J. Am. Ceram. Soc.
, 95 [1] 1–26 (2012)
Journal
Institute for Materials Science, University of Duisburg-Essen, 45141, Essen, Germany
Feature size is a natural determinant of material properties. Its
design offers the technological perspectives for material
improvement. Grain size, crystallite size, domain width, and
structural defects of different nature constitute the classical
design elements. Common ferroelectric ceramics contain micro-
meter grain sizes and submicrometer domain widths. Domain
wall mobility is a major contribution to their macroscopic mate-
rial properties providing approximately half of the macroscopic
output in optimized materials. The extension into the dynamic
nanoworld is provided by relaxor ferroelectrics. Ionic and nano-
scale field disorders form the base to a state with natural nano-
meter-size polar structures even in bulk materials. These polar
structures are highly mobile and can dynamically change over
several orders of magnitude in time and space being extremely
sensitive to external stimuli. This yields among the largest
dielectric and piezoelectric constants known. In this feature
article, we want to outline how lead-free relaxors will offer a
route to an environmentally safer option in this outstanding
material class. Properties of uniaxial, planar, and volumetric
relaxor compositions will be discussed. They provide a broader
and more interesting scope of physical properties and features
than the classical lead-containing relaxor compositions.
I. Introduction
P ERFORMANCE of functional materials in some cases relies
on symmetry and purity of the material like in the fore-
front silicon semiconductor world. In other cases, it may
mostly depend upon imperfections in order or structure.
Colossal effects in complex oxides as an example are criti-
cally related to inherent heterogeneity. Among well-known
effects are colossal magnetoresistance1 and magnetocapaci-
tance2 in doped manganites, high-temperature superconduc-
tivity in doped cuprates,3 and giant dielectric permittivity
and electromechanical coupling in relaxor ferroelectrics
which we will call “relaxors” in the remainder of the docu-
ment.4 In all these quite unlike materials, giant responses to
relatively weak external stimuli are caused by proximity
D. J. Green—contributing editor
Manuscript No. 30125. Received August 05, 2011; approved October 10, 2011.
*Member, The American Ceramic Society.
†
Author to whom correspondence should be addressed. e-mail: vladimir.shvartsman@
uni-due.de
DOI: 10.1111/j.1551-2916.2011.04952.x
© 2011 The American Ceramic Society
Lead-Free Relaxor Ferroelectrics
Vladimir V. Shvartsman† and Doru C. Lupascu*
effects, namely the competition between different ordered
states or phases and related changes on the nano- and meso-
scale domain structures.5 Control over formation of complex
nanoscale structures opens the way to exploring the existing
and even achieving new functionalities. Of particular interest
are functionalities arising from the coupling between different
degrees of freedom, for example, magnetoresistance, magne-
toelectric coupling in multiferroics, and electromechanical
coupling in relaxors.
Since their discovery by Smolensky and co-workers in
1954,6,7 relaxors have attracted continued interest due to
their unusual properties. A generic feature of relaxors is a
broad maximum in temperature dependence of the dielectric
permittivity, whose position, Tm, is shifted to lower tempera-
tures as the frequency of the probing field decreases
(Fig. 1).7 In contrast to conventional ferroelectrics, this maxi-
mum does not correspond to a phase transition from a para-
electric to a long-range-ordered ferroelectric state with
polarization being homogeneous inside macroscopic domains
[Fig. 2(a)].8,9 Instead, in relaxors, the polarization is corre-
lated on a local scale resulting in the appearance of polar
nanometer-size regions [PNRs, Figs. 2(b)–(d)]. Large dielec-
tric permittivity, e ~ 104–105 [Ref. 10] observed in a broad
temperature range and high piezoelectric coefficients d33 of
2500 pC/N, accompanied by an almost hysteresis-free actua-
tion strain of more than 0.6%11 have made relaxors a mate-
rial of choice for high-end industrial applications converting
mechanical into electrical forms of energy and vice versa.12
Several reviews have been devoted to relaxors, most of
them to the lead-containing systems.8,9,13,14 Existing surveys
on lead-free relaxors15,16 focused on particular systems and
are ~10 years old. In the present feature article, we intent to
overview the state of the art for the most interesting lead-free
relaxor systems, stressing features which are particular to
these materials as compared to the “canonical” relaxors, like
PbMg1/3Nb2/3O3 (PMN).
In what follows, we will briefly characterize relaxors in
general and then delineate the properties, similarities, and
differences for lead-free relaxors with respect to the more
commonly discussed lead-containing systems. Volumetric,
planar, and uniaxial relaxor systems will be discussed.
II. Characteristics of Relaxors
(1) The Polar Nanoregions and their Dynamics
The properties of relaxors are closely related to their unique
polar structure, namely to the existence of polar nanometer-size
Feature
2 Journal of the American Ceramic Society—Shvartsman and Lupascu Vol. 95, No. 1

regions (PNRs) and their response to external stimuli. These

Fig. 1. The temperature dependence of the real part of the
dielectric permittivity measured at different frequencies for a single
crystal of the canonical relaxor compound Pb(Mg1/3Nb2/3)O3 (from
Ref. 9).
regions of locally correlated polarizations appear at the
“Burns” temperature, TD, which is typically far above the
maximum point of permittivity, Tm.17 While the spatial sym-
metry is broken inside the PNRs, relaxors retain the higher
symmetry of the parent paraelectric phase macroscopically.
In the absence of an external electrical field, the dipole
moments of the PNRs, Pl, are randomly distributed. There-
fore,
Pno2 measurable remanent polarization exists. However,
as Pl 6¼ 0, the existence of PNRs becomes apparent in
properties depending on P2, for example, in the deviation of
temperature dependences of the refractive index17,18 or the
thermal expansion coefficient13 from the behavior predicted
for the paraelectric state (Fig. 3). For normal ferroelectrics,
the refractive index n decreases linearly with decreasing T,
starting from the high-temperature paraelectric phase down
to the Curie temperature, below which only n(T) deviates
from linearity.19 This deviation is proportional to the square
of polarization. Burns and Dacol found that in the case of
relaxors, like PMN, this deviation already starts at
TD = 620 K, which is about 350 K above Tm (at
f =10 kHz).17 Highly dynamic polar nanoregions have been
made responsible for this effect. The existence of PNRs was
later confirmed by elastic diffuse neutron scattering experi-
ments20,21. In PMN single crystals, a significant diffuse scat-
tering appears below TD with increasing intensity for
decreasing temperature.21 This diffuse intensity has been
associated with the PNRs. Various neutron and X-ray scat-
tering experiments have been carried out to investigate how
PNRs are formed, and what sizes and polarization values

(a) (b)

(c) (d)

Fig. 2. (a) 180- and 90-degree domains in a ferroelectric PbTiO3 single crystal at RT (the sample has been provided by Prof. J. Dec, University
of Silesia, Katowice, Poland); (b) polar structures in a relaxor Pb0.9125La0.0975(Zr0.65Ti0.35)0.976O3 ceramic below the transition temperature [Ref.
286]; (c) polar nanoregions in a relaxor Sr0.61Ba0.49Nb2O6 single crystal above the transition temperature [Ref. 240]; (d) polar nanoregions in a
BaTi0.85Sn0.15O3 ceramic above the transition temperature [Ref. 83]. Polar structures were observed by piezoresponse force microscopy. Blue and
red colors correspond to polarization oriented up and down, respectively. Yellow contrast marks regions with a negligible response.
January 2012 Lead-Free Relaxors
Fig. 3. Temperature dependences of the linear thermal expansion,
Dl/l, (a) and the refractive index, n, (b) for Pb(Mg1/3Nb2/3)O3
showing deviations from linear behavior starting at a temperature
(TD) much higher than the peak (Tm) of the dielectric permittivity.
After G. A. Samara,13 reprinted with permission by Institute of
Physics Publishing Ltd.
develop at different temperatures.14,22 The correlation length
of the atomic displacements contributing to diffuse scattering,
which is a direct measure of the PNRs’ size, is inversely pro-
portional to the width of the diffuse peak. According to
high-resolution neutron diffuse scattering performed on
PMN single crystals, the PNRs grow from about 1.5 nm at
TD to ~10 nm at 10 K upon cooling. The most significant
change of their size was observed around the freezing tem-
perature Tf ~ 210 K. This temperature coincides with those
estimated from the analysis of the dynamic dielectric
response of relaxors and corresponds to the slowing-down of
the relaxation related to the reorientation of PNRs.9 The
number of PNRs estimated from the integrated intensity of
scattering shows a monotonic increase upon cooling, starting
from TD, and then, an abrupt decrease at about Tf due to
the merging of smaller PNRs into larger ones.23 Qualita-
tively, similar results have been obtained for other relaxor
compounds.14,24,25
The microscopic origins of PNRs are closely related to the
inherent structural and charge inhomogeneities typical of
relaxors. In PMN, these inhomogeneities are due to the coex-
istence of two B-site cations (Mg2+ and Nb5+) with different
charges and chemical bonding characteristics in the ABO3
perovskite structure. High-resolution electron microscopy has
revealed an inhomogeneous distribution of B-site cations:
nanosized chemically ordered regions (CORs, ~2–5 nm) exist
in a disordered surrounding.26,27 Based on X-ray dispersive
spectroscopy measurements, Davies and Akbas suggested that
one of the B-sublattices inside the CORs is occupied exclu-
sively by B5+ ions, while the other one contains a random
distribution of B2+ and B5+ ions in a 2:1 ratio.27 Both, ran-
domly distributed B-site cations and CORs are believed to be
the sources of quenched random electric fields (RFs).18,28,29
This means that, additional to the external electric field and
the fields locally generated by polarization mismatch at grain
boundaries arising in all polycrystalline ferroelectrics to some
extent, relaxors contain sources of local electric fields within
the individual grains. These are randomly ordered according
to the disorder induced by the differently hetero-charged sub-
stitutional ions in the lattice. Different from pure acceptor- or
donor-type defects, these are overall compensated within the
structure and only exhibit local charge mismatch, yielding the
local random electric fields.
Imry and Ma have argued that in systems with continuous
symmetry of the order parameter, the quenched RFs which
3
are conjugated to the order parameter (the electric polariza-
tion in case of ferroelectrics and relaxors) will destroy the
transition to a long-range-ordered state.30 In the case of re-
laxors with the perovskite structure (“cubic” relaxors), like
PMN, the local polarization has eight allowed directions tak-
ing into account the local rhombohedral symmetry, and
hence, can be considered quasi-continuous. An equilibrium
phase transition into a long-range-ordered ferroelectric state
is therefore excluded. Indeed, the low-temperature state in
PMN is a short-range-ordered glassy-like state.
At the same time, at temperatures below TD, the RFs pro-
mote nucleation of PNRs with polarity controlled by the fluc-
tuations of the RFs.28 In the vicinity of the Burns
temperature, the PNRs are considered to be dynamical entities
with their dipole moments thermally fluctuating between
equivalent polarization directions.31 The dipole moments of
the PNRs are weakly correlated and are free to reorient. After
an external excitation, the system returns to the state with
lowest free energy. It is always the same state regardless of the
initial conditions. To distinguish this state from the paraelec-
tric PNR-state, it has been termed the ergodic relaxor (ER)
phase.9 The thermally activated reorientation of dipole
moments of the PNRs in the ER phase yields the major con-
tribution to the dielectric permittivity of relaxors.31 On cool-
ing, the interaction between the PNRs grows stronger
resulting in a slowing down of their dynamics. A broad distri-
bution of PNR sizes and randomness of interactions between
them yield a broad distribution of relaxation times giving rise
to a broad peak of dielectric permittivity versus temperature.
Finally, in systems like PMN, the divergence of the longest
relaxation time at a finite temperature results in the freezing
of PNR dynamics and in the transition to a glassy-like
state.32,33
The freezing temperature, Tf, may be derived from fitting
the frequency dependence of the temperature of the dielectric
permittivity maximum, Tm, to the phenomenological Vogel–
Fulcher law:
 
