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Local characterization of nanostructured high sensitivity piezoelectric

BiScO3-PbTiO3 ceramics by piezoresponse force microscopy

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DOI: 10.1063/1.4896731

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 JOURNAL OF APPLIED PHYSICS 116, 124108 (2014)

Local characterization of nanostructured high sensitivity piezoelectric

BiScO3-PbTiO3 ceramics by piezoresponse force microscopy
Norberto Salazar,1,a) Miguel Alguero
,2 Harvey Amorın,2 Alicia Castro,2 Adriana Gil,1
s Ricote2
and Jesu
1
Nanotec Electr onica S.L, Tres Cantos, 28760 Madrid, Spain
2
Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, 28049 Madrid, Spain
(Received 5 July 2014; accepted 17 September 2014; published online 26 September 2014)
Piezoresponse force microscopy has been used for the local characterization of high sensitivity
piezoelectric BiScO3-PbTiO3 ceramics with compositions close to the morphotropic phase
boundary, with decreasing grain sizes down to 28 nm. The use of this high resolution technique has
allowed not only the analysis of the evolution of the ferroelectric domain configurations, with the
disappearance of ferroelastic domains at the nanoscale, but also to establish the existence of
correlations among the polarization of adjacent single-domain grains and the formation of inversion
superdomains. The effect of the grain size reduction on the piezoelectric coefficients was also stud-
ied. Finally, piezoelectric loops have been obtained on the smallest grains, and some distinctive
features, such as an atypical clockwise hysteresis is discussed and related to high resistivity grain
boundaries. VC 2014 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4896731]

I. INTRODUCTION Grain size effects have been studied in ferroelectric

ceramics of the simple perovskite BaTiO3 down to a size of
The current miniaturization trends in ceramic technolo-
20 nm.10,11 Large attention has also be drawn to nanostruc-
gies for microelectronics demand a drastic reduction of
tured ceramics of several high sensitivity piezoelectric sys-
grain sizes down to nanoscale to keep the reliability of these
tems, like Pb(Mg1/3Nb2/3)O3-PbTiO3 and Pb(Zn1/3Nb2/3)O3-
polycrystals integrated into ever smaller devices.1 The fea-
PbTiO3 that also show MPBs and size effects studies have
sibility of these miniaturized devices depends on how func-
been reported for grain sizes down to 15 nm.12,13 However,
tional properties behave with the grain size reduction to the
these are relaxor-based solid solutions and the main size
nanoscale. An understanding of the mechanisms that rule
effect is a slowing down of the kinetics of the ferroelectric to
these size effects is, therefore, essential. In the case of fer-
relaxor transition,14 until the high temperature relaxor state
roelectrics, the studies of nanostructured materials have
stabilizes for grains with sizes around 10 nm.15,16 For a sys-
become highly topical,2 and of large interest for the applica-
tem without any relaxor states as BiScO3-PbTiO3 (BSPT),
tions involving high sensitivity piezoelectric ceramics or
the study of nanostructured ceramics down to 80 nm grain
thin films as transducer elements of microelectromechanical
size show that functional properties are maintained,17 in
systems.3
agreement with the observation that nanocrystals of 15 nm
The most studied piezoelectric materials for these appli-
still keep the ferroelectric monoclinic Cm perovskite distor-
cations are ferroelectrics that display a transition region in
tion.18 It must be noted that not only crystal size is relevant,
their phase diagrams, known as morphotropic phase bound-
but also the nature of the grain boundaries, which become
ary (MPB), where the crystal structure changes with compo-
increasingly important as their relative volume increases as
sition and the electromechanical properties are maximal,4 as
grain size is reduced. For BSPT nanostructured ceramics, it
a result of a mechanism of polarization rotation between fer-
has been reported that the large resistivity of their grain
roelectric polymorphs.5 Specifically, the ferroelectric lead
boundaries is responsible of the apparent vanishing of ferroe-
zirconate titanate, Pb(Zr1xTix)O3 (PZT), system is used for
lectricity in them.19
a large number of commercial high-performance piezoelec-
The analysis of grain size effects in nanostructured
tric devices. The large piezoelectric coefficients in the PZT
ceramics requires local studies that reveal information close
system are found for compositions near a MPB between
to the behaviour of the individual grains. The electromechan-
rhombohedral and tetragonal phases, but its usage is limited
ical characterization of ceramics is very sensitive to extrinsic
at high temperatures due to its low Curie transition tempera-
factors such as porosity, secondary phases, or electrode/ce-
ture.6,7 In the search for alternative MPB compositions that
ramic electrical contact, which can hide the real size effects.
can operate in harsh environments, the perovskite solid solu-
The local characterization of the functionality of the individ-
tion system (1  x)BiScO3-xPbTiO3 (BSPT) becomes a
ual grains allows us, among other things, to confirm that the
promising candidate: for MPB (x  0.64) high Curie temper-
fundamental size limit below which ferroelectricity vanishes
ature (Tc > 450  C) and large piezoelectric coefficients
has not been reached.15,19 The best option to perform this
(d33  460 pC/N) have been reported.8,9
characterization in ferroelectrics is the use of the piezores-
ponse force microscopy (PFM), based on detecting the local
a)
Author to whom correspondence should be addressed. Electronic mail: deformations of the sample induced by an electrically biased
[email protected] probing tip.20,21 The PFM allows the observation of

