
solid–solution (LSS) phase transfer,117 seed-mediated growth in
aqueous system,121 and procedures mediated by molten
composite-hydroxide.81 In co-precipitation, sintering of coordi-
nate precursors and sol–gel processes using titanium alkoxides
and barium salts, organic capping reagents were usually
employed to coordinate the metal ion or stabilize the particles
against agglomeration. Hydrothermal and solvothermal
methods involved high-pressure approaches by using titanium
alkoxide or oxide gels as the precursor and barium salt or
hydroxide as the barium source.72 The procedures mediated by
molten composite-hydroxide avoided the use of organic capping
reagents and were based on a reaction between a metallic salt
and a metallic oxide in a solution of molten mixed potassium
hydroxide and sodium hydroxide eutectic at 200
C.81
In addition to the efforts of synthesizing titanates by using
traditional chemical methods, biomimetic methods provided
an environmentally benign alternative.28,79,80 In 2006, we repor-
ted our “Room temperature synthesis of ferroelectric barium
titanate nanoparticles using peptide nanorings as templates”.
Later in that year, a vapor-diffusion sol–gel route,80 and a
fungus-mediated approach,79 were also reported as room-
temperature syntheses of barium titanate under biomimetic or
bioinspired conditions.
1.5 Computational modeling in perovskite-type
ferroelectrics
First-principles computational methods have been extensively
used in the study of ferroelectric perovskite-type oxides.122,123
These has greatly expanded our theoretical understanding of
this important class of materials. Major focuses of the modeling
work have been on their lattice dynamics, phase transitions,
dielectric and piezoelectric properties, and the study of defects
and surfaces. Since the 1990s, when nanoscience emerged,
attention has been increasingly focused on the crystal structure,
phase transition and size effect on ferroelectricity of perovskite-
type oxides.124 Those modeling studies on materials at
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nanometer scale usually use several experimental techniques,
for example X-ray diffraction, and a calculation model, for
example Rietveld or pair distribution function (PDF), to simu-
late the experimental result.58,124
Important studies include a paper from Fu and Bellaiche.87
In this paper, the authors investigated, from rst principles, the
ferroelectric properties of BaTiO3 colloidal nanoparticles—and,
in particular, to answer whether there is ferroelectricity in
ferroelectric nanoparticles and how these particles respond to
applied electric elds.87 In addition, they also developed a rst-
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principles derived effective-Hamiltonian approach coupled with
Monte Carlo simulations. The effective Hamiltonians of
previous works, which are derived from rst principles and
possess a comparable accuracy, have been successfully applied
to many ferroelectric materials, including simple BaTiO3,
PbTiO3, and KNbO3 systems, and complex Pb(Zr,Ti)O3 and
Pb(Sc,Nb)O3 solid solutions. Based on the calculations, it was
found that (i) large ferroelectric off-center displacements exist
in very small (<5 nm) dots. This result solves a long-standing
puzzling question in experiments, namely, whether there exists
ferroelectricity in colloidal ferroelectric dots under zero eld.
This discovery also opens a possibility of tremendous increase
in ferroelectric-memory density. (ii) Ferroelectric displacements
in dots exhibit an unusual and hitherto unknown vortex
pattern. This pattern is found to cause rather peculiar eld-
induced polarization responses. (iii) The ferroelectric instability
in dots is found to be robust against the organic capping
materials. (iv) The poling eld is predicted to decrease drasti-
cally with increasing size, which is important for practical
controls of FE nanostructures by use of external electric elds.
(v) The polarization responses of FE dots at stage II are found to
be strongly nonlinear, while the electromechanical responses in
dots are found to be remarkably smaller than those in the
bulk.87
The example of pioneer modeling works opened a door and
provided theoretical endorsement for chemists to synthesize
ferroelectric perovskite oxides in nanoscale. Accordingly, many
studies have reported successful syntheses of ferroelectric
nanomaterials since 2006.28,79
The combination of experimental techniques and modeling
was used for the crystal structure and phase transition (para-
electric–ferroelectric) studies.58,124 In Smith's paper, it was
found that BaTiO3 nanoparticles underwent a cubic-to-tetrag-
onal phase transition over a wide temperature range, in contrast
to the sharp transition found in the bulk material. The XRD data
show that the tetragonal metric was reduced from the bulk
value with decreasing size, but particles as small as 26 nm
remain in the tetragonal phase until near the bulk transition
temperature. By using a combination of Rietveld and PDF
analysis of synchrotron X-ray diffraction data, they established a
trend of increasing distortion in Ba–Ti distances and titanium
off-centering with decreasing particle size. It was concluded
that although the smaller particles have a greater distortion, a
loss of coherence relative to the bulk material is responsible for
decreased c/a values. These results signicantly contrast with
the accepted wisdom that BaTiO3 becomes less distorted for
smaller particle sizes.
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In Petkov's paper, the atomic arrangement in nanocrystal-
line BaxSr1xTiO3 (x ¼ 1, 0.5, 0) was studied by synchrotron
radiation scattering experiments and Rietveld and atomic PDF
techniques. The materials were found to possess an atomic
arrangement well dened over 2–2.5 nm distances and resem-
bling the one occurring in the crystalline perovskites. Although
the structural coherence length in the nanostructured materials
is greatly reduced, their structure still may be described in
terms of a repetitive unit cell containing only a few atoms.
SrTiO3 and Ba0.5Sr0.5TiO3 possessed atomic arrangements that
were cubic type at both short and longer range interatomic
distances. The local symmetry with nanocrystalline BaTiO3 was
tetragonal but the slight tetragonal distortions seemed to
average out and the structure of the material was better
described in terms of a cubic-like ordering at longer range
distances. That is presumably the reason nanocrystalline
BaTiO3, similarly to SrTiO3 and Ba0.5Sr0.5TiO3, does not show
spontaneous polarization at room temperature.58
Those pioneer modeling works are very important for both
fundamental ferroelectricity at nanometer scale and applica-
tions for electronic industry. Using the Multi-Layer Ceramic
Capacitor (MLCC) industry as an example, the particle size of
the MLCC materials is currently larger than 1 mm. The progress
in miniaturization of particle size depends on the smallest
particle size which can be the critical size of the ferroelectricity.
If the modeling work suggests the disappearance of ferroelec-
tricity in nanometer scale occurs at 40 nm, then that may be the
smallest size for further development of MLCCs.
2 Synthesis methods of ferroelectric
nanomaterials
Over the last decade, nanomaterials have received extensive
studies from the scientic and engineering viewpoints. They
exhibit different properties from those of bulk materials due to
their small size and large surface-to-volume ratios, and become
promising candidates for nanometer scale electronic, optical,
and mechanical devices. In the past, ceramic methodology was
usually utilized to produce perovskite oxides. The individual
metal oxide components or their precursors are stoichiometri-
cally mixed and heated together to form perovskite oxides. Since
it requires long diffusion distances and high temperatures, the
drawbacks of this method include poorly-controlled crystal
morphology, grain size, and grain shape of the nal material.
Therefore, various other synthetic methods for perovskite
ferroelectric nanomaterials have been developed.27,72,125 The
techniques include high-temperature sintering,75,83 sol–gel
technique,86,125,126 hydrothermal synthesis,14,73,76,84,85,121,127,128 sol-
vothermal synthesis,58,61,129 emulsion precipitation
130,131
method, reverse-microemulsion,131 electrospinning
method,118 supercritical uids,116 nanotubes/template,28,126,132
sol precipitation,127,133,134 pyrolysis and decomposition of bime-
tallic alkoxide precursors in the presence of coordinating
ligands,72,73 liquid–solid–solution (LSS) phase transfer,117
composite-hydroxide-mediated approach,81 bioinspired
79,135
synthesis methods, etc. In this review, we introduce the
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most common techniques for synthesis of perovskite nano-
materials, and discuss the differences between them.
2.1 Ceramic methods
The ceramic method is a high-temperature solid-state reaction.
In this method, to synthesize ABO3 perovskite materials, near-
stoichiometric ratios of A- and B-containing precursors are
sintered in a crucible at temperatures above the eutectic point
of the binary system. The nal products of this method are
subject to parameters such as particle size, morphology, purity,
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and chemical composition of the precursors since the param-
eters inuence the atomic diffusion during the solid state
reaction. The ceramic method cannot provide control over the
oxide grain size at the nanometer scale, with grains typically >1
mm, due to the absence of control of nucleation and growth. The
method is usually applied to the synthesis of perovskite BiFeO3
powders.136,137 Recently, Mao, et al.75 investigated the fabrication
of BaTiO3 nanomaterials in the presence of NaCl and a nonionic
surfactant. Using this method, BaTiO3 nanowires were obtained
having diameters from 50 to 80 nm and an aspect ratio larger
than 25, and also SrTiO3 nanocubes with a mean edge length of
80 nm.
2.2 Sol–gel/sol-precipitation synthesis
In this wet chemical method,138–141 precursors including metal
oxides and metal chlorides form a colloid system through
undergoing hydrolysis and polycondensation reactions, which
can be accelerated by an acid or base. Aer the reactions, the
colloid system consists of solid particles from 1 nm to 1 mm
dispersed in a solvent. When temperature increases, the parti-
cles precipitate and solvent evaporates. This method produces
variable grain sizes ranging from tens of nanometers to a few
microns. However, the grain size usually increases with sinter-
ing. The ideal synthetic pathway for these perovskite nano-
materials is to obtain the appropriate grain size, shape, and
crystallinity in the absence of an additional sintering step.
Modied sol–gel techniques were developed to synthesise
barium titanate nanoparticles.72,73 In these techniques, hydro-
lysis of metal alkoxide precursors was performed with the aid of
hydrogen peroxide at a temperature of 100
C and oleic acid was
applied as a passivating ligand. Crystalline nanoparticles
between 4 and 12 nm with the cubic phase were obtained by
adjusting experimental parameters, such as the BaTi(OR)6/oleic
acid ratio and the amount of peroxide solution. Spherical
BaTiO3 nanoparticles between 40 and 250 nm were obtained
through another modied sol–gel method.142 In this technique,
mixtures of titanyl acylate with barium acetate formed a gel in
the aqueous solution of acetic acid. Addition of potassium
hydroxide (KOH) further catalyzed the formation of BaTiO3.
Cubic crystalline structure of BaTiO3 powder with a particle size
of 40–250 nm formed at 45
C. The cubic crystalline structure of
barium titanate particles transformed to a tetragonal structure
upon heating to 1000
C for 1 hour. BaZrO3 nanoparticles with
sizes in the range of 30–40 nm were prepared by a sol–gel
process.143 Sol–gel methods were also utilized to synthesize
BiFeO3 nanomaterials.144–147
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The sol-precipitation process is similar to the sol–gel
process.127,133 The differences of strong alkaline conditions and
the control of the reaction temperature lead to formation of
crystalline perovskite nanomaterials at low temperature (Fig. 2).
However, in the sol–gel process, amorphous gel is further
crystallized at high temperature, e.g. 600–700
C. Without any
post-treatment, a one-step sol-precipitation method was applied
to produce cubic phase barium titanate nanoparticles with an
average diameter of 20 nm at 80
C for 5 hours.127 The BaTiO3
nanoparticles formed under strong alkaline conditions and
showed no aggregation. The same method was applied to
produce strontium titanate nanoparticles of 40–60 nm in size.133
2.3 Hydrothermal/solvothermal synthesis
The hydrothermal method,128 also called the autoclave method,
is similar to the solvothermal method. The only difference is
that the precursor solution for a hydrothermal method is
usually an aqueous medium, while that for a solvothermal
method is usually an organic medium. They are very popular
methods for synthesizing perovskite nanomaterials, because
the synergetic effects from solvent, temperature, and pressure
can offer stable nal products and prevent the formation of
unwanted compounds. Hydrothermal synthesis is also used to
prepare BaTiO3,115,148 BiFeO3,149,150 Ba1xSrxTiO3,151–153
SrTiO3, 115,154–156
PbTiO3, 157–162
and PbZr1xTixO3 nano-
materials.163–166 A composite system of SrTiO3/BiFeO3 was
synthesized via the hydrothermal synthesis method and inves-
tigated for photocatalytic activities.167 In this synthesis, BiFeO3
was rstly sonicated in ethanol and added to a HNO3/H2O/
CH3CH2OH solution containing TiO2 (sol) and aqueous Sr2+.
NaOH was then added to the solution to slowly precipitate Sr2+
at pH 13. The ltrate was heated to 240
C under hydrothermal
conditions to crystallize the SrTiO3. The particle sizes/
morphologies, optical absorption, and photocatalytic properties
were studied. The hydrothermal synthesis was reported to
fabricate lead titanate,158,159 and lead zirconate titanate (PZT)
powders with acicular morphology.157,159,163,168 The phase
composition and morphology of PZT particles in the method
were dependent on the tetramethylammonium hydroxide pen-
tahydrate (TMAH) concentration as shown in Fig. 3.168 At high
TMAH concentration, cubic-shaped PZT were formed mainly via
a dissolution–precipitation process. At lower TMAH concen-
tration, the acicular shape was preserved, resulting in the PZT
powder with acicular morphology.
Single crystalline tetragonal PZT nanorods with diameters of
150–175 nm and lengths of 1–1.6 mm were fabricated in the
addition of polymers such as polyvinyl alcohol (PVA) and poly-
acrylic acid (PAA).163 Hydrothermal reaction was conducted at
200
C for 12 hours.
Bao et al.153 reported the controlled synthesis of barium
titanate nanostructures using Na2Ti3O7 nanotubes and nano-
wires as synthetic precursors through the autoclave method. In
this method, they successfully synthesized BaTiO3 nano-
particles with various morphologies, including nanowires,
nanosheets, nanocubes, hexagonal nanoparticles, nanorods,
starsh-like nanostructures and sword-like nanostructures. It
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Fig. 2 Flow charts for SrTiO3 synthesis. (a) Sol–gel process, (b) sol-precipitation.133 Reprinted with permission from Springer, Copyright ª Springer.
was found that the shape of the various BaTiO3 products was
dependent on the concentration of Ba(OH)2, the temperature
and the nature of the precursors (Fig. 4).
The solvothermal method was reported to produce BaTiO3
and BaZrO3 as representatives of the perovskite family by Nie-
derberger et al.61 and Huang et al.169 Metallic barium and tita-
nium isopropoxide (Ti(OiPr)4) were used as precursors in
benzylic alcohol for this synthesis. Nanoparticles with average
size of 6 nm were produced through C–C coupling between
benzylic alcohols and alkoxide molecules at 200–220
C.
Nanowires of PZT were reported by a solvothermal technique.165
2.4 Microemulsion method
Reverse microemulsion methods were applied for the synthesis
of perovskite nanomaterials by several groups.131,170 The micro-
emulsion technique is of great attraction since the nanosized
Fig. 3 Proposed PZT particle formation mechanism under hydrothermal conditions using TMAH as an organic mineralizer.168 Reprinted with permission from Elsevier,
Copyright ª Elsevier.
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aqueous droplets act as nano-reactors for the synthesis of
nanoparticles. In the reverse microemulsion system, water phase
is a dispersed phase which is surrounded by the continuous
phase which is oil. The size of the nano-reactor (water phase) is
controlled by the ratio between water and the surfactant. The
chemical reaction occurs inside the water phase, which prevents
impurities from approaching. Su et al.131 developed a reverse
microemulsion system containing oil phase (cyclohexane),
nonionic surfactant (Triton X-100), co-surfactant (n-butanol) and
water phase, for the synthesis of BaTiO3, SrTiO3, and BaxSr1x-
TiO3. The size of the above nanomaterials was controlled via
controlling the ratio between water and the surfactant. The
highest dielectric constant value was reported when x equals 0.7.
Chen and Zhu170 also reported fabrication of nanorods of
Ba0.7Sr0.3TiO3 with a diameter of 60–100 nm and a length of 450–
1200 nm using a similar method at room temperature, which
show a single-crystalline tetragonal structure.170 In the synthesis
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Fig. 4 TEM and HRTEM images of BaTiO3 nanostructures prepared at different conditions from Na2Ti3O7 nanotubes: (a1) and (a2) show hexagonal BaTiO3 nano-
particles [in 0.2 M Ba(OH)2 at 80
C] and (a3) shows their corresponding crystalline structure; (b1) and (b2) show coral-like nanostructures of assembled nanorods [in 0.1
M Ba(OH)2 at 120
C] and (b3) shows their corresponding crystalline structure. TEM and HRTEM images of BaTiO3 nanostructures prepared from Na2Ti3O7 nanowires:
(c1) and (c2) show starfish-like BaTiO3 nanoparticles [in 0.2 M Ba(OH)2 at 80
C] and (c3) shows their crystalline structure; (d1) and (d2) show sword-like BaTiO3
nanostructures [in 0.1 M Ba(OH)2 at 120
C] and (d3) shows their corresponding crystalline structure.153 Reprinted with permission from ACS, Copyright ª ACS.