Ea
f ¼ f0 exp ; (1)
kðTm  Tf Þ
where Ea is an activation energy, f0 is an attempt frequency,
and k is the Boltzmann constant.31 In this state, the polar
order remains short-range. Polarization is correlated on the
nanometer scale inside the PNRs [Figs. 2(b)–(d)], but the sys-
tem remains nonpolar on a macroscopic scale. As relaxors
display various characteristics of nonergodic behavior below
Tf, viz. an anomalously wide relaxation time spectrum,34
aging,35 and dependence of the state on the thermal and field
history of the sample,18,33,36 this state is often called the
nonergodic relaxor (NR) state.9
A long-range-ordered ferroelectric-like state may be
induced in relaxor compounds when poling by an electric
field larger than a critical strength,37 by applying a mechani-
cal strain,38 or even by thermal annealing stimulating cation
ordering.39 A crossover from the relaxor to the ferroelectric
behavior may also be provided by chemical substitution,
which is, for example, the case in (1x)PbMg1/3Nb2/3O3–x
PbTiO3 (PMN-PT) with large Ti4+ content (x > 0.35)40 or
SrxBa1xNb2O6 (SBN) with large Ba2+ content (x  0.5).41
Compounds from an intermediate concentration range com-
bine both relaxor and ferroelectric properties. On the one
hand, they show strong frequency dispersion of the dielectric
permittivity around Tm and evidence of the existence of
PNRs far above Tm.42 On the other hand, their low-tempera-
ture state exhibits typical ferroelectric properties, such as fer-
roelectric hysteresis, pyro-, and piezoelectricity, etc.9
Nevertheless, there are some differences between this state
and a “normal” ferroelectric state. The PNRs appear to per-
sist even in the low-temperature ferroelectric state.43,44 Some
compounds exhibit specific macroscopic phase inhomogene-
4 Journal of the American Ceramic Society—Shvartsman and Lupascu
ity. Namely, depth-resolved X-ray diffraction experiments
performed on single crystal (1x)PbZn1/3Nb2/3O3–xPbTiO3
(PZN-PT)45 and PMN-PT46 revealed that the structural
phase transition to the rhombohedral ferroelectric phase only
occurs in an outer layer (thickness several tens of micro-
meters), while the interior part remains cubic, similar to the
NR state of PMN.
(2) Lead-Free and Lead-Containing Systems
While the relaxor behavior was initially discovered in Ba-
TiO3–BaSnO3 solid solutions,6 most of the subsequent
research activity has focused on lead-containing systems,
such as PMN-, PZN-based solid solutions, (Pb,La)(Zr,Ti)O3
ceramics, etc., which is due to their larger material output
coefficients. The formation as well as the evolution of the
relaxor state have been thoroughly investigated for these
materials using a broad spectrum of experimental methods.
Several theoretical models have been developed.9,28,47,48
During the last few years, interest in the lead-free relaxor
compounds has grown considerably. According to the ISI
Web of Knowledge, the portion of articles devoted to lead-
free relaxor systems among all articles devoted to relaxors
has continuously increased from ~25% in 2000 to around
45% in 2010. The growth is stimulated by the increasingly
severe restrictions on the use of lead in industry as a hazard-
ous substance. According to the directive for the Restriction
of the use of certain Hazardous Substances in electrical and
electronic equipment (RoHS)49 adopted by the European
Parliament in the year 2006, the maximum allowed concen-
tration of lead is established to be 0.1 wt% in homogeneous
materials for electrical and electronic equipment used in
households as well as industry. Some specific applications are
exempt from the directive, if their elimination is technically
or scientifically impracticable, lead-containing ferroelectrics
being one of them. They will be prohibited once a practicable
substitution is available. Similar regulations have been estab-
lished in a number of other countries.
Lead-free relaxors also exhibit a broader variety of phe-
nomena in comparison with the “canonical” lead-containing
compositions. Some of them transform to relaxor behavior
by isovalent substitution, i.e. without a nominal charge disor-
der, some show re-entrant relaxor behavior, and others show
antiferroelectric (AFE) relaxor states, just to mention a few.
Properties like large dielectric tunability,50 high dielectric per-
mittivity at elevated temperatures,51,52 large electrically
induced mechanical strain,53 a strong photorefractive effect,54
and other properties render the lead-free relaxor systems
attractive for a number of applications.
III. Lead-Free Relaxor Systems
(1) Lead-Free Relaxors with Perovskite Structure
(A) BaTiO3-Based Relaxors: The BaTiO3–BaSnO3
was the first system in which relaxor properties were discov-
ered.6 A number of relaxor compounds based on BaTiO3
(BT) have been found since. The BT is among the most stud-
ied and most widely used ferroelectrics. The discovery of fer-
roelectricity in this compound in the 1940s55,56 has triggered
a new era in the investigation of ferroelectrics. The BT crys-
tallizes in the cubic perovskite structure (point group m3m)
above its Curie temperature, TC = 393 K (Fig. 4). Below TC,
it successively transforms to three ferroelectric phases: first to
the tetragonal (4mm), then to orthorhombic (mm) at about
278 K, and finally, to a rhombohedral (3m) phase at 183 K.
The spontaneous polarization in the three ferroelectric phases
lies along [001], [011], and [111] direction of the parent cubic
structure, respectively [Fig. 5(a)]. Above TC, the dielectric
permittivity follows a Curie–Weiss law e = C/(Th) with the
Curie–Weiss temperature, h < TC, indicating a first-order
phase transition.
Vol. 95, No. 1
Fig. 4. The crystallographic structure of BaTiO3.
When solid solutions with other perovskite type com-
pounds are formed, BaTiO3 yields relaxor compositions
with a number of interesting features, some occurring in
certain compositions, others in several, and again some con-
currently:
1. Relaxor behavior in compositions without nominal
charge disorder.
2. Diffuse phase transitions as an intermediate state
between relaxor and ferroelectric states.
3. Existence of ferroelectric domains above the transition
temperature.
4. Coexistence of static and dynamic PNRs in a broad
temperature range.
5. Re-entrant behavior.
In the following, we will distinguish between these differ-
ent properties and outline which compositions offer which
peculiarities.
A crossover to the relaxor state was observed in BaTiO3
by both heterovalent and isovalent ionic substitutions. In the
first case, the relaxor behavior is induced by substitutions
either on A- or B- or on both A- and B-sites of the perov-
skite lattice ABO3, for example, in Ba1x(Sm0.5Na0.5)xTiO3,57
Ba1x/2 x/2(Ti1xNbx)O3 ( denotes a vacant site),58 and
BaTiO3–BiScO359–61 or BaTiO3–La(Mg0.5Ti0.5)O3,62,63 respec-
tively. In the second case, the relaxor behavior appears in
compounds with substituted B-site cations, such as BaTiO3–
BaSnO36 or BaTiO3–BaZrO3.64
In most cases, the dielectric properties of BT transform
according to the following scenario:
First, the temperatures of the transition between different
ferroelectric phases increase and come close to each other.
Simultaneously, TC goes down [Fig. 6(a)].
Second, at a certain concentration of substituting ele-
ments, all these transitions merge, a so-called pinched transi-
tion occurs.64 The system then directly transforms from the
cubic paraelectric to the rhombohedral ferroelectric state.
The corresponding peak of e′(T) is usually much broader
than that in BaTiO3, however, without the frequency shift of
Tm typical of relaxors. Such behavior is occasionally denoted
as a diffuse phase transition (DPT) to distinguish it from the
relaxor one. Another hallmark of the DPT is a deviation of
the dependence of the real part of the dielectric permittivity e
′(T) from the Curie–Weiss law at T > Tm [Fig. 6(b)]. This
deviation usually starts at temperatures significantly larger
(up to hundreds of degrees) than Tm.
Several phenomenological approaches have been devel-
oped to describe the DPT behavior. One is based on the
January 2012 Lead-Free Relaxors 5

Fig. 5. (a) Phase transitions in BaTiO3 according to the displacive scenario with Ti ions shifted from the center. (b) Phase transitions in BaTiO3
according to the order–disorder scenario with Ti ions exhibiting jumps between eight off-center positions. Shades of gray from bright to dark
illustrate occupancy probabilities from most to less probable (Refs. 117,119).