0021-8979/2014/116(12)/124108/8/$30.00 116, 124108-1 C 2014 AIP Publishing LLC

V

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 124108-2 Salazar et al. J. Appl. Phys. 116, 124108 (2014)

ferroelectric domain configurations with high lateral resolu- cantilevers with a force constant of 42 Nm1. An external
tion and the characterization of local properties through AC voltage with amplitude of 1 V and frequency of 50 kHz
switching spectroscopy,22 which is very valuable informa- was applied between the tip and the sample, while the deflec-
tion for the studies of size effects. The fact that flat surfaces tion and torsion signals from the cantilever were detected by
are needed requires that ceramic surfaces must previously be lock-in amplifiers, in order to obtain the out-of-plane (OP)
prepared, without introducing any artifact. This is not neces- and the in-plane (IP) piezoelectric responses. Local in-field
sary when PFM is carried out on fresh surfaces, like in the (measurements with the DC bias applied) and remnant
studies on single crystals or thin films. In the present work, (measurements after the DC is removed) piezoelectric hys-
PFM is used to carry out a systematic study of the evolution teresis loops were measured at different locations to prove
of ferroelectric domain configurations of BSPT ceramics the switching characteristics of individual grains. For each
with decreasing grain size. The transgranular correlations PFM experiment, a calibration of the piezoresponse signal
among the polarization of adjacent single-domain grains are was carried out using the detector sensitivity.22 The conver-
analyzed together with the complexity of the configurations sion factor between the mechanical displacement of the tip
observed. The feasibility of local switching of these domains and the electric deflection signal is obtained from the slope
under an electric field is also studied, which is found to show of the linear dependence of a deflection-displacement (F-z)
anomalous, very distinctive features in the case of the small- curve, where the deflection of the cantilever is measured
est grains. The results of the study clearly indicate the per- while the z-scanner pushes the sample towards the tip in con-
sistence of ferroelectricity at the nanoscale, but with a strong tact mode. This allows us to determine and control the inter-
effect from the grain boundaries. The influence of these size action force between the tip and the surface, knowing the
effects on the functional properties of these nanostructured cantilever spring constant, which is estimated through the
ceramics is discussed. measurement of the free resonance curve following the
Sader method.27 In order to minimize the electrostatic contri-
II. EXPERIMENTAL PROCEDURE butions we tried to perform measurements in the strong in-
dentation regime,28 with tip-surface forces around 100–200
Dense ceramics with tailored grain sizes of nN. As the electromechanical characteristics of the cantile-
(1  x)BiScO3-xPbTiO3 compositions (BSPT) within the ver influence PFM results, stiff cantilevers are used,29,30
Morphotropic Phase Boundary (x ¼ 0.620-0.625) were pre- which in the strong indentation regime favors electrome-