of bismuth ferrite nanoparticles via this technique,171 a micro-
emulsion system consisting of CTAB/water/isooctane/butanol
was designed. Microemulsion A contains bismuth nitrate and
ferric nitrate in the water phase, while microemulsion B contains
oxalic acid in the water phase. Microemulsions A and B were
mixed under stirring and precipitation occurred with time. Pure
bismuth ferrite nanoparticles were obtained aer calcination at
a temperature of 400
C.171
2.5 Template synthesis
The template method involves the use of nanoporous silicon,
polycarbonate, alumina, etc., as templates, which ll up with
the suitable polymeric precursors. The solution containing the
template is then heat treated to form the ferroelectric materials.
The template is then removed by etching. Synthesis of ferro-
electric nanostructures through templating can provide the
following advantages: (a) the structure of the nanoarray is
subject to the structure of the template, (b) the channels of the
template control the dimension of the materials, (c) pore walls
of template prevent the aggregation of the material and (d) a
large amount of nanowires or nanotubes can be produced. The
technique was applied for the fabrication of perovskite nano-
materials such as BaTiO3,126,132,172–174 Ba1xSrxTiO3,175
BiFeO3,176–180 PbTiO3,126,181–184 PbZrO3,185 and
PbZr1xTixO3. 132,172,186–195
In combination with the sol–gel