where e′m is the maximum of the dielectric permittivity at a

given frequency, Tm is the corresponding temperature, and
the parameter d determines the degree of diffuseness of the
transition. However, this quadratic law barely fits experimen-
tal e(T) dependences of many compounds showing DPT
behavior. Another empirical description was later proposed
by Santos and Eiras65

e0 m
e0 ¼ TT c ; (3)
1þ d
m

Here, Tm and d have similar meanings as in Eq. (2). The

parameter c gives information on the character of the phase
transition: c = 1 corresponds to a “normal” ferroelectric
transition, c = 2 indicates so-called complete diffuse phase
transition, and c 2 (1, 2) represents an intermediate state, a
so-called incomplete DPT with a certain degree of diffuseness
of its phase transition. Obviously, the Curie–Weiss law and
Eq. (2) are limiting cases of Eq. (3). This equation is more
general and better describes a variety of intermediate states
in between purely ferroelectric and relaxor behavior. In
particular, the frequency dispersion region around Tm can be
fitted maintaining the parameters d and c frequency-indepen-
dent.65 Instead of Eq. (3), another function, 1=e0  1=e0m ¼
ðT  Tm Þc =C, proposed by Uchino and Nomura,66 is often
Fig. 6. (a) Temperature dependences of the real part of the used to describe the DPT. While it is very similar to the Eq.
dielectric permittivity measured at 102–106 Hz for heterovalent- (3) and yields the same values of the parameter c, the dimen-
substituted (1x)BaTiO3–xLa(Mg1/2Ti1/2)O3 compounds. (b) sionality of the parameter C depends on the value of c,
Temperature dependences of the reciprocal permittivity for same which makes this notation physically difficult to interpret.
compositions fitted by the Curie–Weiss law. Reprinted with At higher substitution, Tm starts to show frequency disper-
permission from Ref. 63. Copyright Taylor & Francis Group, http:// sion matching the Vogel–Fulcher law [Eq. (1)]. This is often
www.informaworld.com.
used as a criterion of a completed crossover to relaxor
model proposed by Kirillov and Isupov.47 In this model, the behavior. Sometimes, especially when data of the frequency
DPT is considered to be due to local composition fluctua- dispersion of e(T) are missing, the relaxor state is associated
tions, resulting in microregions with different local Curie with the condition c = 2 [Eq. (3)]. For example, for the
points distributed in a Gaussian fashion around a mean (1x)BaTiO3–xLa(Mg0.5Ti0.5)O3 system, the parameter c
Curie temperature. The following equation was obtained to changes from 1.1 to 1.9 when x increases from 0 to 0.075,
describe the temperature dependence of the dielectric permit- respectively (Table I).63 Correspondingly, compounds with
tivity in the vicinity of Tm: x  0.075 show a distinct Tm(f) dispersion [Fig. 6(a)].
The degree of the crossover from the ferroelectric to the
e0 m relaxor state depends on the substitution type. Ravez and
e0 ¼ e01 þ 2 ; (2)
1 þ ðTT mÞ Simon systematized the effects of various substitutions on the
2d2 properties of BaTiO3.15,67 Most experimental data agree well
6 Journal of the American Ceramic Society—Shvartsman and Lupascu Vol. 95, No. 1

Table I. Summary of the Dielectric Characteristics for (1x)BaTiO3–xLa(Mg0.5Ti0.5)O3 Ceramics

x 5
em (10 Hz) Tm, K (105 Hz) DTm, K (102–106 Hz) c Tf , K Ea, eV f0, Hz

0.025 5300 331 0.5 1.34

0.05 5500 257 1.5 1.72
0.075 6400 181 3.5 1.91
0.10 4800 101 9 1.91 87 0.02 2.3∙1010
Here, em is the peak value of the dielectric permittivity at 100 kHz, DTm is the difference between positions of the maximum in the e(T) dependences, Tm, mea-
sured at 106 and 102 Hz, the parameter c reflects a degree of diffuseness of the e(T) peaks according to Eq. (3). Tf, Ea, and f0 are the Vogel–Fulcher fitting parame-
ters, according Eq. (1) [Refs. 62,63].

with their classification. In particular, the relaxor state is
induced by a relatively low doping level in the case of hetero-
valent substitutions on both A- and B- sites of the perovskite
structure [e. g., x = 0.055 for (1x)BaTiO3–xLa(Mg0.5Ti0.5)
O3,63 x = 0.075 for (1x)BaTiO3–xNaNbO368, x = 0.10 for
(1x)BaTiO3–xBiScO359] or on both B- and oxygen-sites
[x = 0.04 for Ba(Ti1xLix)O33xF3x69] (Table II). Heterova-
lent B-site substitution is exemplified by Nb-doped BaTiO3,
where the relaxor behavior has been reported for Nb concen-
trations higher than 7.5 at.%.58 However, in this case, A-site
vacancies are required for charge compensation and the exact
stoichiometry becomes Ba1x/2x/2(Ti1xNbx)O3.58 Thus,
these compounds can be also considered as both A- and B-
site hetero-substituted. For heterovalent substitution on the
A-site relaxor behavior is induced at moderate doping levels
(e.g., x = 0.10 for Ba1xBi2x/3x/3TiO370 or x = 0.20 for
Ba1xKx/2Lax/2TiO371). In solid solutions with isovalent-
substituted Ti4+, like BaTi1xZrxO372–74 or BaTi1xSnxO36,75–78,
the relaxor state is only observed at a fairly large substitution
levels x > 0.25–0.30.
The latter systems are of particular interest. First, the
more gradual crossover from the ferroelectric to the relaxor
behavior allows investigating this process in more detail than
for compounds with heterovalent substitutions. Second,
appearance of the relaxor behavior in systems without nomi-
nal charge disorder is unique and has not been well under-
stood so far.
(B) Crossover to the Relaxor State in BaTiO3–BaMO3
(M = Zr, Sn) Solid Solutions: The isovalently substituted
BaTiO3–BaMO3 (M = Zr, Sn) solid solutions show a more
gradual crossover to the relaxor state than heterovalent-
substituted compositions. The merger of all polymorph trans-
formations of parent BaTiO3 (pinched phase transition)
occurs at x ~ 0.1079 and x ~ 0.0880 for (1x)BaTiO3–xBaZrO3
(BTZr) and (1x)BaTiO3–xBaSnO3 (BTSn), respectively.
Compositions in the concentration ranges
0.10  x  0.18 (BTSn) and 0.15  x  0. 20 (BTZr)
show DPT behavior (Fig. 7). The nature of this phase transi-
tion is still a matter of discussion. Some researchers attribute
it to the relaxor state with the distinction between a fre-
quency-independent DPT and a frequency-dependent relax-
or-like behavior due to different sizes of the PNRs yielding
different relaxation times.81 When these relaxation times are
close to the experimental observation rates, relaxor behavior
is observed; when they differ much, only DPT behavior is
expected. However, there is an evidence that the DPT corre-
sponds to the ferroelectric phase transition. Ferroelectric
domains have been observed in compounds with DPT behav-
ior in the vicinity of Tm both in BTSn82,83 and BTZr74
ceramics. Broad-band dielectric spectroscopy reveals a contri-
bution to the dielectric permittivity related to the relaxation
of pinned ferroelectric domain walls (Fig. 8).74,83 This relaxa-

Table II. Critical Concentrations Corresponding to the

Ferroelectric-Relaxor Crossover for Some BaTiO3-Derived
Systems
Type of
substitution Solid solution x0 Ref. Fig. 7. Temperature dependences of the real part of the dielectric
permittivity measured at different frequencies for isovalent-
Isovalent: BaTi1xZrxO3 0.30 74 substituted (1x)BaTiO3–xBaSnO3 compounds [Ref. 76].
B-site BaTi1xSnxO3 0.25 76
BaTi1xCexO3 0.20 279
Heterovalent: Ba1xBi2x/3x/3TiO3 0.10 70
A-site Ba1xKx/2Lax/2TiO3 0.25 71
Ba1x(Sm0.5Na0.5)xTiO3 * 0.20 57
Heterovalent: Ba1x/2x/2(Ti1-xNbx)O3 0.075 58
A- and Ba1xLax[Ti1x(Mg0.5Ti0.5)x]O3 0.055 63
B-site Ba1xNax[Ti1xNbx]O3 0.075 68
Ba1xBix[Ti1xScx]O3 0.10 59
Ba1xBix[Ti1xAlx]O3 0.10 280
Ba1xLax[Ti1xFex]O3 0.10 281
Heterovalent: Ba[Ti1xLix]O33xF3x 0.04 69
B- and
anion-site
 denotes vacant site.
*
While BaTiO3 doped by Nb5+ nominally corresponds to B-site substitu-
tion, A-site vacancies are needed for charge compensation in this case. Thus, Fig. 8. Frequency spectra of the imaginary part of the dielectric
one has actually the situation corresponding to both A- and B-site heterova- permittivity for (1x)BaTiO3-xBaSnO3 ceramics with DPT (15% of
lent substitution. Sn) and relaxor (30% of Sn) behavior (Ref. 76).
January 2012 Lead-Free Relaxors
Table III. Summary of the Dielectric and Relaxor Characteristics for (1x)BaTiO3–xBaZrO3 Ceramics.
Parameters are the Same as for Table I [Ref. 74]
x em (105 Hz) Tm, K (105 Hz) DTm, K (102–106 Hz)
0.15 31900 344.5 0.5
0.20 30200 317 0.6
0.25 13500 279.5 3 1.93
0.30 11900 233 6 1.86
0.35 9960 198 25
0.40 4600 161 42
tion already appears above Tm, which correlates with the
observation of ferroelectric domains in the same temperature
range for BTSn ceramics with x = 0.10, 0.15.83 The existence
of ferroelectric domains in some temperature interval above
Tm has also been reported for the heterovalent-substituted
solid solution (BaTiO3)0.975–(LaMg1/2Ti1/2O3)0.025 also show-
ing DPT behavior.84
In compositions with larger content of Sn (or Zr), a shift
of Tm with frequency following the Vogel–Fulcher law is
observed, which is typical of the relaxor behavior
(Table III).74,83 The dielectric spectra change qualitatively as
compared to compositions with a diffuse phase transition:
the domain wall-related relaxation disappears, while another
contribution in the high-frequency range becomes dominant
(Fig. 8 shows the dielectric spectra for the BTSn ceramics
with x = 0.30). This new component corresponds to the low-
f wing of the Debye-like relaxation process related to the
reorientation of PNRs with characteristic frequencies
between 106 and 109 Hz.85 A slowing down of the PNR
dynamics upon cooling is reflected in a broadening of the
relaxation time distribution and in its shift toward longer
relaxation times. The shape of e′′ (f) changes accordingly. In
both BTSn (x  0.20) and BTZr (x  0.25) ceramics, a
shift of the PNR-related relaxation down to lower frequen-
cies was observed for decreasing temperature.74,76,77 The
spectra broaden strongly and become almost flat at tempera-
tures below 110–130 K. This is attributed to a transition to a
NR state accompanied by a freezing of the relaxation
dynamics. The transition takes place approximately at the
same temperature for BTSn 0.20  x  0.30 and BTZr
0.25  x  0.35 ceramics irrespective of composition, while
the freezing temperatures estimated from the Vogel–Fulcher
fits of Tm(f) differ for these compositions.74,76 For BTSn with
20% and 25% of Sn4+, for example, Tf is substantially
higher than the temperature corresponding to complete freez-
ing of PNRs relaxation. An explanation is that Tf estimated
from the Vogel–Fulcher fit corresponds to the appearance of
an infinite percolated cluster with frozen polarization, while
some re-orientable PNRs continue to exist below Tf. Bokov
et al. similarly suggested that in BTZr (x = 0.35), two inter-
penetrating sets of PNRs exist below Tf: static (large) PNRs
and dynamic (small) ones.73 They point out that in some
cases, the fulfillment of the VF law does not imply the freez-
ing of the relaxation.86 A maximum in the temperature
dependence of static permittivity and a gradual broadening
of the dielectric spectrum upon cooling necessary for such a
kind of behavior are satisfied for BTZr (x = 0.35) in the tem-
perature range around Tm.73 In compositions with relatively
high substitution rate, x  0.30 (BTSn), x  0.40 (BTZr)
Tf approximately matches complete freezing of the PNR
dynamics found from temperature-dependent dielectric per-
mittivity.
Maiti et al. have investigated the BTZr solid solutions on
the Zr-rich side.64,87 In compounds with Zr content
0.80  x  0.95, the relaxation peak in the dielectric per-
mittivity, Tm, follows the Arrhenius law, f = f0exp(Ea/kTm).
The authors attributed this relaxation to PNRs appearing
around the ferroelectrically active Ti4+ cations introduced
into the nonpolar matrix of BaZrO3. As the Ti content
7
c Tf , K Ea, eV f0, Hz
1.29
1.46
278 5 9 104 8.9 9 107
228 0.001 1.2 9 107
1.96 165 0.02 108
1.9 70 0.13 1.5 9 1012
increases beyond 25%, a critical size and distribution density
of PNRs was reached where the interaction between them
becomes essential. Correspondingly, BTZr compounds start
to show relaxor behavior with finite freezing temperature
gradually increasing from 4 to 122 K when x decreases from
0.75 to 0.35.
Figure 9 shows a phase diagram for (1x)BaTiO3–xBaZrO3
solid solutions based on experimental data by several
authors. After a pinched transition at x ~ 0.10, the low-tem-
perature state below Tm is ferroelectric (with rhombohedral
symmetry) in compositions with 0.10 < x  0.20. For
0.25  x  0.35, a percolation transition (one assumes
ferroelectric order inside the percolating clusters) occurs at
Tf, but regions with dynamic PNRs simultaneously exist
below the transition temperature.74 In the range
0.35 < x < 0.80, canonical behavior is found transiting into
the NR state with macroscopic cubic symmetry below Tf.
Finally, compounds with 0.80  x  0.95 remain in the
ER state (or in a superparaelectric (SPE) state) down to the
lowest temperatures investigated (near 0 K). For some BTZr
compositions, the Burns temperature was estimated from
thermal expansion measurements.64 At high temperatures,
the strain follows a linear temperature dependence normal
for the paraelectric state. Below TD ~ 440 K, a deviation
from linear behavior was observed indicating an electrostric-
tive strain due to formation of the local spontaneous polari-
zation. Thus, TD corresponds to the appearance of PNRs, i.
e. to a transition from the paraelectric state to the ER state.9
Approximately, the same temperature for the paraelectric–
ergodic relaxor transition has been reported for Raman data
BTSn with x = 0.30.88
There is still some controversy regarding the nature of the
low-temperature relaxor state in the isovalent-substituted
BaTiO3 compounds. Some authors argue that it is qualita-
tively different from canonical PMN-type relaxors64,89 based,
for example, on results of heat capacity measurements,89
Fig. 9. Phase diagram of the (1x)BaTiO3–xBaZrO3 system.
Transition temperatures were determined based on the dielectric
permittivity measurements: 0.00  x < 0.10 (Ref. 79), 0.10  x 
0.40 (Ref. 74), 0.40  x  0.95 (Refs. 64,87): solid and open
squares correspond to Tm (at 100 kHz) and Tf, respectively. The
Burns temperature (stars) was estimated based on data of the
acoustic emission for x = 0.00 (Ref. 125) and thermal expansion
measurements for 0.40  x  0.70 (Ref. 64).
8 Journal of the American Ceramic Society—Shvartsman and Lupascu Vol. 95, No. 1