pared from nanocrystalline powder obtained by mechanosyn- chanical contrast.
thesis from the binary oxides.23 A coarse-grained ceramic
(CGC), grain size of 1.6 lm, was obtained by conventional
sintering at 1100  C for 1 h,24 and nanostructured ceramics III. RESULTS AND DISCUSSION
(grain size < 100 nm) were obtained by Spark Plasma The characterization by scanning force microscopy of
Sintering (SPS, 2080 Sumitomo apparatus) with a careful ceramics requires first a preparation process of their surfaces,
control of the SPS conditions.25 In this work 650  C under which usually consists in polishing to a mirror-like finish.
uniaxial pressures of 75 and 120 MPa during 3 min were Additionally, in order to reveal the grain boundaries, a pro-
used to obtain grain sizes of 80 nm (fine-grained ceramic- cess of thermal quenching, followed by a gentle annealing, is
FGC) and 28 nm (nanostructured ceramic-NC), respectively also carried out. In order to study if these processes alter the
(Table I). ferroelectric domain configurations studied, a comparison
Samples for microstructural characterization were pre- between the images obtained on a polished sample and on
pared by polishing the ceramic surface to a mirror finish another after thermal quenching is shown in Figure 1 for the
using alumina suspensions with decreasing particle size FGC. Note that domains have characteristic sizes of the
down to 0.1 lm. Grain boundaries were revealed by thermal order of the grain size in the case of the thermally quenched
etching always at temperatures below the sintering: 845  C sample, as expected, while they are less defined and signifi-
for CGC and 500  C for FGC and NC. The local electrome- cantly larger in the case of the only polished surface. This
chanical response of the ceramics was studied by piezores- effect may be attributed to the presence of a layer on the sur-
ponse force microscopy (PFM) implemented in a face of the just-polished sample that is not responding to the
R
commercial scanning force microscope (NanotecV with electric field of the tip in the same way as the bulk. As a con-
WSxMV software26) using conductive Pt/Ir coated tips on
R

sequence, the real deformation of the ceramic due to the pie-

zoelectric effect is only occurring just below this layer. Thus
TABLE I. Sintering conditions (temperature, pressure, and time) and grain
the tip is sensing the piezoelectric deformation of the bulk
size of ceramics processed by SPS and conventional methods.
transmitted through this top layer, therefore producing a dis-
Sintering conditions Grain size torted image of the ferroelectric domains and reducing
strongly the PFM resolution. A similar effect has been
CGC Conventional sintering 1.6 lm (Ref. 24)
reported previously,31 when ferroelectric domains below an
1100  C/1 h
ion-implanted, non-piezoelectric active layer were observed.
FGC SPS 80 nm (Ref. 17)
650  C/75 MPa/3 min
PFM images show broadened domain walls, with more con-
NC SPS 28 nm (Ref. 25) trast the larger the driving voltages used, which demonstrates
650  C/120 MPa/3 min the contribution of the deep piezoelectric regions of the crys-
tal to the image.