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technique (Fig. 5), multiferroic BiFeO3 nanotubes were
produced.78,126,176,187,196 Size, shape, and structural properties of
the nal products are simply controlled by the used templates.
In these methods, since capillary force in the templates is the
only driving force, the sol concentration is another important
parameter for a successful fabrication. If the concentration of
the sol is too high, it is very difficult to ll up the template,
especially a template with a small pore diameter. On the other
hand, if the concentration of the sol is too low, serious
shrinkage and cracking may occur during annealing.
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Polycarbonate membranes with pore sizes of 100 or 200 nm
were used as templates for electrophoretic growth193 of PZT
nanorods197 and lead titanate.182 The same method was also
applied to fabricate barium titanate nanotubes.126,132,198 Nanor-
ings of perovskite PZT with internal diameters down to 5 nm
and ring thicknesses of 5 to 10 nm were fabricated as nano-
porous alumina membranes made on silicon substrates as
template were immersed in a precursor solution.199 Block copoly-
mers were reported to self-assemble as template and nucleation
sites for growth of patterned BaTiO3 at nanometer scale.200
2.6 Electrospinning method
The electrospinning method was recently developed to fabricate
one-dimensional ferroelectric perovskite nanomaterials such as
nanowires or nanobers. In this approach, the formation of
electrospinning bers is dependent on the uniaxial stretching
(or elongation) of an electried jet derived from a highly viscous
polymer solution. The evaporation of solvent prompted the
formation of solid bers. In this method, as usual, polymer was
dissolved in organic solvent to obtain a homogenous solution.
Then, perovskite powder was added to the polymer solution to
form composites. The mixture was transferred to a syringe
which was mounted on an electrode. A high voltage between
syringe and collector was applied to electrify pendent droplets
of the solution from the syringe. As a result, the electried jet
experiences a stretching and whipping process, which led to the
formation of long and thin threads.201 The electrospinning
technique was applied to fabricate BaTiO3 nanobers in
combination with sol–gel methods.118,202–204 The nal diameter
of the bers was between 80 and 190 nm.118 Various nanowires
consisting of perovskite materials such as PbTiO3,205
Fig. 5 Multiferroic bismuth ferrite (BiFeO3) nanotubes have been synthesized
using a modified template methodology.176 Reprinted with permission from Royal
Society of Chemistry, copyright ª Royal Society of Chemistry.
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PbZr1xTixO3,168,206–210 Ba1xSrxTiO3,211 and BiFeO3,212 were
produced by the electrospinning technique and investigated for
different applications.
2.7 Bio-inspired synthesis methods
The above synthesis methods of perovskite ferroelectric nano-
materials require temperatures higher than 100
C and/or
extreme pH conditions. The ideal synthesis methods need to be
performed under benign and facile conditions, which include
room temperature, ambient pressure, and near-neutral pH. The
development of benign synthetic techniques is also important
from the viewpoint of green-chemistry principles, and potential
to scale up in energy-efficient ways. Therefore, several innova-
tive research works have been performed to realize the goal of
low temperature synthesis of these nanocrystals. Biomineraliz-
ing molecules extracted or adopted from biological systems
have been applied to catalyze and template the formation of
perovskite ferroelectric nanomaterials.213,214
Nuraje et al.28 have fabricated BaTiO3 nanocrystals at room
temperature using synthetic peptides to facilitate nucleation
and growth. In this method (Fig. 6), oligopeptide bolaamphi-
philic molecules were self-assembled as nano-rings, which
effectively avoid the inuence of effects of depolarization elds
and provide a pure environment for formation of ferroelectric
nanocrystals. The chelation between carboxylate groups and
Ti4+ ions was considered to be an important step for formation
of nanorings. The diameters of the resulting nanocrystals were
between 6 and 12 nm. XRD analysis of the nanomaterials
conrmed the existence of the tetragonal phase. Electrostatic-
force microscopy was utilized to demonstrate polarization
switching of nanoparticles.
Bansal et al.79 used a biological approach to synthesize
BaTiO3 nanocrystals by incubating Ba(O2CCH3)2 and K2TiF6
with a pathogenic fungus, Fusarium oxysporum, for 24 hours at
room temperature. The extracted fungal mycelia from F. oxy-
sporum acted as both a hydrolyzing agent and structure direct-
ing template in the precipitation of ferroelectric BaTiO3
nanoparticles. The hydrolytic enzymes in F. oxysporum per-
formed a crucial role in conversion of the TiF62 feedstock via
the hydrolysis of Ti–F bonds. This synthesis produced BaTiO3
nanocrystals with diameters between 4 and 5 nm.
In a different approach for biological synthesis of BaTiO3
ferroelectric nanocrystals, the phage-display method135 was
applied to identify the biomolecules with specic affinities for
crystalline BaTiO3 as shown in Table 2. The specic peptides
were used to synthesis ferroelectric BaTiO3 nanocrystals at
room temperature and near-neutral pH. The size of produced
ferroelectric BaTiO3 nanocrystals at ambient conditions was
50–100 nm. The formed BaTiO3 particles have ferroelectric
properties as they show polarization hysteresis in Fig. 7.135
Nuraje et al.215 used genetically modied-M13 (AEEE) virus as
template to grow perovskite nanowires of strontium titanate
and bismuth ferrite (Fig. 8). SrTiO3 and BiFeO3 nanowires were
successfully fabricated with templating on the viruses. SrTiO3
nanoparticles were around 5 nm in diameter and possessed
cubic phase structure. The same M13 viruses were also applied
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Fig. 6 (a) Illustration of the nanoring structure of the precursors that self-assemble with the peptide.28 Reprinted with permission from WILEY-VCH, Copyright ª
WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Table 2 Barium titanate peptides.135 Data reproduced with permission from spontaneous polarization properties. Especially, with
ACS, copyright ª American Chemical Society increasing demand for ultrafast portable electronic devices,
which have ultrahigh-density data storage and low power
Amino acid
Peptide sequence pIa

BT1 HQPANDPSWYTG 5.1

BT2 NTISGLRYAPHM 8.8
a
Isoelectric point calculated using pI/mass program at http://
ca.expasy.org.

to grow multiferroic bismuth ferrite nanowires. The resulting

virus-templated nanoparticles were between 10 and 30 nm in
diameter.

3 Fabrication of nanostructured
ferroelectric materials
Ferroelectric oxides have been widely studied for applications in Fig. 7 Polarization versus applied electric field.135 Reprinted with permission
non-volatile data storage devices due to their reversible from ACS, copyright ª American Chemical Society.