Raman spectroscopy,90 or X-ray diffraction.91 However, data

reported by different groups are often contradictory. Naga-
sawa et al. have not observed an anomaly in specific heat
measurements of relaxor BTZr (x = 0.35) ceramics,89 which
would be typical of PMN.92 On the contrary, Gorev et al.93
have reported anomalous specific heat contributions for this
composition in the temperature ranges 250–350 and 150–
200 K, relating them to the appearance of PNRs and their
freezing, correspondingly. In PMN, long-range order can be
induced by field cooling from the paraelectric state.94 Sciau
et al. have not observed any electric field-induced long-range
polar order in BaZr0.35Ti0.65O3 by X-ray diffraction measure-
ments under electric field.91 Bokov et al. have argued that
the presence of nanometer-size nonpolar Zr-rich regions90,95
restricts the growth of PNRs in the BTZr relaxors and pre-
vents their transformation to macroscopic ferroelectric
domains even under a strong enough external electric field.73
Pyroelectric experiments on the other hand reveal that appli-
cation of suitable electric fields can induce a ferroelectric
order below Tf in BTZr relaxor compounds with
0.35  x  0.45.64 The zero-field cooling/field heating
(ZFC/FH) experiments reveal a decay of this electrically
induced state at depolarization temperatures ~81 (x = 0.35),
~46 (x = 0.40), and ~33 K (x = 0.45). These temperatures lie
below the corresponding freezing temperatures estimated
from Tm(f). The authors attributed this depolarization to a
transition from the field-induced ferroelectric state back to a
NR state.
(C) BaTiO3–BiScO3, A Re-Entrant Relaxor: A pecu-
liar behavior has been observed in (1x)BaTiO3–xBiScO3
relaxors. The BiScO3 is a paraelectric with a monoclinic dis-
torted perovskite structure characterized by both oxygen Fig. 10. (a) The peak (Tm) and freezing temperature (Tf) as a
octahedra tilting and antiparallel displacement of B-cations.96 function of BiScO3 concentration for (1x)BaTiO3–xBiScO3
Solid solution (1x)BaTiO3–xBiScO3 shows a fast crossover ceramics (from Ref. 59). (b) Remanent polarization as a function of
from the ferroelectric to the relaxor behavior typical of temperature in (1x)BaTiO3–xBiScO3 ceramics showing re-entrant
heterovalent substitutions.59,61 At x  0.10, the samples relaxor behavior. Reprinted with permission form Ref. 61.
show VF-type behavior with an activation energy Ea ~ 0.1– Copyright 2011, The American Physical Society.
0.2 eV, a value about one order of magnitude larger than in
PMN.59 Such values of Ea imply a weak interaction between
PNRs classifying this system as a “weakly coupled relaxor,” preted as a long-range-ordered state with a remanent polar-
where the PNRs are isolated and frustrated in a matrix that ization developing below Tm between the ER and the NR
provides only weak coupling between neighboring polar states in (1x)BaTiO3–xBiScO3 (0.10  x  0.45). Bharad-
regions.59 waja et al. assumed that re-entrant features in this system are
Contrary to most BT-derived relaxors, an increase of both due to a competitive dipole interaction between local ferro-
Tm and Tf was observed in compounds with higher BiScO3 electric and AFE order and/or local stresses.61 Guo et al.
content starting from x = 0.10 [Fig. 10(a)].59 Such enhance- observed by piezoresponse force microscopy that the disor-
ment of the transition temperature at relatively small amount dered state with presence of PNRs grows within the normally
of the second component is unusual in BT-based solid solu- ordered ferroelectric phase.102 They concluded that polar
tions. It was reported only when Ba was partially substituted clusters develop from a ferroelectric state and re-enter the
either by Pb97 or by Bi98. It was assumed that the Bi–O frozen disordered phase, instead of emerging from a para-
bonding due to its partially covalent nature99 induces a dif- electric state as in most other relaxor ferroelectrics.102
ferent component of polarization in the structure pushing the Similar re-entrant relaxor behavior has also been reported
transition temperature to higher values.98 A similar type of for some other lead-free systems, like 0.99BaTiO3–0.01
Tm(x) dependence with a minimum has been reported for AgNbO3103 and Ba2Nd1xPrxFeNb4O15104 [Fig. 11(b)].
some other systems, for example, (1x)BT–xKNbO3100 and (D) BaTiO3-Based Relaxors: Microscopic Properties: There
(1x)BT–xNaNbO3101 solid solutions. However, in these are many evidences that at the microscopic scale, BaTiO3-
cases, the increase of Tm starts at rather high concentrations based relaxors behave similar to pure barium titanate. The
of the second component, x = 0.7 and 0.5, respectively, Raman spectra of BT-derived relaxors, for example, look
reflecting a dilution of the high TC KNbO3 and NaNbO3 very much like those recorded in the paraelectric phase of
compounds by BaTiO3. BaTiO3 with broad bands centered at ~285 and 520 cm1
Another marked phenomenon reported for the BaTiO3– (Fig. 12).58,88,90,105,106 Even though a perfect cubic symmetry
BiScO3 system is re-entrant relaxor behavior called so analo- forbids any Raman modes, the Raman spectrum in the para-
gously to re-entrant magnetic spin glass systems.61,102 A more electric phase of pure BaTiO3 has been reported at tempera-
ordered state first develops at higher temperatures before tures up to 570 K. It is considered as an indication of a
going back to a more disordered state at low temperature. strong local disorder due to random displacement of Ti4+
Taking the remanent polarization, for example, it first ions at high temperatures.107,108 Presence of these bands in
increases as the temperature is lowered, but drops again on BT-derived relaxors implies that the local structure around
further cooling essentially vanishing at low T [Fig. 10(b)].61 the BO6 octahedra deviates from the perfect cubic symmetry.
Another manifestation of re-entrant behavior is a relaxation It was conjectured that the local structure of BTZr relaxors
peak related to the freezing of PNRs occurring below is rhombohedral.105 A high-frequency mode at ~780 cm1
another frequency-independent transition attributed to the (BTZr), not existing in pure BT is often considered as a sig-
ferroelectric phase transition [Fig. 11(a)].102 This was inter- nature of the relaxor phase.88,105,106 In contrast to ferroelec-
January 2012 Lead-Free Relaxors
Fig. 11. Temperature dependence of the real part of the dielectric
permittivity measured between 102 and 106 Hz for (a) (1x)BaTiO3–x
BiScO3, x = 0.05 (Reprinted with permission from Ref. 102. Copyright
2008, American Institute of Physics) and (b) Ba2PrxNd1xFeNb4O15,
x = 0.6 ceramics each showing re-entrant relaxor behavior. Reprinted
from Ref. 104 with permission by Institute of Physics Publishing, Ltd.
trics, BT-derived relaxors exhibit a continuous variation of
the overall intensity of the Raman spectra with temperature
without any significant change in peak positions or band-
width.58,105,106,109 That is, from the Raman point of view,
they do not show any structural phase transition. On the
other hand, for relaxor BTZr, the integrated Raman intensity
Fig. 12. Temperature evolution of Raman spectra for (1x)BaTiO3–xBaZrO3 ceramics with x = 0.00 and 0.35. Reprinted with permission from
Ref. 109. Copyright 2009, American Institute of Physics.
9
(for the 520 cm1 line) shows saturation below the freezing
temperature, indicating a saturation of the correlation func-
tion of polarization,58,88,105 whereas for ferroelectric com-
pounds, a continuous increase of the Raman-integrated
intensity of most lines was observed reflecting the onset of
long-range order.58
Investigation of the local structure of BTZr relaxors by
neutron pair distribution function analysis also indicates that
the Ti4+ displacements present in the ferroelectric BaTiO3
persist in BTZr relaxors.110 Moreover, the local dipole
moments associated with the Ti4+ are similar in BTZr and
BT. This similarity shows that the difference in the dielectric
properties of ferroelectric BT and relaxor BTZr only lies in
different correlations between the cation displacements.
Using first principle calculations, the same group showed
that contrary to BT, where the Ti displacements are all the
same in amplitude and direction along a <111> direction; in
BTZr relaxors, other types of displacement also appear:
along <110>, <100> directions, and even nearly canceled.111
The type of Ti polar displacement is entirely determined by
the Ti/Zr distribution in the adjacent unit cells. The underly-
ing mechanism involves local strain effects that ensue from
the large size mismatch between the Ti4+ and Zr4+ cations.
Random strains lead to a reorganization of the covalent
bonds between the Ti atoms and their oxygen neighbors in
BTZr resulting in a reorientation of the Ti shifts.111 A ran-
dom distribution of the Ti displacement symmetries among
the Ti–O6 octahedra impedes a perfect alignment of all the
Ti displacements as it exists in ferroelectric BT at low
temperatures. Nevertheless, the local distribution of the
substituted cations does not completely determine the Ti
off-centering: <111> displacements can be directed in eight
possible directions, four possible directions for <110> dis-
placements, and two possible directions for <100> displace-
ments. It was argued that this degree of freedom allows
partial correlations of the polar displacements, and thus the
formation of polar nanoregions.111
Off-centering of Ti4+ ions in BTZr solid solutions was
confirmed by the analysis of neutron total scattering mea-
surements by a reverse Monte Carlo approach,112 while the
Zr4+ ions remain in centers of the oxygen octahedra. The
correlation of the Ti4+ displacements results in polar nanore-
gions, whose polarization direction evolves on a few nanome-
ter length scale. Comparison between BTZr with different Zr
content shows that this correlation is stronger and extends
further for compositions with ferroelectric behavior
(x = 0.20) in comparison with relaxor BTZr (x = 0.35).112
10 Journal of the American Ceramic Society—Shvartsman and Lupascu
Electron diffraction experiments on both isovalent and
heterovalent-substituted BaTiO3 relaxors reveal diffuse scat-
tering, which implies existence of highly correlated aniso-
tropic chain dipoles along the <001> directions.113,114 These
chains were attributed to one-dimensional PNRs. The simi-
larly correlated anisotropic <001> chain dipoles are also
known to be the characteristic of the paraelectric phase of
BaTiO3 itself,115,116 being induced by covalent hybridization
between Ti 3d and O 2p orbitals along the <001> directions.
Liu et al. suggested that development of the long-range fer-
roelectric order in BaTiO3 is due to transverse correlations
between <001> chain dipoles.114 In the relaxor compositions,
the dopant ions set up random local electric and strain fields,
suppressing transverse correlations of these <001> chain
dipoles and frustrating the development of long-range ferro-
electric order.114 This interpretation of the diffuse electron
scattering has been criticized by Miao et al.,109 who point
out that diffuse scattering is a general phenomenon observed
in a broad number of ferroelectric/relaxor compositions and
it is not necessarily related to the correlation length of polar
order. In other words, the appearance of diffuse scattering
does not directly relate to the presence of PNR. Indeed, these
authors found that the electron diffraction data obtained
from a broad range of BTZr compositions, 0.05  x 
0.35, in which the polar order varies from the ferroelectric to
the relaxor state, show a self-consistent set of diffuse streaks
with the same diffraction conditions and qualitatively the
same intensity.109
Summarizing, results of the different experiments probing
properties of materials at the microscopic to atomic scale
indicate that the polar behavior of both pure BaTiO3 and
BaTiO3-based relaxors (at least in systems where the second
component is paraelectric) are substantially related to
displacements of Ti4+ ions from the center position in the
oxygen octahedra.
(E) Origin of the Relaxor Behavior in BaTiO3-Based
Systems: The origins of the crossover to the relaxor state
in BT-based compositions are now discussed. The relaxor
behavior requires two main “ingredients”: the existence of
quenched RFs and of randomly interacting PNRs at temper-
atures much higher than Tm.29,48 Random interactions are at
the origin of the nonergodic glass-like behavior, while RFs
prevent an equilibrium phase transition to a FE state, at
least when the local symmetry of the order parameter is
rhombohedral, that is close to be continuous.29 These two
ingredients are linked mutually: nucleation of PNRs at
higher temperatures is assumed to be promoted by fluc-