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 124108-3 Salazar et al. J. Appl. Phys. 116, 124108 (2014)

The analysis of the topographic, out-of-plane and

in-plane PFM images for each of the ceramics studied
(Figures 2–4) allows the study of the evolution of ferroelec-
tric domain configurations with the decrease in grain size
down to the nanoscale. While the PFM amplitude images
reveal all grain boundaries and domains walls as black (no
piezoelectric response) and the different values of the effec-
tive piezoelectric coefficients (dzz for out-of-plane and dxz
for in-plane analysis) within each grain, the PFM phase
images provide information on the polarization direction:
pointing either towards the substrate or the film surface
(out-of-plane PFM images) and left or right respect to the
scanning direction (in-plane PFM images). The combina-
tion of this information gives us a very accurate picture of
the evolution of the domain configuration in these
ceramics.
When the grains of the ceramics are large enough, like
in the coarse-grained ceramic, CGC, the comparison of the
topography line profiles and the OP phase PFM images
(Figure 2) clearly shows the existence of polydomain grains.
Inside most of the grains analyzed there are a number of do-
main walls which corresponds to the formation of complex
configurations of twins, as reported previously for ferroelec-
tric ceramics with relatively large grains.36,37 If we combine
the information of both OP and IP phase PFM images, we
can produce a reconstruction of the distribution of the polar-
ization directions, as it can be seen in the schematic repre-
sentation of polarization directions drawn on the topographic
image of two grains in Figure 2(e): both ferroelastic domains

FIG. 1. OP phase PFM images for (a) only polished and (b) polished and
thermally quenched, FGC BSPT ceramic (grain size: 80 nm).

It is well known that polishing introduces much stress

on the sample surface, which can modify strongly its ferro-
electric domain configuration32 and piezoelectric behavior.
The use of thermal annealing removes this residual stress,
so this differentiated top layer will disappear easily in any
thermally treated sample. This is what happens in this
study, where a ferroelectric domain configuration that now
matches the ceramic grain size can be observe in the PFM
images of the thermally quenched ceramic (Figure 1(b)).
Therefore, in order to avoid any artifacts in the study of
ferroelectric domains on ceramic surfaces, it is necessary to
carry out an annealing of the sample after polishing. All
results shown in this paper were carried out on thermally
annealed samples. It must be pointed out that this annealing
procedure is not reported in other PFM studies of polished
ceramic surfaces,33–35 where the grain size is in the FIG. 2. PFM study of the coarse-grained ceramic (CGC) (a) and (b) OP and
IP amplitude images; (c) and (d) OP and IP phase images; (e) surface topog-
micrometer range and the lateral resolution needed for the raphy with a superimposed scheme of the domain configurations for two
ferroelectric domains observation is lower than in nano- grains; (f) comparison of the topography and OP phase line profiles marked
structured ceramics. in the images.

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 124108-4 Salazar et al. J. Appl. Phys. 116, 124108 (2014)

(straight domain walls, as they correspond to twinning planes

in the crystal) and inversion (180 ) domains (wavy domain
walls) are easily identified.
Very different domain configurations are found in the
ceramics with smaller grain sizes, FGC and NC (Figures 3
and 4). Neither straight ferroelastic domain walls nor wavy
inversion domain walls are observed within the grains.
When representative topographic profiles are compared with
the PFM out-of-plane (OP) amplitude profiles in Figures 3(f)
and 4(f), it can be seen that the ferroelectric domain walls
(where the PFM amplitude goes to a minimum) coincide
with the grain boundaries, i.e., grains are typically single-
domain. Furthermore, if we observe the OP and IP phase
images in both ceramics, there is a tendency of forming
groups of neighboring grains with the same sense of the OP
or IP component of the polarization vector, which will be an
indication of the presence of correlations among the polar-
ization of adjacent grains to form what could be called inver-
sion superdomains. The PFM phase profiles show how
several grains share the same OP phase but show different
values for the OP amplitude (Figures 3(f) and 4(f)), which
corresponds to single domain grains with their OP compo-
nent pointing in the same direction. This clearly indicates the
existence of transgranular correlations, which can be attrib-
uted to the necessity of reducing the system electrostatic
FIG. 3. PFM study of the Fine Grained Ceramic (FGC) (a) and (b) OP and
energy when this is not attained by the formation of ferro-
IP amplitude images; (c) and (d) OP and IP phase images; (e) surface topog- electric domains within each grain. The appearance of these
raphy; (f) comparison of the topography and OP amplitude and phase line superdomains will be a mechanism for reducing the electric
profiles marked in the images. bound charge accumulation at the surface and the associated
depolarization field. They appear only when the individual

FIG. 4. PFM study of the NC (a) and

(b) OP and IP amplitude images; (c)
and (d) OP and IP phase images; (e)
surface topography; (f) comparison of
the topography and OP amplitude
and phase line profiles marked in
the images; (g) surface topography
obtained with a non-coated tip.