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Fig. 8 (a) Scheme for growth of strontium titanate nanowires. (b) TEM and HRTEM images of strontium titanate nanowires.215 Reprinted with permission from WILEY-
VCH, copyright ª WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
consumption, it is essential to develop ferroelectric capacitors
at nanometer scale. Therefore, the fabrication of ferroelectric
nanostructures is not only important to the development of
non-volatile data storage devices, but also enables us to
understand the fundamental physics of ferroelectrics at nano-
meter scale which include surface properties, strain effects from
substrates, and size reduction. A thin lm of perovskite ferro-
electric materials is usually fabricated via different deposition
techniques including pulsed laser deposition, solution deposi-
tion, etc. Pulsed laser deposition216 was applied to deposit
bismuth ferrite thin lms with 300 nm thickness on strontium
titanate [001] substrates with a 248 nm wavelength KrF Lambda-
Physik laser. BFO thin lms were fabricated by RF magnetron
sputtering deposition217 on vicinal STO (001) substrates.
Fabrication of ferroelectric nanostructures usually consists
of two methods: top-down approach and bottom-up approach.
In this section, the advantages and limitations of the top-down
and bottom-up approaches are discussed.
3.1 Top-down approaches218,219
The top-down approach involves the construction of small size
structures from large size structures through etching and
removal of parts. In this method, lithography usually is applied
to produce structures with assistance from energetic particles
such as photons, ions, or electron beams. Focused ion beam
(FIB) milling and electron beam (EB) direct writing (EBDW) are
popular techniques for fabrication of ferroelectric nano-
structures with controlled size and shape. During the
construction procedure of ferroelectric nanostructures, pre-
grown metal–organic precursor lms were annealed at high
temperature for crystallization aer FIB or EBDW were applied
to create certain structures. Furthermore, as shown in
Fig. 9,218–220 a pre-grown ferroelectric capacitor with the lm
stacking conguration of top electrode/ferroelectric/bottom
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electrode layers was prepared. For preparation of ferroelectric
lms in stacking conguration, lm deposition techniques
such as pulsed laser deposition (PLD) or metal–organic chem-
ical vapor deposition (MOCVD) techniques are applied to grow
an excellent quality of metal–organic lms. The surface of the
top electrode is covered with a thin protecting layer of platinum
which avoids the ion beam penetration. Then, desired shape
and feature size of ferroelectric nanostructures to the bottom
electrode are manufactured by ion-beam milling. The diameter
of the ion beam is 6 nm. Therefore, the ferroelectric nano-
structures with feature sizes smaller than 100 nm are easily
produced. FIB based nanofabrication provides advantages in
production of ferroelectric ultrahigh density non-volatile
memories without changes of the chemical composition of the
starting ferroelectric material. Ganpule et al.218 fabricated
ferroelectric Pb(Nb0.04Zr0.28Ti0.68)O3 and SrBi2Ta2O9(SBT)
capacitors with sizes ranging from 1 mm2 to 0.01 mm2.
In contrast to the FIB technique, the EBDW technique does
not require a mask for generation of ferroelectric nano-
structures. Aer a metal–organic precursor thin lm is depos-
ited on the top of the bottom electrode, the desired
congurations are generated by irradiation of the EB over the
sample surface with induced chemical reactions. The structures
are further established by dissolving the unexposed areas in a
specic solvent. The resulting metal–organic patterns are
annealed to ferroelectric oxide at high temperature. Alexe
et al.220,221 created patterns of ferroelectric SBT and Pb(Zr0.7Ti0.3)-
O3 (PZT) with a pattern density of ca. 1 Gbit cm2. Conventional
EB lithography was utilized to fabricate PZT nano-islands with
different feature sizes.222 The ferroelectric nano-islands with
feature sizes below 300 nm exhibited very high piezo-response.
Advantages of top-down approaches are to precisely position
and control the shape and size of nanostructured ferroelectrics.
However, drawbacks of the techniques are the time-consuming
and low-throughput character of these processes.
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the structure–property relationships of PTO nano-islands using

synchrotron X-ray diffraction (XRD) and piezoresponse force
microscopy (PFM) and found an abrupt increase of piezores-
ponse with decrease of the size of PTO. The phenomena were
explained by the reduced substrate clamping effect and the
reduced a-domain contribution. High-resolution transmission
electron microscopy (HRTEM) was applied to investigate the
effect of disorders at the interface between the ferroelectric
nano-islands and the underlying oxide substrate on the polar-
ization instability.229 The interfacial dislocation accounts for the
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low mobility of twin walls in lms and ferroelectric polarization

in nanometer scale ferroelectrics.230

3.3 Combination of both top-down and bottom-up

approaches231–240
Ferroelectric nanostructures were also constructed with
combination of both top-down and bottom-up approaches. In
detail, this novel method use advantages of both top-down and
bottom-up approaches to grow ferroelectric nanomaterials
selectively in predened locations. Fig. 11 shows that ferro-
electric materials have been grown selectively onto prepatterned
seeds.232,238 In this method, EB lithography was applied to create
Fig. 9 Two typical example of top-down approaches for nanostructured ferro- TiO2 patterns which have been widely employed as seed
electrics: (a) focus ion beam (FIB) milling,218 (b) EB direct writing (EBDW).220 patterns for growth of PTO because TiO2 dots trap the PbO
Reprinted with permission from American Institute of Physics, copyright ª
molecules. Either sputtering or CSD techniques were applied to
American Institute of Physics.
deposit ferroelectric materials onto TiO2 seed patterns. Selective
growth of ferroelectrics was done using a combination of a
mask and physical vapor deposition (PVD) by several
3.2 Bottom-up approaches223,224
Building blocks such as atoms, molecules, or nanoparticles are
self-assembled to form ferroelectric nanostructures. In
comparison to the top-down approach for nano-fabrications,
this approach possesses certain merits. Ferroelectric nano-
materials can be directly manipulated at the nanometer scale.
In addition, the formed nanostructures are made of single
crystalline ferroelectric nanomaterials and do not possess
lattice defects near the surface. Demerits of the bottom-up
nano-fabrication exist in control of size and shape as well as
precise positioning of ferroelectric nanomaterials since they
rely on either thermodynamically driven reorganization or self-
assembly processes.
To construct ferroelectric nanostructures, bottom-up
approaches have been explored extensively. Among them,
chemical solution deposition (CSD)225 and MOCVD226 are
popular techniques using the microstructural instability of thin
precursor lms at high temperatures, which drive to minimize
their interface energy between the lm and the substrate under
a certain lm thickness (Fig. 10). Both the size and shape of
the resulting ferroelectric nanostructures are controlled by the
initial lm thickness, the annealing temperature, and the
crystallographic orientations of the substrate. Fujisawa et al.227
used MOCVD to construct PTO nanostructures (thickness ¼ 1.7
nm, diameter ¼ 38 nm), which exhibited ferroelectric polari-
Fig. 10 Two typical examples of bottom-up approach: (a) chemical solution
zation switching behaviour. Chemical solution deposition deposition (CSD)225 and (b) metal–organic chemical vapor deposition (MOCVD).226
(CSD) was applied to create ferroelectric PTO nanostructures.228 Reprinted with permission from American Institute of Physics, copyright ª
The authors also investigated extensively the size effect and also American Institute of Physics.

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groups.233–237 This approach used metal membranes with hier-
archically organized arrays of nanotubes, hexagonally close-
packed arrays of microspheres, and oxide membranes perfo-
rated with nano-holes as stencil masks for the deposition of
ferroelectric materials. Block-copolymer micelles were
employed as templates for growth of PTO nano-grains arrays
with uniform diameter (z2 nm) and thickness (z7 nm) on a
single crystal substrate. Then, PTO precursors attached to the
cores of self-ordered arrays of micelles, and further converted to
ferroelectric PTO through an annealing process at high
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temperature. PTO nano-arrays with extremely small volume
(z2.6  103 nm3) demonstrated piezoresponse properties.240 In
this approach, the post-annealing process oen results in
undesired changes of shape or volume of ferroelectric
nanostructures.
Table 3 summarizes advantages and limitations of various
approaches for fabrication of nanostructured ferroelectrics of
nano-capacitor and nano-island types.219
4 Characterization of perovskite
ferroelectric nanomaterials
To date various approaches including X-ray diffraction and
imaging, optical characterization, scanning probe microscopy,
high-resolution electron microscopy and spectroscopy, have
been developed to probe both the macroscopic and microscopic
details of perovskite ferroelectric nanomaterials. In this review,
we want to introduce these techniques and provide general
information on them. Recently, transmission electron
Fig. 11 Selective growths of PbTiO3 nano-islands (a)238 and well-ordered large-
area arrays of ferroelectric La-substituted Bi4Ti3O12 (BLT) nanostructures prepared
by pulsed laser deposition using gold nanotube membranes as masks (b).241
Reprinted with permission from American Institute of Physics, copyright ª
American Institute of Physics.
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microscopy has been demonstrated to image the domain wall
structure at the atomic scale. However, the techniques applied
widely to detect actual functional properties of the domain walls
include scanning probe microscopy (SPM) (scanning tunneling
microscopy, atomic force microscopy, conducting AFM (c-AFM),
and the related piezoresponse force microscopy) techniques.
4.1 High-resolution electron microscopy and spectroscopy
The transmission electron microscopy technique is able to
probe the lattice distortion across the domain wall and measure
the continuous deviation of a set of planes with respect to the
undistorted lattice.242–247 At present, the most advanced tech-
niques permit atomic scale resolution at 0.5 Å through aberra-
tion-corrected imaging (Fig. 12). The reconstruction approach
excludes the effects of objective lens spherical aberrations.
Therefore, the projection of the atomic columns is the basis of
images to be directly inferred.248
4.2 Scanning probe microscopy
SPM have been become a revolutionary method in probing non-
destructive domain structures of ferroelectric thin lms and
testing the nanometer scale ferroelectric structures for the rst
time. It also provides new pathway in nanometer scale domain
patterning for potential application in FeRAM,249 and ferro-
electric lithography.250 The SPM technique provides informa-
tion in two different modes which are non-contact and contact
based on the property of interaction force, attracting or repel-
ling, between the SPM tip and a sample. In the non-contact
mode, the tip is lied around 10–100 nm from the surface and
scans. The interaction between tip and sample includes the
long range polarization and electrostatic forces. The change of
resonant frequency of the cantilever provides information.251
Therefore, this mode, called electrostatic force microscopy
(EFM), can be used to probe the electrostatic eld of the surface
polarization charges,252,253 and predominantly applied to
domain imaging in ferroelectric crystals or in thin lms with
micrometer-sized grains.254–263 The lateral resolution of this
technique in ambient environment is around 40 nm. The
approaches, including scanning surface potential microscopy
(SSPM) or Kelvin probe force microscopy (KPFM), are able to
obtain quantitative information,264–266 and provide important
information on the distribution of polarization and screening
charges and their evolution during phase transitions. KPFM is
to monitor the stability of the ferroelectric domains and control
surface electrochemical reactivity.267 Scanning capacitance
microscopy (SCM) is applied to image trapped charges via
measuring local tip–sample capacitance.268 SCM still has diffi-
culty in providing quantitative information since it requires
more accurate parameters. Weaknesses of non-contact mode
are that it is susceptible to screening effects, sensitive to
substrate surface conditions and low resolution.
Although the imaging approach of SPM in contact mode
provides a high lateral resolution (below 10 nm), and an effec-
tive control of nano-domains, the domain images are difficult to
interpret due to the existence of cross-talk between different
mechanisms in the domain contrast formation. This approach
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Table 3 Various approaches for fabrication of nanostructured ferroelectrics of nano-capacitor and nano-island types.219 Data reproduced with permission from WILEY-
VCH, copyright ª WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Approach Advantages Disadvantages Minimum size (nm) Type