tuations of RFs.28
It is natural to assume that the development of the relaxor
state in hetero-substituted BaTiO3 systems is closely related
to the quenched RFs arising due to the introduced charge
disorder. This is similar to lead-containing relaxors, like
PMN or (Pb,La)(Zr,Ti)O3. However, for the isovalent-substi-
tuted BT-based relaxors, the role of random fields, or even
their existence, is not obvious.
To explain the appearance of relaxor properties in B-site
(both isovalent and heterovalent)-substituted barium titanate,
Simon et al.72 recalled that the ferroelectric polarization in
pure BaTiO3 results mainly from cooperative off-center shifts
of the Ti4+ (B-site) cations in the oxygen cages. This is con-
trary to the lead-containing ferroelectrics, where off-centrality
of Pb2+ cations on the A-site plays a major role. In BaTiO3,
substitution of Ti4+ breaks the correlations in displacement
of B-site cations and related long-range polar order. Simon
et al. proposed a model, where each substituted atom is
assumed to perturb the surrounding BaTiO3 host lattice in a
finite volume creating a polarized cluster.72 The size of these
perturbed clusters depends on the correlation length of the
host matrix. They grow at decreasing temperature and reach
their maximal size at the Curie temperature, TC. When the
concentration of substituted cations is below a critical thresh-
old, the number of the perturbed clusters is small, but each
Vol. 95, No. 1
such cluster can reach maximal size. In this situation, the sys-
tem maintains ferroelectric behavior. When the concentration
of the impurities approaches and exceeds the threshold, the
concentration of clusters increases, but they cannot reach
their maximal size. The relaxation of these small clusters
results in the dispersion of the dielectric permittivity and re-
laxor behavior of the system. The interaction between them
finally yields blocking of their relaxation at Tf. The model of
Simon et al. correlates PNRs with the clusters appearing
around substituting ions. However, it does not explain the
polar nature of the PNRs, i.e. how nonpolar inclusions like,
for example, Sn4+ can create a polar cluster. To account for
the different degrees of crossover to the relaxor state in cases
of isovalent and heterovalent substitutions, the authors have
considered a perturbation strength exerted by the introduced
ions. This phenomenological parameter is not related to any
physical or chemical property of the substituting ions,
although.
Considering appearance of the relaxor behavior in isova-
lent-substituted BaTiO3, Shvartsman et al. proposed that the
crossover from the ferroelectric to the relaxor behavior corre-
sponds to a transformation from a predominately broken
bond-type (at a lower degree of substitution) to a predomi-
nately random-field-type (for higher substitution) disorder.83
Usually, the B-site substituting cations do not go off-center,
giving rise to random breaking of Ti–O bonds. On the one
hand, spatial fluctuations of the defected bonds result in
fluctuations of the polar correlations, which in turn are
responsible for the formation of precursor clusters, seen, for
example, in BTSn ceramics by PFM.83 On the other hand,
the RFs were suggested to arise not only in compounds with
heterovalent (due to the inherent charge disorder), but also
with isovalent substitutions. In the latter case, the RFs are
mainly related to the existence of nanoscale regions with
enriched concentration of substituting cations.95,105 In these
regions with accumulated concentration of broken bonds, the
polar correlations are strongly diminished and polar domains
are less likely to nucleate. However, due to the distortions
arising around the substituting ions, a redistribution of the
charges and a local formation of charged centers results.
These are sources of local random fields. Clearly, this kind
of RFs is much weaker than that stemming from heterova-
lent cation substitution. Hence, the crossover to relaxor
behavior requires relatively high doping levels. It was sug-
gested that ferroelectric or relaxor behavior is reflected in the
interrelation between the three characteristic temperatures:
TD, TC, and Tf. If the strength of the random-field fluctua-
tions is weak, it might be insufficient to correlate the fluctuat-
ing dipole moments of the individual unit cells at high
temperature. In that case, the nominal Burns temperature,
TD, will be relatively low. If it is below the Curie tempera-
ture, no PNRs are expected and the conventional ferroelec-
tric transition occurs. Even when the dynamic PNRs appear,
their freezing temperature Tf, may lie below TC given by the
random bond fluctuations. In this case again, a transforma-
tion into the ferroelectric long-range-ordered state will take
place. This scenario is assumed to be realized in composi-
tions with DPT behavior, which shows both domain-like and
PNR relaxation in the dielectric spectra.73,74,83 Only if the
nominal TC lies below Tf, a transition to a NR state should
take place.
The aforementioned models consider that the PNRs
appear in the relaxor state originating from fluctuations of
the random fields or polarized regions around substitutional
defects. However, there is experimental evidence that a
dynamic polar disorder is inherent in the paraelectric state of
pure barium titanate. In particular, diffuse X-ray scatter-
ing115,117 and electron paramagnetic resonance118 data indi-
cate that the Ti4+ ions randomly occupy one of the eight
equivalent off-center sites along the [111] cubic directions
[Fig. 5(b)]. Nuclear magnetic resonance experiments119 and
terahertz dielectric spectroscopy120 point out a coexistence of
January 2012 Lead-Free Relaxors
displacive and order–disorder features for the ferroelectric
phase transition of BaTiO3. Brillouin scattering,121 wide band
dielectric spectroscopy,122 and photon correlation spectros-
copy123 give evidence that “jumps” of Ti4+ ions in between
different positions are correlated in neighboring unit cells
resulting in polar clusters with a size of a few nanometers far
from TC and up to 200 nm123 in the vicinity of the transition
temperature. These polar clusters resemble PNRs in the
relaxors and manifest themselves in similar ways, for exam-
ple, in a deviation of the refractive index from the linear
temperature dependence,124 or in acoustic emission peaks at
temperatures attributed to their appearance (Burns tempera-
ture) and emergence of some static PNRs.125
It is still an open question, how the dynamic polar regions
observed in barium titanate above TC are related to PNRs in
BaTiO3-related relaxors. A high-frequency (f ~ 108–109 Hz)
dielectric relaxation similar to the one in pure BaTiO3 has
been reported for BTSn composition relaxors with DPT
behavior.76 One can assume that polar clusters in pure
BaTiO3 are precursors of dynamic PNRs in the derived
relaxor compounds. In this case, the crossover to the relaxor
state occurs as soon as the ferroelectric transition related to
correlated displacements of Ti4+ is instable against the ran-
dom electric fields.28,30 Again, for isovalent substitution, the
RFs are relatively weak and such a transformation requires a
relatively large concentration of dopants. It has been argued
that the random strains resulting from chemical substitution
also affect the Ti off-center symmetries among the Ti–O6
octahedra and impede a perfect alignment of all Ti displace-
ments as in ferroelectric BaTiO3.111 One can also assume
that the effect of isovalent substitution is mainly related to a
gradual reduction of the Curie temperature. In that case, the
transformation to the relaxor state occurs in compounds
whose nominal Curie temperature falls below the tempera-
ture corresponding to the freezing of PNR relaxation which
then occurs earlier. In some cases of A-site substitutions, for
example, (1x)BT–x(Na0.5Bi0.5)TiO3, TC increases in compo-
sitions with larger x and no relaxor behavior occurs at least
up to x = 0.30.98
(F) KNN-Based Relaxors: Among the most promising
lead-free piezoelectrics are materials based on (K0.5Na0.5)
NbO3 (KNN) and (Bi0.5Na0.5)TiO3 (BNT).126–128 Search for
new compounds with improved electromechanical response
has resulted in the discovery of a number of systems with
relaxor behavior. The KNN-based relaxors exhibit the
following features:
1. Vogel–Fulcher behavior of Tm(f) typical of relaxors.
2. Diffuse phase transitions.
3. An extremely broad maximum in e(T).
We will now discuss some remarkable properties.
The advantages of solid solutions (K,Na)NbO3 between
ferroelectric KNbO3 and antiferroelectric NaNbO3 are their
relatively high Curie temperatures, several polymorphic phase
transitions (PPT), and the existence of morphotropic phase
boundaries (MPBs).126–130 The compositions around 50% of
NaNbO3 lie in the vicinity of a MPB between two ortho-
rhombic phases and show the best piezoelectric properties, a
longitudinal piezoelectric coefficient, d33 ~ 160 pC/N, and an
electro-mechanical coupling factor kp up to 40%, as well as a
high Curie temperature (693 K).131–133 Besides the paraelec-
tric (cubic) to ferroelectric (tetragonal) phase transition at
TC, other transitions between ferroelectric phases with tetrag-
onal to orthorhombic and orthorhombic to rhombohedral
symmetry change occur at Tt–o = 473 K and To–r = 80 K,
respectively.129,130 Due to the high TC, KNN is a promising
candidate for high-temperature applications. Relaxor behav-
ior has been observed in systems, like (1x)KNN–xBT
(x > 0.10),134 (1x)KNN–xSrTiO3 (x > 0.15),135–137 (1x)
KNN–xSrZrO3 (x > 0.15),138 (1x)KNN–xBiScO3
(x > 0.04),139 etc.
11
Fig. 13. Temperature dependences of the dielectric permittivity
measured at frequencies from 10 kHz to 1 MHz for (1x)KNN–x
SrTiO3 ceramics, x = 0.01 (1), 0.03 (2), 0.06 (3), and 0.10 (4).
Reprinted with permission from Ref. 135. Copyright 2004, Elsevier.
The properties of these different systems have some com-
mon features. As the concentration of the second component
increases, TC (or Tm) shifts down to lower temperatures and
the peak of the dielectric permittivity becomes much broader
than in pure KNN (Fig. 13). The samples with relatively
high x show a deviation from Curie–Weiss behavior above
Tm and the parameter c describing the degree of diffuseness
of the transition [Eq. (3)] increases. The Tt–o shifts to lower
values and the anomaly in the temperature dependence of
the dielectric permittivity becomes strongly diffuse with pro-
nounced frequency dispersion (Fig. 13). Above a certain con-
centration of the second component. the low-temperature
transition cannot be revealed from the dielectric data. A
change of the crystallographic symmetry from orthorhombic
to tetragonal has been established by X-ray diffraction, for
example, for KNN–BaTiO3 (x = 0.06)134 and KNN–SrTiO3
(x = 0.04)135. At a high enough degree of substitution, for
example, x  0.15 and x  0.10 for KNN–SrTiO3135 and
KNN–Ba0.5Sr0.5TiO3140, respectively, the peak position, Tm,
shows relaxor-like frequency dispersion (Fig. 13). The macro-
scopic symmetry below Tm remains cubic. The polarization
hysteresis loops become slimmer with increasing addition of
the second component.
Like in BT-based relaxors, heterovalent substitution
induces quenched RFs owing to the local charge imbalance
and the local elastic fields in KNN-derived systems. The
fields hinder long-range ordering and give rise to PNRs. The
degree of transformation into relaxor behavior varies from
x ~ 0.04 in KNN–BiScO3 to x ~ 0.15 in KNN–SrTiO3. Some
compounds, for example, 0.96KNN–0.04BiScO3 and
0.85KNN–0.15SrZrO3 show an extremely broad plateau-like
maximum in e(T), for which, the large dielectric permittivity
(~5000) remains almost constant in intervals of 100–150 K
width at temperatures above 300–400 K, respectively.138,139
Based on the similarity between this behavior and that of
dipolar glasses,141 Bobnar et al. have argued that the compo-
sitional mixing for these compounds is so effective that they
can be described as a glass not only on a mesoscopic level
like other relaxors, but also on a microscopic scale.138 The
ability of these compounds, especially KNN–BiScO3, to
maintain large dielectric permittivity in a broad temperature
range makes them quite attractive for high-temperature
capacitors.139
(G) Bi0.5Na0.5TiO3—“Antiferroelectric” Relaxors: Sim-
ilar to KNN, bismuth sodium titanate Bi0.5Na0.5TiO3 (BNT)
is considered as a promising lead-free piezoelectric mate-
rial.126–128 Of particular interest are solid solutions (1x)
BNT–xBT, which form a morphotropic phase boundary at
x = 0.06 separating a rhombohedral (R3c) and a tetragonal
(P4mm) ferroelectric phase isostructural with pure BNT and
12 Journal of the American Ceramic Society—Shvartsman and Lupascu Vol. 95, No. 1