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 124108-5 Salazar et al. J. Appl. Phys. 116, 124108 (2014)

grains are single domain due to their reduced size. The pres- between shear and longitudinal piezoelectric coefficients
ence of these inversion superdomains explains the appear- occurs in crystals where the polarization rotation is the domi-
ance of macroscopic ferroelectric switching in these nant mechanism of piezoelectric response.40 This piezoelec-
ceramics.19 tric anisotropy increases close to ferroelectric-ferroelectric
It must be noted that for the nanostructured ceramics, phase transitions involving polarization rotation, and, there-
NC, the observation of the grains (28 nm) is compromised fore, it can be observed in ceramics with compositions close
due to the limits of the lateral resolution attainable with the to Morphotropic Phase Boundaries of solid solutions like
coated tips used (minimum diameter of 20 nm without the PbZrO3-PbTiO339 and the present BiScO3-PbTiO3.41 The
Pt/Ir coating). As the measurement is the result of the convo- sharp decrease of the values of the dxzeff coefficients for the
lution of the tip and the object, when both have similar sizes, nanostructured ceramics, even below of those of dzzeff cannot
the measured lateral sizes are larger than the real values. In be attributed to the stabilization of phases far from the MPB.
this case, the topography images show grains in the range of Evidences from X-ray diffraction and Raman spectroscopy
the 40–50 nm. The lateral resolution of PFM seems not to be studies on nanostructured BSPT ceramics24 show that there
much better, as the domain size is in the same range. Being a is no significant variations respect to the coarse-grained
contact mode, in which is necessary to work in what is called ceramics. Therefore, the absence of ferroelastic domains
a regime of strong indentation to minimize non- within the grains seems to be the cause of the observed
electromechanical effects,22 wearing of the tip occurs inevi- change. The ceramic stresses produced by the surrounding
tably during the PFM experiments. This results in an increase grains cannot be absorbed anymore by domain reorganiza-
of the tip diameter and thus a reduction of the lateral resolu- tion. For those grains in the surface this is not a problem in
tion. For the sake of comparison, a topography image the out-of-plane direction, as the grains can expand freely in
obtained with a new non-coated tip is shown (Figure 4(g)), that direction under the application of an electric field. As a
where grains of the expected sizes can be observed. result, dzzeff values are only affected by the grain size effects.
It can be concluded that, up to the resolution limits of However, for the shear coefficients, as any in-plane move-
this technique, the reduction of the crystal size below a ment is constrained by the surrounding grains unable to
threshold value results in the disappearance of ferroelastic absorb any deformation, the values decrease even more, as it
domains. The width of these domains is expected to decrease is observed. As a result the observation of the piezoelectric
as the grain size is reduced, until they disappear below a crit- anisotropy is disturbed. Ceramics with single domain grains
ical value,36 which is above 80 nm in the case of BSPT. The will not reveal correctly their correlations between shear and
decrease in the elastic energy obtained by the creation of longitudinal coefficients when local measurements are car-