Top-down FIB High resolution Surface damage 70 Island

Use of high quality lm Low throughput capacitor
Uniform size and array
EBDW High resolution Volume shrinkage 70 Island
Uniform size and array Shape change
No etching process Low throughput
EB-litho High resolution Surface damage 100 Island
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Uniform size and array Low throughput capacitor

Etching process
Bottom-up CSD Easy process Difficulty in uniform size, <10 Island
Easy to generate various array, and shape
size and to access to
extremely small size
MOCVD Easy process Difficulty in uniform size, <10 Island
Easy to generate various size and to array, and shape
access to extremely small size
PLD Easy process Difficulty in uniform size, <10 Island
Access to extremely small feature array and shape
Modied Registered depo Uniform size and array Lithoprocess 50 Island
bottom-up Low throughput
Mask-assisted Uniform size and array o Mask fabrication process 40 Island
depo n large area capacitor
Easy process
High crystallinity
Block copolymer Uniform size on large area Difficulty in uniform array and shape 20 Island
Easy process
Access to extremely small feature

utilizes a special resonator probe which can be operated in the

Fig. 12 Atomic scale TEM image of the PZT nanostructure.247 Reprinted with
permission from Nature Publishing Group, copyright ª Nature Publishing Group.
is classied into static and dynamic. Static approaches, such as
atomic force microscopy (AFM) and lateral (friction) force
microscopy (LFM), are restricted to image domain structures
consisting of antiparallel c-domains in ferroelectrics. Further-
more, the contact mode image of AFM is applied to observe
opposite 180
domains with detection of the static piezoelectric
sample deformation while an external DC bias is applied.269–272
Dynamic methods,273 including scanning non-linear dielec-
tric microscopy (SNDM) and piezoresponse force microscopy
(PFM), are used to observe the electrical and mechanical
response of the sample while an AC voltage applied between a
conductive probing tip and a sample. The SNDM method
microwave frequency range and map nanometer scale domains
for the local voltage-induced change in the sample capacitance
in the surface layer of about 10 nm thick.274 Piezoresponse force
microscopy (PFM) (Fig. 13)275,276 is one of the most popular
techniques for characterization of ferroelectrics at the nano-
meter scale, which is based on the piezoelectric deformation of
a ferroelectric sample in response to an external electric eld
(hence the term “piezoresponse”).251 This technique has high
spatial resolution, easy implementation, effective manipulation
and control of nano-domains and local spectroscopy capabil-
ities. However, there is still debate on whether this technique is
able to provide quantitative information.277–279 Deeper under-
standing of the principles of PFM was recommended in the
literature.273,279 Atomic force acoustic microscopy (AFAM) is
considered to be another dynamic contact SPM method, which
is based on the detection of the cantilever displacement due to
the mechanical excitation of the sample while an ultrasonic
transducer emits longitudinal waves into the sample.273,280,281
5 Applications of nanostructured
perovskite nanomaterials
Perovskite ferroelectric nanomaterials are of great attraction
and show potential applications in different elds including
solar energy conversion, storage memory, etc., since they have
remarkable properties such as ferroelectric, piezoelectric, and