BT, respectively.142 Compositions in the MPB region show

enhanced piezoelectric properties as compared to the end
members: d33 ~ 155 pC/N, and kp ~ 37% qualifying them
for piezoelectric actuators and high-frequency ultrasonic
applications.142,143 Both BNT and BNT-based solid solutions
show such features typical of relaxor ferroelectrics52,144,145
like:
1. A broad peak of the dielectric permittivity.
2. Absence of a structural transformation at Tm.
3. Frequency-dependent anomaly of the dielectric permit-
tivity.
4. Polar nanoregions.
as well as some peculiarities as:
1. local tetragonal symmetry
2. rather AFE than ferroelectric character of PNRs
The temperature evolution of the structure of undoped
BNT is still a matter of discussions.146,147 At room tempera-
ture, it is in the ferroelectric state with rhombohedral (R3c)
symmetry.148,149 Temperature-dependent X-ray and neutron
diffraction studies reveal a change from the rhombohedral to
the tetragonal phase in a broad temperature range between
528 and 593 K,126,149 or according to other reports between
493 and 673 K,146,150 where these phases coexist, and finally,
a transition from a tetragonal to a cubic phase at 813 K.149
The temperature dependence of the dielectric permittivity
shows several anomalies [Fig. 14(a)]: a broad maximum at
Tm ~ 593 K corresponds to a transition from a paraelectric
(according some reports ferroelastic147,150) to a presumed
AFE phase,148,151 and a frequency-dependent hump at
~473 K attributed to a transition to a ferroelectric
state.152,153 As the low-temperature anomaly is accompanied
by a decay of spontaneous polarization, it is often designated
as a depolarization temperature, Td.151,152 The nature of the
state in the temperature range between 473 and 593 K is still
debated. A double polarization hysteresis loop suggests AFE
ordering between Td and Tm.142,143 Neutron diffraction
studies suggest that the AFE phase should take the P4bm
symmetry with antiparallel displacements between A-site and
B-site cations.149 On the other hand, structural investigations Fig. 14. Temperature dependences of the dielectric permittivity
measured at frequencies from 102 to 106 Hz for (a) Bi0.5Na0.5TiO3.
do not reveal any structural transition at Tm,150,154 but indi- (Reprinted with permission from Ref. 153. Copyright 1998), with
cate coexistence of rhombohedral and tetragonal phases in permission from Elsevier), (b) 0.5Bi0.5Na0.5TiO3–0.5BaTiO3, and (c)
this temperature range.150 Weak pyroelectricity and a finite 0.3Bi0.5Na0.5TiO3–0.7BaTiO3 ceramics (Reprinted from Ref. 52.
bottleneck of the double hysteresis loops indicate the exis- Copyright 2004, Elsevier).
tence of polar regions at least at the mesoscale.155 Recent
transmission electron microscopy studies suggested that the
transformation from the ferroelectric rhombohedral into the in compositions with x = 0.05 and then only weakly depends
orthorhombic AFE phase proceeds via an intermediate AFE on the BT content. The temperature corresponding to the
modulated phase consisting of orthorhombic sheets in a transition to the AFE tetragonal state, T2, rapidly drops
rhombohedral matrix in the range between 473 and down and merges with the depolarization temperature, Td, at
573 K.146 The orthorhombic phase is then formed at 573 K x = 0.02-0.03. At x  0.06, Td(x) starts to rise, while T2(x)
and immediately turns into the tetragonal one.146 The inter- continues to decrease, determining the morphotropic phase
mediate state is characterized by polar disorder which boundary (Fig. 16). The transition between paraelectric
becomes apparent in relaxor-like behavior of the low-temper- phases with tetragonal and cubic symmetry also shifts to
ature dielectric anomaly.146,150 The NBT is considered to be lower temperatures approaching Tm at x ~ 0.05.145 It
a relaxor due to a substantial frequency dispersion at Td, remains unclear whether this transition merges with the
absence of a structural transformation at Tm, and indications Tm(x) line at x > 0.05 or dissolves into an average cubic
of phase coexistence at the nanoscale.150,151,156–158 The relax- phase with local tetragonal distortion.145 The nature of the
or behavior was attributed to the presence of ferroelectric region of the phase diagram, defined by 0.05 < x < 0.11 and
rhombohedral clusters embedded in a nonpolar tetragonal Td < T < Tm is not clear yet. Based on the analysis of the
matrix150 or polar Na+TiO3 and Bi3+TiO3 clusters in an elastic compliance, Cordero et al. suggested that for x > 0.05
AFE matrix.156 and T < Td, the phase is pseudocubic with local tetragonal
The structural complexity is intimately related to cation distortions.145 The compositions from this range show relaxor-
disorder in the Na/Bi sublattice.146 It is enhanced in solid like frequency dispersion near Td, which is substantially stron-
solutions with other perovskites, for example, in BNT–BT. ger than that in the parent BNT. Sheets et al. considered the
Indeed, a strong frequency dispersion of the dielectric permit- state between Tm and Td, as a “region of frustration where
tivity around Td has been reported for (1x)BNT–xBT solid multiple domain states are simultaneously available.”159 By
solutions with 0.06  x  0.09 (Fig. 15).144 Figure 16 analogy with other relaxor systems, the frequency dispersion
shows a phase diagram of the BNT–BT system.52,142,145 On of the dielectric permittivity might be related to the existence
the BNT side, Tm corresponding to the transition to a para- of the polar nanoregions, which probably form much above
electric phase decreases from 593 K in pure BNT to ~550 K Tm.150,151 Indeed, room temperature TEM studies reveal that
January 2012 Lead-Free Relaxors
Fig. 15. Temperature dependences of the dielectric characteristics
for (1x)Bi0.5Na0.5TiO3–xBaTiO3 ceramics, 0.04  x  0.11.
Reprinted with permission from Ref. 144. Copyright 2010, American
Institute of Physics.
ferroelectric rhombohedral domains with sizes around 100 nm
forming colonies of complex morphology seen in the composi-
tion with x = 0.04 transform into nanodomains observed for
samples with x = 0.07 and 0.09, which manifest local tetrago-
nal P4bm symmetry.144 Further increase in BaTiO3 content to
x = 0.11 leads to the appearance of large lamellar ferroelectric
domains corresponding to the stabilization of the tetragonal
P4mm phase at room temperature.144
Ma et al. proposed that the relaxor state in compositions
with x > 0.04 has rather an AFE than ferroelectric nature.144
They suggested that the displacements of A-site cations (Bi3+,
Na+, Ba2+) are antiparallel to the displacements of the
B-site cation (Ti4+) within each individual nanodomain. This
is supported by the fact the local P4bm symmetry is identical
to that of the AFE phase of BNT with antiparallel displace-
ments of Bi3+/Na+ and Ti4+ along the [001] direction.149
However, the AFE ordering in BNT–BT is only short-ranged
Fig. 16. Phase diagram of (1x)Bi0.5Na0.5TiO3–xBaTiO3 system
plotted based on results of dielectric, ferroelectric, and anelastic
measurements. The data were taken from Refs. 142,144,145 for the
concentration range 0.00  x  0.20 and for the concentration
range 0.50  x  1.00 from Refs. 52,98,161,162.
13
Fig. 17. Schematic diagram of the nanodomains responsible for the
observed relaxor AFE behavior in BNT–BT. The AFE nanodomains
with P4bm symmetry are embedded in an undistorted cubic matrix
(the white background in the diagram). The antiparallel arrow pairs
denote the cation displacements which fluctuate among the six
equivalent <001>c directions. Reprinted with permission from Ref.
144. Copyright 2010, American Institute of Physics.
being confined within individual nanodomains, which are
embedded in a matrix of an undistorted cubic lattice
(Fig. 17). It was also suggested that the frustrated relaxor
state may be induced by the competition between long-range
AFE and FE orders,160 which arise in this case due to adding
ferroelectric BaTiO3 to antiferroelectric Bi0.5Na0.5TiO3.144
For compositions 0.07 < x < 0.09, the frustration due to the
competing orders was assumed to reach a maximum, leading
to the relaxor behavior persisting to low temperatures. The
charge disorder in the A-sites being randomly occupied by
Bi3+, Na+, and Ba2+ results in the random electric fields,
which may affect the local balance between the off-center
shift of the B-site Ti4+ cation and the displacement of the
A-site cation in the opposite direction. The RFs will destroy
the long-range order and promote local dipole correlations.28
The resulting misbalance provides weak local dipole
moments dynamically fluctuating along the six equivalent
<001> directions. These fluctuations are assumed to be an
origin of the observed frequency dispersion of dielectric per-
mittivity in relaxor BNT–BT compounds.144
Considering this model, Ma et al. assumed that in BNT–
BT, the MPB separates rather a ferroelectric and a relaxor
AFE phase than two ferroelectric phases.144 In this case, the
maximum of piezoelectric properties and large electric field-
induced strain in BNT–BT around MPB seems to profit from
both relaxor-to-ferroelectric and the antiferroelectric-to-ferro-
electric electric field-induced transitions.
The phase diagram for large BT (x > 0.20) content has
been studied less. In compositions with x  0.50, Tm is con-
tinuously shifting from ~520 K (x = 0.50) to 393 K for pure
barium titanate (Fig. 16).52 A strong frequency dispersion
was observed around Tm for compositions with 0.30 
x  0.70 indicating relaxor behavior [Figs. 14(b) and
(c)].52,161,162 Similar to the canonical relaxor, this peak does
not correspond to any change of macroscopic symmetry, but
is attributed to the relaxation of PNRs with local tetragonal
symmetry embedded in a nonpolar matrix.162 Contrary to
the pure NBT and NBT–BT with small concentration of bar-
ium titanate, the low-frequency anomaly at Td is nearly fre-
quency-independent. It corresponds to the transition to a
ferroelectric state with tetragonal symmetry.161,162 Com-
pounds with BNT content between 15% and 30% show a
DPT behavior characterized by a negative difference between
Tm and the Curie–Weiss temperatures as compared to a posi-
tive one for compositions closer to the BaTiO3 side.98
The properties of the BNT–BT system are unusual in com-
parison with other BT-derived relaxors. The Curie tempera-
ture increases when coming from the BT side, while most
other systems show the opposite trend. In spite of the hetero-
14 Journal of the American Ceramic Society—Shvartsman and Lupascu
valent substitution, the relaxor behavior appears only at a
fairly high concentration of BNT. This may be related to a
weaker effect of doping only on the A-site on the correlated
shifts of the Ti4+ ions.15 Low-temperature X-ray diffraction
studies indicate that two PPT, typical of BT, are suppressed
already in compounds with 5% of BNT. This is probably
due to the effect of the local strains generated by doping with
cations of different sizes.98 The tetragonal symmetry of the
ferroelectric state is stabilized by BNT doping contrary to
the rhombohedral one for other BT-based relaxors.
The relaxor behavior has been reported also for other
binary systems containing BNT, for example, in (1x)BNT–
xSrTiO3 (x > 0.25),52,163,164 xBNT–(1x)NaNbO3 (x 
0.175),165 (1x)BNT–xBiFeO3 (x < 0.50),166 (1x)BNT–xBi0.5
Li0.5TiO3 (x < 0.10),167 (1x)BNT–xBa(Al1/2Nb1/2)O3 (x >
0.045),168 and (1x)BNT–xBi0.5K0.5TiO3 (x > 0.06).169 Prop-
erties of the BNT-based binary solid solution were systemized
by Hiruma et al.170 Three types of phase diagrams were con-
sidered. For both type A (e.g., BNT–NaNbO3) and type B