these ferroelastic domains does not compensate the energy ried out in their surfaces.
associated with the formation of the domain walls. This Representative successive in-field local piezoelectric
threshold value depends on the structure and composition of hysteresis loops for the CGC material are shown in Fig. 5(a).
the crystal, but it seems always to be above 100 nm. For They correspond to the expected hysteresis loops that are
example, it is reported a value of around 300 nm for typical of any ferroelectric material: the piezoelectric coeffi-
BaTiO336 and grains of 180 nm still show ferroelastic cient values increase up to saturation and, when the field is
domains in PZT ceramics.38 removed, they are reduced to a remnant value, following the
The appearance of piezoresponse in the ceramics with arrows drawn on the graph. This behavior can be described
the smallest grain sizes (FGC and NC) indicates that the po- as counterclockwise hysteresis. However, the piezoelectric
lar state persists down to crystallite sizes of around 28 nm. hysteresis loops for FGC and NC materials shown in Figs.
This is very relevant as it proves that BSPT nanostructured 5(b) and 5(c) does not follow the same behavior. When
ceramics are functional materials, regardless their small decreasing the applied electric field from the maximum value
grain size, and, therefore, can be used in applications. to zero polarization, the piezoelectric coefficient changes the
Although PFM measurements are not quantitative, an sign, which it can be described as clockwise hysteresis, as
estimation of the effective piezoelectric coefficients can be indicated by the arrows on the graphs. In Figure 5(b) we can
extracted from the amplitude images in order to see their observe that the increase of the electric field results in an
evolution with the decrease of the grain size. It must be noted increase of the piezoelectric coefficient until saturation is
that the maximum amplitude values for the PFM images of reached, but this value is not stable when the electric field
Figures 2–4 have been chosen to show more clearly the fer- decreases, going readily down to zero, even before reaching
roelectric domain configuration and are not comparable. In zero field. And if the field value decreases even more, the
fact the average dzzeff value obtained from several amplitude piezoelectric coefficient changes its sign still at positive
images like the one shown in Figure 4 for CGC decreases for fields and it starts increasing until the field is completely
FGC and NC. Similarly, the dxzeff values show higher values removed. It must be also noted that the starting value for the
for CGC than for FGC and NC, showing the strong decrease second and third loop is slightly smaller that the value
of the piezoelectric response with grain size reduction. The obtained in the precedent loop. This shows that the remnant
disappearance of the ferroelastic domains for these ceramics piezoelectric coefficient relaxes with time rather quickly.
produces a drastic reduction of the extrinsic contributions to This phenomenon can be further analyzed performing
the piezoelectric properties.39 remnant hysteresis loops (Figure 5(d)), measuring the piezo-
It must also be noted that the value of the dxzeff coeffi- electric coefficient after the removal of the DC field. It can
cient for CGC is higher than the dzzeff. This correlation be seen that as soon as the field is removed, the value of the