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Fig. 13 (a) PFM amplitude and (b) PFM phase images of a BFO sample with 109
stripe domains, (c) simultaneously acquired c-AFM image of the same area showing
that each 109 domain wall is electrically conductive.276 Reprinted with permission from The American Physical Society, copyright ª The American Physical Society.
nonlinear optical properties.12,282,283 The most widely investi-
gated perovskite materials include BaTiO3, CaTiO3, PbTiO3,
PbZrTiO3, KaTaO3, and SrTiO3 along with suitable dopants and
multiferroic oxides, BiFeO3, with unique properties of both
ferromagnetism and ferroelectricity. The multiferroic materials
are BiFeO3, CoFeO3, BiMnO3, TbMnO3, TbMn2O5, YMnO3,
LuFeO4 and Ni3B7O13, etc. However, BiFeO3 (BFO) is the only
material which gives ferroelectricity and antiferromagnetism at
room temperature. One of the promising applications of ferro-
electric nanomaterials is a ferroelectric bypass capacitor for 2.3
GHz operation in mobile digital telephones. The product with 6
million chips per month won the Japan Electronic Industry
“Product of the Year” award in 1994.12 In this section, some
important applications of perovskite ferroelectric materials are
introduced. Particularly, this review covers the promising
applications of perovskite ferroelectric nanomaterials for the
rst time.
5.1 Ferroelectric storage memory
The ferroelectric random-access memories (FeRAM)284 are one
of the main applications of perovskite materials to replace
magnetic core memory, magnetic bubble memory systems, and
electrically erasable read-only memory for many applications.12
Especially, during World War II, the discovery of ferroelectric
barium titanate (BaTiO3) with robust structure and chemical
stability encouraged scientists to develop an electrically
switchable and two-state device since such devices were able to
encode the 1 and 0 states, which were essential for the Boolean
algebra of binary computer memories. The intrinsic non-
volatility (retention of memory when power is out) and radiation
hardness of ferroelectric RAMs provide a new pathway to
develop novel computer memories. Furthermore, the dynamic
random access memory (DRAM) is today's memory core in most
electronic systems. Due to leakage of charge, it needs to be
renewed thousands of times per second. This process requires
more power and therefore drains the battery. Also, it can not
store information while the power is off. For example, in
computers,284 the startup of the computer needs longer boot-up
times since its operating system must be copied from the hard
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drive. Non-volatile memories provide the solution for this issue.
One of the future options for storage memory is ferroelectric
RAM (FeRAM) which stores data in the polarization state on the
ferroelectric material. Development of ferroelectric RAMs could
result in signicant improvement in weights, space, power
supply requirements and speed. Ferroelectric memory was
exploited for the rst time in integration with silicon CMOS in
1987.29 The ferroelectric material for this memory was
PbZr0.5Ti0.5O3 (PZT). Starting from 1992, there have been
signicant developments in increase of the capacity and
reduction of the size of FRAM. The current capacity of FeRAM is
64 Mbytes and the length of the FeRAM is reduced to 0.13 mm in
the integrated CMOS transistor gate. For commercial products,
so far there have been the following FeRAM memories produced
by different companies; a Fujitsu 8-kbit FeRAM in every SONY
Playstation 2 consisting of PZT, 32-Mbit PZT FeRAM fabricated
at Samsung, and 4-Mbit strontium bismuth tantalate (SBT)
FRAMs at Matsushita.285 The tetragonal perovskite structure has
two polarization states as shown in Scheme 1. The Ti4+ ions
occupy the centers of the cubic structure of lead titanate
(PbTiO3); the Pb2+ ions are sited at the corners of the crystalline
units; and O2 ions are placed on each face of crystalline units.
However, the ferroelectric crystalline structure is stable at room
temperature and has a net dipole (spontaneous polarization, Ps)
of a few tens of microcoulombs per square centimeter, which is
produced primarily by the displacement up or down of the Ti4+
ions. The regions of up and down polarization in a crystal of
PbTiO3 are called “ferroelectric domains”. When a large electric
eld is applied to the specimen (order of a few kilovolts per
centimeter), all the domains are directed in the same direc-
tion.286 In memory applications, it is important to switch the
directions of polarization domains from up (+1) to down (0). As
usual, short voltage pulses are applied to write information in
such a memory. Each voltage pulse is half of the nominal
switching voltage, Vs (Vs ¼ ECd, where d is the lm thickness).
In the most current ferroelectric prototype memories,
ferroelectric lms have been widely applied. FeRAMs demon-
strated promising features. In more detail, their write and read
cycle times are in the sub-100 ns range and also they have low
power consumption. Table 4 shows a set of device parameters
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for ferroelectric memories during 1989.12 Ferroelectric oxides
used in FeRAM devices so far are of thin lm types as follows:
perovskite structures such as PbZrxTi 1xO3 (PZT) or BiFeO3;
bilayer structures such as SrBi2Ta2O9 (SBT), (BiLa)4Ti3O12 (BLT)
or Bi4Ti3O12 (BTO). To construct FeRAM in memory devices, a
few properties of the materials are considered.287 A high
remnant polarization value Pr is required since it shows the
sensing difference between the two states representing 0 and 1.
The coercive eld Ec is required to be small, which relies on the
operating voltage of the FeRAM. The crystallization temperature
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is also an important parameter to be considered. Table 5 lists
the most common materials in FeRAM devices. The lower
temperatures provide better incorporation of a ferroelectric
material into the device assembly. In addition, fatigue
describing the steady loss of remnant polarization is an
important criterion to evaluate constructed devices. The reason
for fatigue in FeRAM is that oxygen vacancies occur during
switching cycles.288 Another factor for polarization decay is
imprint, i.e. imperfections of the materials or interface, which is
usually caused by hydrogen and plasma processing in capacitor
structures.289 In FeRAM production, the goal is to overcome
fatigue problems and achieve 1013 cycles. Minimum ten year
retention of polarization at 85
C is required. Fig. 14 shows a 3D
FRAM cell with PZT.285 The higher the density of FeRAMs, the
more cells. To obtain high density FeRAM, the minimization of
cell size is required. The voltage also needs to be reduced as
scaling continues as we discussed previously. Therefore, the
stability of remnant polarization is a critical issue for future
application of FeRAM.286,290
Other alternative approaches for nonvolatile storage have
been developed on the basis of ferroelectric materials, which
include ferroelectric eld effect transistors (FeFETs), ferror-
esistive based storage devices, and scanning probe related
methods. For the description of these methods, we recommend
the following nice review articles12,29,282,283 to readers, as this area
is not in the scope of the present article.
Since the density of FeRAM nonvolatile-memory is increased
thousands-fold by reading and writing in nanoparticle-based
FeRAM, nanowires,74,287 nanotubes,132,291,292 and nano-
particles28,72,125 have been investigated for potential application
in storage memory. The 100 nm2 area of nonvolatile
Table 4 Optimum device parameters for ferroelectric memories12
Parameter Value
Minimum cell size 2 by 2 mm2
Read time 10 ns
Erase/rewrite time 10 ns
Operating temperatures 100
C to +300
C
Minimum access voltage 1.0 V
Activation eld 120 kV cm1
Breakdown voltage 40 V
Fatigue to 50% Q 1012 cycles
Retention 5 years (real time)
Radiation hardness 5 Mrad cm2 (X-rays)
1011 rad cm2 s1 (X-rays)
1014 cm2 (neutrons)
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Table 5 Properties of various ferroelectric materials.29 Data reproduced with
permission from American Institute of Physics, copyright ª American Institute of
Physics
Property PZT SBT BLT
Pr (mC cm2) 10–40 5–10 10–15
Ec (kV cm1) 50–100 30–75 30–75
Crystallization temperature 450–650 650–800 650–750
polarization domains is equivalent to a data storage density of
about 1 terabit cm2 in a real memory device. Urban et al.73
demonstrated polarization-switching in a nanowire-based
system. Individual BaTiO3 nanowires with a diameter of 10 nm
were studied for nanoscale ferroelectric switching properties by
ultrahigh vacuum electrostatic microscopy.74 Fig. 15 shows the
switching polarization directions with external eld and that
the polarization domains were written and reversed repeatedly
on these wires.
Nuraje et al.28 investigated the synthesis of ferroelectric
nanomaterials using peptide template methods at room
temperature and polarization response of the free nanoparticles
around 12 nm using electrostatic force microscopy. Fig. 16(a)
explains the work mechanism of electrostatic force microscopy
schematically. In their work, a Vwrite of +12 V between the
conductive AFM tip and the substrate containing free nano-
particles was applied rst. Then, aer the local electric polari-
zation of the nanoparticles on the conductive substrate was
written, subsequently the conductive tip with a lower voltage
(+2 V), Vprobe, was scanned to probe the polarization using EFM
by measuring the shi in the resonance frequency. In the
reading step, the conductive AFM tip was raised at a certain
height above the nanoparticles to image only the contribution
from the local electric polarization of the BaTiO3 nanoparticles.
The EFM image of those nanoparticles gave a brighter contrast
because of the repulsive electrostatic interaction between the
tip and the nanoparticles. The same nanoparticles on the
conductive substrate were applied by Vwrite of 12 V to reverse
the polarization direction. As shown in Fig. 16(d), the
EFM image of those nanoparticles scanned by a Vprobe of
2 V displayed a darker contrast due to the attractive
electrostatic interaction. In the control experiments, the tip with
Vprobe ¼ 2 V was applied to probe reverse EFM images and
conrmed that the probe voltage did not affect with the written
polarization.
5.2 Microsensors and microactuators
Ferroelectric lms as functional materials have been extensively
explored for various sensor and actuator applications. The
development of piezoelectric based microdevices started in the
1990s. The new area called microelectromechanical systems
(MEMS) emerged. During the late 1990s, with the mass
production of portable telephones, piezoelectric based thin
lms played vital roles in the miniaturization and better
performance of these devices. MEMS include devices or arrays
of devices which integrate electronics with other constituents
including sensors, transducers, and actuators. Integrated
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Fig. 14 Samsung 32 Mb ferroelectric random access memories.285 Reprinted with permission from John Wiley and Sons, copyright ª John Wiley and Sons.
Fig. 15 (a) Three-dimensional topographic image of a BaTiO3 nanowire. (b)–(f)
Successive EFM images showing that four distinct polarization domains can be
independently manipulated by an external electric field.74 Reprinted with
permission from American Chemical Society, copyright ª American Chemical
Society.
circuit (IC) batch processing techniques are applied for
construction of the devices. The merits of piezoelectric
devices293 include a high generated force and good actuating
range, a wide frequency range of operation, and low power
consumption. The well-studied ferroelectric materials are
Pb(Zr,Ti)O3 (PZT) and PbTiO3 for piezoelectric actuator and
transducer applications. The cantilevers and membranes are
prototype structures in these applications since they are sensi-
tive to residual stresses.294 The piezoelectric based microdevices
embrace ultrasonic micromotors,295,296 micropumps and
microvalves,297 accelerometers and gyroscopes,298 acoustic
sensors,299 sensing and actuating elements in atomic force
microscope (AFM) cantilevers,300 and ultrasonic transducers for
medical301 and sonar302 applications. PZT is applied in these
devices and is a suitable material due to the high piezoelectric
and electromechanical coupling coefficients of PZT. The pie-
zolms differ from piezoelectrics in the clamping of the lm by
the substrate. The clamping results in a reduction of the out-of-
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plane longitudinal coefficient of a lm sandwiched between two
electrodes and deposited on a substrate.
Piezoresponse force microscopy is to measure the piezores-
ponse of local environments of the materials. The out-of-plane
longitudinal coefficient is increased when the lateral clamping is
released by fabrication of piezoelements with lateral dimen-
sions of 100 nm or less (Fig. 17).222 The piezoelectric coefficient
varies with applied stress or eld and is signicant in thin lms
since the applied elds or forces are usually high. Besides, the
extrinsic response has to be considered, which is the combi-
nation of all nonlattice effects—domain wall movements, and
pinning by the substrate and by defects. Piezomicrodevices
include cantilever based devices, and membrane structures.
The piezoelectric microcantilevers are based on demonstrations
of single elements, such as PZT coated Si cantilevers for sensing
and actuation in AFM heads300 and the microsystems include
arrays of microactuators. LG group reported a cantilever array
with integrated heaters and piezoelectric sensors for micro-
cantilever-type data-storage systems303 (Fig. 18). This represents
a modication to the IBM Miliped concept which employs
resistive sensing. The piezoelectric version is faster and has
lower power consumption.
Membrane based devices are also based on single element
demonstrators, e.g., micromotors, to membrane arrays. They
have been mostly used in ultrasonic applications recently. The
integration with CMOS, silicon based microdevices, offers a
high precision and a better resolution, and an easy fabrication
of transducers. The greatest challenge in fabrication of large
membranes is to get uniform thickness using semiconductor on
insulator (SOI) wafers (Fig. 19). Yamashita et al.304 demonstrated
a ring array of micromachined diaphragms coated with PZT
possessing high directivity for a short distance presence sensor
in air. The achieved value for PZT lm membranes is 3% for
clamped membranes and 6% for suspended membranes
(Fig. 19) in contrast to the calculated value of 20%.
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Fig. 16 (a) Schematic representation of manipulating and probing the electric polarization of BaTiO3 nanoparticles with EFM. (b) Topological AFM image of barium
titanate nanoparticles; scale bar ¼ 30 nm. (c) EFM image of barium titanate nanoparticles with Vprobe ¼ +2 V after Vwrite ¼ +12 V was applied on the nanoparticles across
a conductive AFM tip and a gold substrate; scale bar ¼ 30 nm. (d) EFM image of barium titanate nanoparticles with Vprobe ¼ +2 V after Vwrite ¼ 12 V was applied on the
nanoparticles across a conductive AFM tip and a gold substrate; scale bar ¼ 30 nm.28 Reprinted with permission from WILEY-VCH, copyright ª WILEY-VCH Verlag GmbH
& Co. KGaA, Weinheim.

and CaTiO3)306 thin lms have been investigated for some time.
In the thin lm devices of these materials, especially BaxSr1x-
TiO3 (BST), high electric elds and reasonable tenability are
obtained at room temperature at low dc voltages. BaxSr1xTiO3
has become the ideal choice for industrial applications and the
most studied material at microwave frequencies. In addition,

Fig. 17 Amplitude of piezoresponse of PZT patterns with lateral size of 100–200

nm on SrTiO3 substrate.222 Reprinted with permission from American Institute of
Physics, copyright ª American Institute of Physics.