(e.g., BNT–KNbO3, BNT–SrTiO3) solid solutions, the range
of existence of the relaxor state broadens significantly for
increasing concentration of the second component. The BNT–
KNbO3 and BNT–SrTiO3 show relaxor behavior at room
temperature in compositions with x > 0.08 and x > 0.28,
respectively. The range where the rhombohedral and tetrago-
nal phases coexist also broadens for the type A solid solu-
tions. However, it disappears in solid solutions of the type B
and C. For the latter (e.g., BNT–BT, BNT–PbTiO3, BNT–
(Bi0.5K0.5)TiO3), the relaxor state is stabilized at higher tem-
perature, while the low-temperature state is ferroelectric with
the rhombohedral (R3c) and tetragonal (P4mm) symmetries
for compositions with small and large x, respectively. The cor-
responding MPBs lie at x ~ 0.06 (BNT–BT), x ~ 0.20 (BNT–
BKT), and x ~ 0.14 (BNT–PT).
Relaxor properties have also been reported for ternary sys-
tems, like Bi0.5Na0.5TiO3–K0.5Bi0.5TiO3–BaTiO3 (Ref. 171),
Bi0.5Na0.5TiO3–NaNbO3–BaTiO3 (Ref. 172), Bi0.5Na0.5TiO3–
K0.5Bi0.5TiO3–NaNbO3 (Ref. 173), Na0.5Bi0.5TiO3–Bi0.5K0.5
TiO3–BiCoO3 (Ref. 174), Bi0.5Na0.5TiO3–BaTiO3–K0.5Na0.5
NbO3 (Ref. 175). Compounds belonging to the latter system
exhibit relatively large and virtually temperature-insensitive
dielectric permittivity (De/e425 K < 10% from 316 to 592 K,
e425 K ~ 2000)175 and giant unipolar strain (0.45%).53 These
make them promising for applications in high-capacitance
capacitors operating at high temperatures and electrome-
chanical devices. The superior properties originate from the
relaxor nature of the BNT–BT–KNN compounds. The large
unipolar strain appears to be a consequence of the presence
of nonpolar regions at zero electric field destabilizing and
randomizing the electrically induced ferroelectric order.
These nonpolar regions drive the system back into its unp-
oled state once the applied electric field is removed.176
(H) NaNbO3-Based Relaxors: Sodium niobate, NaN-
bO3 (NN), is another lead-free base for relaxor compounds,
such as heterovalent-substituted (1x)NaNbO3–xBaSnO3
(x > 0.1),177 (1x)NaNbO3–xLiNbO3 (0.01  x  0.04),178
(1x)NaNbO3–xBi0.5Na0.5TiO3 (x  0.175),165 (1x)NaNb
O3–xSrCu1/3Nb2/3O3 (x  0.125),179 (1x)NaNbO3–xGd1/3
NbO3 (x > 0.15),180 etc.
Basic features of these systems are:
1. A frequency dispersion of Tm above certain concentra-
tion threshold typical of relaxors.
2. A DPT in isovalent-substituted solid solutions.
3. The extrapolated Curie–Weiss temperature lies below
Tm.
The parent composition NaNbO3 exhibits a complex
sequence of phase transformations, for which, the number of
transitions as well as the symmetry of the individual phases
are still a matter of discussion. According to the most
accepted scheme, NaNbO3 is in a ferroelectric state with
rhombohedral symmetry (R3c) at liquid helium tempera-
Vol. 95, No. 1
tures.181 Upon heating, it transits to an AFE orthorhombic
(Pbma) state at ~230 K. This first-order phase transition
exhibits a large thermal hysteresis, ~100 K.182 Several transi-
tions between AFE states with different orthorhombic sym-
metry follow. At ~753 K, a transition to the paraelectric
orthorhombic (Pnmm) phase takes place, which transform
further to orthorhombic (Ccmm), tetragonal (P4/mbm), and
finally, cubic (Pm3m) at 793, 848, and 913 K, respec-
tively.181,183 The temperature dependence of the dielectric
permittivity shows a rather sharp maximum at Tm ~ 625–
645 K associated with a first-order phase transition between
two AFE phases (Pbma and Pmnm).182,184,185 Neutron dif-
fraction186 and Raman scattering187 data indicate the coexis-
tence of the ferroelectric and AFE phases in a broad
temperature range from 70 to 250 K. Competing ferroelec-
tric and AFE interactions were suggested to result in the
frustration of local dipole ordering and in the relaxor-like
behavior.160 Lanfredi et al. reported on smeared dielectric
relaxation peaks (much smaller than the main maximum at
~630 K) showing frequency dispersion over the temperature
range of 80–250 K.188 Theoretical calculations suggest that
the free energies of the ferroelectric and AFE phases over
this temperature range are quite close. The small energy dif-
ference between the two phases makes it possible to easily
switch from the AFE to the ferroelectric state at moderate
electric fields.186 The NN is such an example where also
small amounts of dopant ions, like Li+ or K+, will induce a
transition.180 There is evidence that local fluctuations of Na
content or oxygen vacancies are responsible for the coexis-
tence of the AFE and ferroelectric phases in NaNbO3 single
crystals at room temperature and even above.189
The solid solutions based on NaNbO3 can be divided into
two groups.180 In the first, the high-temperature ferroelectric
state is already stabilized at a few mol% of substitution, the
temperature dependences of the dielectric permittivity are
sharp, and the transition temperature smoothly depends on
the degree of substitution. This occurs when the second com-
ponent is either a ferroelectric or paraelectric with tolerance
(Goldschmidt) factor t > 1, t = (RA + RO)/√2(RB + RO),
where RA, RB, and RO are the radii of A-, B-site, and oxygen
ions, respectively.190 Examples are (Na,Li)NbO3 and (Na,K)
NbO3.180,191 In the second group, the AFE state remains sta-
ble up to a comparatively high degree of substitution. The
peak position Tm decreases smoothly up to a certain thresh-
old concentration x = x0. For x > x0, an abrupt drop of Tm
along with a drastic broadening of the e(T) maximum is
observed [Fig. 18(b)]. Compositions with x > x0 exhibit a fre-
quency dispersion of Tm typical of relaxors.179,180 Such
behavior is observed when the second component is either an
AFE or a paraelectric with t < 1.190
Both x0 and the degree of the frequency shift of Tm
depend on the type of substitution. For the isovalent-substi-
tuted solid solutions, like, for example, (1x)NaNbO3–xNa-
TaO3, x0 is about 0.45, and the dielectric peak position only
shifts by a few K for two frequency decades indicating rather
a DPT than relaxor behavior.179 On the contrary, heterova-
lent cation substitutions, like, for example, in (1x)NaNbO3–x
SrCu1/3Nb2/3O3 (Ref. 179) and (1x)NaNbO3–xNa0.5Bi0.5
TiO3 (Ref. 165), or heterovalent substitution accompanied by
formation of cation vacancies like in (1x)NaNbO3–xGd1/
3NbO3 (Ref. 180) result in a substantial frequency dispersion
at x > x0 (e.g., DTm ~ 40 K for 0.7NaNbO3–0.3Na0.5Bi0.5
TiO3)179 Similar to the canonical relaxor, Tm(f) dependences
can be well described by the Vogel–Fulcher law. The devia-
tion from the Curie–Weiss behavior is observed in a broad
temperature range above Tm for all these solid solutions.
In the case of NaNbO3-derived relaxors, the extrapolated
Curie–Weiss temperature, h, is much lower than Tm. This
is in contrast to the behavior of other relaxor systems
(PMN- or BaTiO3-based relaxors), where h is usually larger
than Tm. It was suggested that this difference is a conse-
quence of the AFE character of pure NaNbO3.180
January 2012 Lead-Free Relaxors
Fig. 18. (a) Temperature dependences of the dielectric permittivity
of (1x)NaNbO3–xSrCu1/3Nb2/3O3 (b) Concentration dependences
of the Tm for different binary NaNbO3-based solid solutions showing
a crossover to relaxor behavior. The second components of the solid
solutions are: (1) SrCu1/3Nb2/3O3, (2) Gd1/3NbO3, (3) Bi0.5Na0.5TiO3,
(4) Sr0.5NbO3, and (5) NaTaO3, respectively. Reprinted with
permission from Ref. 179. Copyright Taylor & Francis Group,
http://www.informaworld.com.
(2) Lead-Free Relaxors with Two-Dimensional Order
Parameter: Compounds with the Aurivillius Structure
Bismuth layer structured ferroelectrics (BLSF) were synthe-
sized and described for the first time by Aurivillius.192 They
have a very anisotropic structure consisting of oxygen octa-
hedral (perovskite-like) blocks interleaved with (Bi2O2)2+
layers (Fig. 19). The c parameter, along the normal to the
fluorite-like (Bi2O2)2+ layers, is much larger than a and b
parameters of the orthorhombic or tetragonal unit cell. The
general chemical formula of the BLSF compounds is
(Bi2O2)2+(Am1BmO3m+1)2-, where m is an integer between 1
and 5 indicating the number of the perovskite-like blocks
between two adjacent (Bi2O2)2+ layers. 12-coordinated A-
sites are usually occupied by Pb2+, Bi3+, alkaline, or alka-
line earth cations, whereas in 6-coordinated B-sites cations of
transition metals, such as Ti4+, Nb5+, or Ta5+, are found.
The structural anisotropy of the Aurivillius compounds
results in highly anisotropic electric properties.193,194 Namely,
the spontaneous polarization lies predominately in the (a,b)-
plane being quasi two-dimensional.194 The interest to investi-
gate BLSF compounds is motivated by
1. their fairly high Curie temperature, for example,
875 K for Bi4Ti3O12 and 928 K for Na0.5Bi4.5Ti4O15
(Ref. 195),
2. relatively low dielectric permittivity, and
3. large anisotropy in the electromechanical coupling fac-
tor opening possibilities to use them for high-tempera-
ture piezoelectric applications.128 Moreover, their
4 excellent stability against repetitive polarization switching
(fatigue endurance)196 make them major candidates for
the development of nonvolatile ferroelectric memories.197
Relaxor compositions of the BLSF material family can be
formally divided into three groups. To the first group belong
compounds with the A-site completely or partially occupied
by Ba2+ ions BaBi2Nb2O9198–201, BaBi2Ta2O9,198,202 BaBi4
Ti4O15,203,204 and Ba2Bi4Ti5O18.205 Materials where cations with
15
Fig. 19. Aurivillius crystal structure, BaBi2Nb2O9, some Ba2+
substitute Bi3+ in [Bi2O2]2+ layers.
different valence occupy the same positions in the perovskite
blocks of the Aurivillius structure, like K0.5La0.5Bi2Nb2O9,206
and K0.5La0.5Bi2Ta2O9,207 form the second group. Compounds
where the relaxor behavior is induced by substitutions for Bi3+
in the (Bi2O2)2+-layers, for example, SrBi1.6Nd0.4Nb2O9,208
SrBi1.65La0.35Nb2O9,209 Bi2LaTiNb2O9,210 SrBi3LaTi4O15,211
and Bi2.75La1.25Ti3O12,211 may be put into the third group.
All these compositions again show typical relaxors behav-
ior (frequency dispersion of the dielectric permittivity, Tm(f)
dependence following the Vogel–Fulcher law, and deviation
of the e(T) dependences from the Curie–Weiss law above
Tm). Some characteristic parameters for various Bi-layered
relaxors are listed in Table IV. Contrary to canonical perov-
skite relaxors like PMN, it is difficult to induce long-range
order in Bi-layered relaxors with m = 2 even when applying
strong electric fields.199 Typically, no polarization nonlinear-
ity and apparent ferroelectric hysteresis are found for these
materials below Tm.199,212,213 However, BaBi4Ti4O15 (m = 4)
and Ba2Bi4Ti5O18 (m = 5) exhibit remanent polarization val-
ues ~15 and 12 lC/cm2, respectively.214 It was argued that
the remanent polarization is large in BLSFs having high
Curie temperatures. Indeed, Tm is much larger for BaBi4-
Ti4O15 and Ba2Bi4Ti5O18 than for the relaxors with m = 2.
The coercive electric field is smaller in compounds with a lar-
ger value for m supposedly due to the decrease in the strain
energy of the BO6 octahedrons from the bismuth layer, lead-
ing to an easy movement of the octahedral cations in the
direction of applied external electric field.214 This facilitates
poling these compounds.
The solid solutions between BLSFs with ferroelectric
and relaxor properties, for example, (1x)SrBi2Nb2O9–x
BaBi2Nb2O9215,216 and (1x)CaBi2Nb2O9–xBaBi2Nb2O9217
or compounds from the third group with small concentration
16 Journal of the American Ceramic Society—Shvartsman and Lupascu Vol. 95, No. 1