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FIG. 5. Local in-field piezoelectric

hysteresis loops for (a) CGC, (b) FGC,
and (c) NC. (d) Local remnant loops
corresponding to those of (c) for NC.

piezoelectric coefficient decreases, showing a large and separation of charges produced is therefore restricted to a
almost instant relaxation of the piezoelectric effect. Besides, small volume, and it is easily redistributed within the crystal.
the value obtained is always in antiphase with the electric Local piezoelectric loops of ceramics with large enough
field applied (negative piezoelectric coefficient for positive grains, like CGC, are therefore not disturbed and show a con-
electric fields and vice versa). This situation responds to the ventional behavior. Only when the grains approach the nano-
appearance of a large internal electric field within the grain scale, the volume of separated charges may reach the grain
opposite to the applied electric field that does not disappear boundaries, where they are normally easily compensated, not
when this is removed. Furthermore, this internal field is affecting the local hysteresis loops. However, in the case of
intense and larger than the coercive field. BSPT ceramics, grain boundaries have been proven to be
The observed clockwise piezoelectric hysteresis highly resistive,19 so in this case charges may accumulate for
observed in the nanostructured ceramics was initially long times in them. The result is the inducement of a stable
thought to be attributed to the appearance of piezoelectric internal electric field within the grains that stays even when
dissipation, in particular the so called Maxwell-Wagner pie- the external field is removed. As the density of the accumu-
zoelectric relaxation42 that occurs in heterogeneous piezo- lated charges must be directly related to the intensity of the
electric structures. If we consider that the boundary and the electric field applied, the higher the external field applied,
core of grains have very different piezoelectric coefficients, the higher the internal field induced. This correlation can
when an electric field is applied the total deformation con- lead to internal fields above the coercive field, if the external
sists of two contributions: one is purely piezoelectric and the field applied is intense enough. This situation corresponds to
second is due to the stress generated in the interface between the piezoelectric coefficient values in the local remnant loops
the two layers with different deformations. Although this sit- obtained after the removal of voltages above 5 V for the
uation leads, under certain conditions, to the appearance of NC ceramics (Figure 5(d)). For the in-field loops, the values
piezoelectric relaxation effects and clockwise hysteresis of measured for the coefficients respond to the balance between
the charge versus pressure, and, similarly of the deformation the external and internal fields of opposite signs. The value
versus electric field, like those observed in the piezoelectric of the induced internal field in the grain increases with the
hysteresis loops of the BSPT ceramics, it cannot explain the increase of the applied electric applied in the first part of the
observed permanence of the phenomena once the external loop, but the latter is always larger and the polarization and
field is removed. The uncompensated strains in the interface the piezoelectric coefficients also increase up to their satura-
between grain core and boundary will disappear almost im- tion values. The maximum induced internal field in this first
mediately. And neither can it explain the polarization rever- part of the loop is stable once it is created, and, therefore, a
sal after field removal. decrease of the external field produce a decrease of the net
A more permanent effect of the electric field that indu- electric field applied and a subsequent decrease of the values
ces a large internal field (higher than the coercive one) must of polarization and piezoelectric coefficients observed in the
be searched. It must be considered that around the tip the second part of the loop, producing the observed clockwise
electric field is very intense, and this field may cause a cer- hysteresis (Figures 5(b) and 5(c)). When the external applied
tain degree of electromigration in the material. The electric field becomes smaller than the internal field of the

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 124108-7 Salazar et al. J. Appl. Phys. 116, 124108 (2014)

grain, the net electric field changes its sign and produces the been demonstrated by the observation of inversion superdo-
switching of the polarization when it reaches the value of the mains. The movement of these inversion walls under an elec-
coercive field. It must be noted that the value at which tric field explains the reported macroscopic polarization
the piezoelectric coefficient goes to zero in these loops does switching in these polycrystals with single domain grains.
not correspond to the coercive field of the crystal, but to the The highly resistive nature of the grain boundaries in BSPT
induced internal field. Therefore, this value rises with the nanostructured ceramics has been related in this work with
increase of the maximum voltage applied in the first part of the observation of distinctive effects on the local piezoelec-
the loop. However, the peculiar behavior of the local piezo- tric loops, which show an atypical clockwise hysteresis.
electric hysteresis loops of these ceramics, caused by their More importantly, the ferroelectric behavior has been dem-
highly resistive grain boundaries, does not invalidate the fact onstrated in BSPT ceramics with grain sizes down to 28 nm.
that the grains still show polarization switching, and, there-
fore, ferroelectric behavior down to 28 nm. ACKNOWLEDGMENTS
To sum up, the local analysis by PFM of BSPT ceramics N.S. acknowledges the financial support of the Initial
has revealed that the reduction of the grain size to the nano- Training Network “Nanomotion” (Grant Agreement No.
scale results in the disappearance of ferroelastic domains, 290158) of the European Commission FP7 and the Spanish
which causes the reduction of the extrinsic contributions to Foreign Affairs Ministry Grant. This work was funded with
functional properties, such as the piezoelectric coefficients. the Spanish project MAT2011-23709.
However, the fact that no ferroelectric domains can be found
inside the grains should hamper strongly the switching of the 1
C. Pithan, D. Hennings, and R. Waser, Int. J. Appl. Ceram. Technol. 2, 1
net polarization. This is not the case as from transgranular (2005).
2
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3
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