5.3 Ferroelectric varactors and devices

Although both ferroelectric and paraelectric phases of perov-
skite materials have been applied in tunable microwave Fig. 18 Partial image of the 100  100 thermopiezoelectric cantilever array.29
devices,305 the paraelectric phase is oen favored due to the Reprinted with permission from American Institute of Physics, copyright ª
absence of hysteresis. Therefore, paraelectric (SrTiO3, KTaO3, American Institute of Physics.

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the Curie temperature of the materials can be easily tuned by
simply varying the Ba composition. The ferroelectric devices
rely on parameters including the composition of the lm, the
strain, defects, electrode/ferroelectric interface chemistry,
fabrication method, design, etc. Ferroelectric varactors and
devices have parallel-plate or coplanar-plate designs as shown
in Fig. 20. The parallel-plate design provides lower tuning
voltages, while the coplanar-plate format offers relatively higher
tunability.
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5.4 Solar energy conversion
Perovskite materials have been actively explored for solar energy
conversion307–309 since they can have high conduction band gap
position, stability, and solar absorption band gap. Among the
perovskite materials for solar energy storage, the following
perovskite materials have been mostly investigated: PbTiO3,310
SrTiO3,311–313 KTaO3,314 NaTaO3,314 BaTiO3,307 CaTiO3,315
La2TiO5,316 BiFeO3167,179,317 etc. BiFeO3 was investigated for
production of oxygen under UV179 conditions. However, Luo and
Maggard167 reported that BiFeO3 nanoparticles coated with
SrTiO3 can produce H2 under visible light irradiation while pure
BiFeO3 failed to generate hydrogen evolution. In this system, a
small-bandgap metal oxide, BiFeO3, was utilized as a visible-
light sensitizer in a SrTiO3 photocatalytic material. Joshi et al.318
demonstrated the O2 production ability of BiFeO3 nanocubes
synthesized via microwave technique in the photocatalytic
reaction from an aqueous FeCl3 solution as shown in Fig. 21.
Recently Deng et al.317 reported hydrogen generation of BiFeO3
nanoparticles in 1 (M) KOH solution under simulated solar
light. However, the results on hydrogen generation of BiFeO3
are contradictory to a previous report.167
Among them, SrTiO3 and NaTiO3 show excellent hydrogen
production under UV-light irradiation.307,309 Since most perov-
skite materials primarily absorb UV light, their harvesting of
solar energy is not performed efficiently. In this articial
photosynthesis or water splitting, perovskite nanomaterials
absorb the light and generate hole–electron pairs. To reduce the
water, the electron–hole pair has to be separated and reach the
surface individually as shown in Fig. 22. The excited electron in
the conduction band is transported to the surface of the
perovskite material and reduces the water into hydrogen gas. At
the same time, the hole in the valence band of the perovskite
nanomaterials migrated to the surface and oxidizes water into
oxygen. As discussed in Fig. 22(B), the three steps are very
Fig. 19 Process flow for the fabrication of suspended membranes.29 Reprinted
with permission from American Institute of Physics, copyright ª American Insti-
tute of Physics.
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Fig. 20 Parallel-plate (a) and coplanar-plate (b) ferroelectric varactors.
important to efficiently split water under sunlight exposure.
They need to have the right band gap for visible light absorption
since UV light is only 4% of the whole sunlight spectrum.309 For
efficient charge separation, the small size and high crystallinity
of perovskite nanomaterials are important since the small size
provides higher diffusion length and electrons or holes easily
reach the surface for reaction. The highly crystalline structure
avoids electron trapping inside the particles. Kudo and co-
workers309,314 investigated the photocatalytic water splitting of
perovskite nanomaterials such as NaTaO3, and KTaO3 and
reported higher activities under UV irradiation.
Construction of active sites on the surface is also important.
To utilize the perovskite nanomaterials for water splitting, the
following two approaches are applied to design systems. (1)
Chemical doping of perovskite nanomaterials with either
metallic or non-metallic elements. This approach is to insert an
interband between the valence and conduction bands of the
perovskite nanomaterials with the valence band of doped
elements. For example, SrTiO3 doped with Sb/Cr,319 Ru, Rh and
Ir320 produced hydrogen under visible light irradiation. (2) Dye-
sensitized perovskite nanomaterials. This approach adopts the
concept of dye-sensitized solar cells. In this system, dyes in the
hybrid system are applied to absorb the visible light, then the
electrons in the excited state of the dye migrate to the conduc-
tion band gap of the metal oxides. The separated electrons are
further moved to the cocatalyst surface of the metal oxide where
water molecules are reduced as shown in Fig. 23(a). Photo-
catalytic water reduction of biotemplated SrTiO3 nanowires was
investigated using methanol as a hole scavenger and Pt nano-
particles as a co-catalyst. Under UV light irradiation, the
hydrogen evolution rate of SrTiO3 nanowires is ten times higher
than that of titania (Degussa, P-25), and commercial SrTiO3
nanopowders (Wako Pure Chemical Industries, Ltd.).215 The
improved performance of virus-templated SrTiO3 nanoparticles
is explained by the smaller particle size which enables electron–
hole pairs to reach the surface easily, and by the high crystal-
linity preventing charge recombination. Under visible light
irradiation, Eosin Y dye was used to sensitize SrTiO3 nanowires
loaded with Pt nanoparticles and diethanol amine to regenerate
the electron decient dye.
For overall water splitting under visible-light irradiation,
there are usually two strategies applied as follow. Fig. 24 shows
the z-scheme conguration, which does not require an external
circuit or wire to transport electrons. The redox mediator carries
the charges between two photocatalysts. Kudo and Miseki309
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Fig. 21 (a) Photocurrent density–potential curves of BiFeO3 nanocubes (i) and BiFeO3 bulk (ii) thin film electrodes under illumination. (b) Photocatalytic oxygen
evolution under visible light irradiation over BiFeO3 nanocubes. Reprinted with permission from American Institute of Physics, copyright ª American Institute of Physics.
made a signicant contribution to the development of a
z-scheme system consisting of chemically doped SrTiO3, and
tantalate based photocatalysts under solar light. Table 6
provides the overall water splitting performance of different
photocatalyts in z-scheme systems.308 The second case is the
dye-sensitized photoelectrochemical cell,321 which requires an
external circuit or wire to transport the electrons from one
electrode to the other. In most cases, dye is required to sensitize
the porous electrodes made of metal oxide nanoparticles. In
this system, it is very important to have a high conduction band
position which provides higher open circuit voltage. This indi-
cates that separated electrons are easily transported from the
photoelectrode to the counterelectrode and produce hydrogen.
In the photoelectrochemical cell system, perovskite nano-
materials such as strontium titanate are good candidates to be
investigated. For the water splitting applications of perovskite
nanomaterials, the readers are directed to some recent review
articles.307–309
5.5 Solar electricity
Perovskite nanomaterials are of great attraction for the photo-
voltaic community to investigate their potential as candidate
Fig. 22 Schematic illustration of water splitting principle (a) and main steps in electron–hole transport during water splitting (b).308 Reprinted with permission from
American Chemical Society, copyright ª American Chemical Society.
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materials for photovoltaic devices since they have not only
semiconducting, ferroelectric properties, but also availability of
controlled synthesis methods. With the appearance of global
issues in energy, photovoltaic study becomes a critical tech-
nique in solving energy issues. Dye-sensitized solar cells
(DSSCs) were developed by Grätzel.322 The development of
DSSCs shows promise due to low manufacturing costs and
considerably high energy-conversion efficiency. A number of
different metal oxide nanoparticles and their core–shells,
including perovskite nanomaterials, have been explored for
potential improvement of DSSC device performance. Briey, the
working principle of DSSCs is described as follows. When
sunlight directly enters the DSSC through the transparent
conductive oxide (TCO) top coat on the glass surface (working
electrode), the dye molecules attached to the surface of semi-
conductor nanoparticles absorb the light. The photons absor-
bed by the dye molecules create an excited state of the dye
molecules' electrons, where, in turn, these electrons can be
injected into the conduction band of the semiconductor
nanoparticles. The semiconductor nanoparticles transfer the
electrons to the TCO through the conduction band of metal
oxides and then to the circuit. At the same time, the dye
molecule quickly is regenerated by receiving one electron from
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Fig. 23 (a) Energy band diagram for hydrogen production of dye-sensitized SrTiO3 under visible light irradiation. (b) Hydrogen gas production by water-splitting
utilizing virus-templated SrTiO3 nanowires deposited with Pt nanoparticles under UV irradiation and visible light irradiation with dye sensitization.215 Reprinted with
permission from WILEY-VCH, copyright ª WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

have produced DSSCs with efficiencies greater than 10%.323 The

Fig. 24 z-Scheme based water splitting system under visible light irradiation.309
Reprinted with permission from Royal Society of Chemistry, copyright ª Royal
Society of Chemistry.
iodine in the electrolyte. Then, triiodide recovers through
accepting electrons from the counter electrode aer following
through the external circuit. Anatase TiO2 nanoparticles are
oen used as a photoelectrode semiconductor material and
theoretical maximum open circuit voltage (Voc) of the device can
be determined by the difference in energy between the Fermi
level of the photoelectrode material (TiO2) and the redox
potential of the electrolyte. Grätzel’s group324 investigated the
performance of a DSSC using strontium titanate nanocrystals as
photoelectrode. In comparison with titania semiconductors, the
perovskite strontium titanate (SrTiO3) has similarities in
structure and can be considered as a highly doped TiO2 struc-
ture. However, strontium titanate has a higher atband poten-
tial and is expected to have a higher Voc for a SrTiO3-based DSSC
than for an anatase titania DSSC. At AM1.5, open circuit volt-
ages of a SrTiO3-based DSSC were roughly 100 mV higher than
those produced using nanocrystalline titanium dioxide
(anatase) as expected. However, photocurrents of SrTiO3 cells
were roughly one third of TiO2 (anatase)-based cells. The low
photocurrents are explained by the low dye loading and possibly
suboptimal dye–oxide interactions in the SrTiO3 system. Jose
et al.325 also discussed the poor performance of SrTiO3-based
DSSCs and explained it as being due to the specic surface
structure of SrTiO3. The energetically favored surface of SrTiO3

Table 6 z-Schematic photocatalytic system for water splitting to hydrogen and oxygen under visible-light irradiation.308 Data reproduced with permission from Royal
Society of Chemistry, copyright ª Royal Society of Chemistry

Activity
(mmol h1 g1)

H2 photocatalyst O2 photocatalyst Mediator Light source Incident light H2 O2 QY

Pt/TaON (0.2 g) Pt/WO3 (0.2 g) IO3/I 300 W Xe >420 nm 120 60 0.4 (420 nm)
Pt/CaTaO2N (0.1 g) Pt/WO3 (0.1 g) IO3/I 300 W Xe >420 nm 43 21
Pt/BaTaO2N (0.1 g) Pt/WO3 (0.1 g) IO3/I 300 W Xe >420 nm 67 33 0.1 (420–440 nm)
Pt./SrTiO3:Cr/Ta (0.2 g) Pt/WO3 (0.325 g) IO3/I 300 W Xe >420 nm 80 24.6 1 (420 nm)
Pt/ZrO2–TaON (0.025 g) Pt/WO3 (0.05 g) IO3/I 300 W Xe >420 nm 1040 266 6.3 (420.5 nm)
Pt/TaON (0.05 g) RuO2/TaON (0.05 g) IO3/I 300 W Xe >420 nm 60 30 0–0.2
Ru/SrTiO3:Rh (0.05 g) BiVO4 (0.05 g) Fe3+/Fe2+ 300 W Xe >420 nm 378 179 0.3 (420 nm)
Pt/SrTiO3:Rh (0.02 g) Bi2MoO6 (0.02 g) Fe3+/Fe2+ 300 W Xe >420 nm 950 445 0.2 (440 nm)
Pt/SrTiO3:Rh (0.02 g) WO3 (0.02 g) Fe3+/Fe2+ 300 W Xe >420 nm 390 200 0.2 (440 nm)
Pt/SrTiO3:Rh (0.02 g) BiVO4 (0.02 g) Fe3+/Fe2+ 300 W Xe >420 nm 750 360 0.3 (440 nm)
Pt/ZrO2–TaON (0.05 g) Ir/TiO2/Ta3N5 (0.05 g) IO3/I 300 W Xe >400 nm 45 22
Coumarin/Pt/H4Nb6O17 (0.05 g) IrO2–Pt/WO3 (0.1 g) IO3/I 300 W Xe >400 nm 48.3 12.1 <0.1 (500 nm)
Ru/SrTiO3:Rh BiVO4 300 W Xe >400 nm 400 190 1.7 (420 nm)

8772 | Nanoscale, 2013, 5, 8752–8780 This journal is ª The Royal Society of Chemistry 2013

Review
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Fig. 25 (a) Schematic diagram for a liquid junction solar cell made of BFO nanoparticles. (b) Photovoltaic properties of a solar cell using virus-templated BFO
nanoparticles as the photoanode.215 Reprinted with permission from WILEY-VCH, copyright ª WILEY-VCH.
is the (001) face which can end with two possible groups, SrO or
TiO2. Since the SrO surface is more basic, the surface poorly
adsorbs the negatively charged carboxylate group of the sensi-
tizer. In addition to SrTiO3, perovskite BiFeO3 (BFO) recently is
also receiving more attention due to its ferroelectric properties
and visible light band gaps.326,327 Bulk photocurrent induced by
high-energy light illumination without external bias (a photo-
voltaic (PV) effect) has been studied in ferroelectrics.328
Furthermore, under exposure of a ferroelectric material to
ultraviolet light, a high photovoltage was observed in the
direction of the electric polarization in an open circuit. Ferro-
electric materials show different PV effect distinctly from the
typical PV effect in semiconductor p–n junctions.326 There has
been much research conducted on Pb-based ferroelectric
oxides.329,330 However, they did not show any signicant photo-
current,328,330 on the order of a few nanoamperes per cm2, which
is attributed to mainly poor bulk conduction of the ferroelectric
materials. The PV effect of ferroelectrics is still under debate
including the excitation of electrons from asymmetric impurity
potentials,326 interfacial effects for polarization-dependent band
bending,328 etc. To enhance power conversion efficiency in solar
energy applications, small-optical-gap ferroelectrics with good
carrier transport properties and large absorption of visible light
extending into the red range might be a promising route.
Among the perovskite materials, BiFeO3 are receiving great
attention due to a direct bandgap corresponding to the wave-
length of visible light, and ferroelectricity. The photovoltaic
properties of single crystal and thin lm BiFeO3 have been
studied by two groups.217,326,327 They proposed a different
mechanism for photovoltaic charge separation in BiFeO3 thin
lms which is the major challenge in both photovoltaic and
water splitting, in comparison with conventional solid-state
photovoltaics where electron–hole pairs were separated by the
electric eld in the depletion region, and produced higher
voltages than the bandgap. The charge separation occurs at
ferroelectric domain walls in multiferroic BiFeO3. Also, the
photo-properties of these materials were controlled by control-
ling the domain structure in such BiFeO3 lms. Nuraje et al.215
reported BiFeO3 nanoparticle based solid–liquid junction
photovoltaic devices for the rst time. Virus-templated BiFeO3
nanoparticles were utilized to fabricate liquid junction solar
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View Article Online
Nanoscale
cells. Under illumination with an AM1.5 solar simulator at 100
mW cm2, the device achieved an open circuit voltage of 0.578 V
and a short circuit current density of 0.735 mA cm2 (Fig. 25)
and solar power conversion efficiency of 0.17%.
6 Conclusion and outlook
In the introduction part of this account we described the
fundamentals of ferroelectric nanomaterials, including size
effects of ferroelectric nanomaterials properties and computa-
tion and modeling theory in perovskite-type ferroelectrics. With
guidance of development of modeling theory, various synthesis
methods for perovskite ferroelectric nanomaterials were intro-
duced for the realization of the synthesis of ferroelectric
nanomaterials at low temperature. The different assembly
approaches were discussed for the fabrication of devices of
ferroelectric nanomaterials. The recent applications of perov-
skite ferroelectric nanomaterials in storage memory and solar
energy conversion were introduced. Therefore, this review will
be a good tutorial material for non-expert readers for under-
standing these topics. Also it provides important updates to
experts in these research areas. We are optimistic to see the
deeper understanding of the fundamentals of ferroelectric
nanomaterials with the development of advanced technology,
and believe that ferroelectric nanomaterials have important
applications not only in the area of nanoelectronics, but also in
energy elds including solar energy, fuel cells, and energy
storage.
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