Table IV. Dielectric and Relaxor Characteristics of Some Relaxors with the Aurivillius-Type Structure. Parameters are the Same
as for Table I
Composition em (105 Hz) Tm, K (105 Hz) DTm, K (103–106 Hz) c Tf , K Ea, eV f0, Hz Ref.
13
BaBi2Nb2O9 550 450 115 1.94 97 0.63 10 199
390 460 90 100 0.56 4.7 9 1013 217
BaBi2Ta2O9 525 345 60 113 0.25 8 9 1012 202
Sr0.5Ba0.5Bi2Nb2O9 669 506 40 1.6 371 0.194 1.5 9 1012 216
Ca0.2Ba0.8Bi2Nb2O9 380 583 32 1.73 525 0.11 1.54 9 1011 217
K0.5La0.5Bi2Nb2O9 480 480 27 2 428 0.04 1010 206
K0.5La0.5Bi2Ta2O9 387 437 11 1.93 396 0.06 1.3 9 1013 207
BaBi4Ti4O15 2350 685 20 1.9 635 0.02 5.8 9 1011 203
1150 675 35 1.7 204
BaBi4Ti3Fe0.5Nb0.5O15 750 580 16 558 0.002 6.5 9 108 282
Ba2Bi4Ti5O18 2100 625 30–40 205
SrBi1.65La0.35Nb2O9 258 339 9 326 0.0088 2.2 9 109 209
SrBi1.8Pr0.2Nb2O9 471 290 7 1.45 224
SrBi1.6Nd0.4Nb2O9 195 342 15 331 0.012 109 208
Bi2LaTiNbO9 225 443 65 1.98 296 0.15 1.7 9 1011 210
Bi2.75La1.25Ti3O12 310 250 15–20 211
SrBi3LaTi4O15 413 510 3 211
Sr2Bi3.5La0.5Ti5O18 470 380 6 211
SrBi6.5La1.5Ti7O27 660 640 5 211

of substituting elements208,210,211 show a continuous cross-
over from ferroelectric to relaxor behavior. Chen et al. have
analyzed the threshold La content, x0, which is necessary to
induce relaxor behavior in Sr-containing BLSFs with differ-
ent numbers of perovskite-like blocks, m.211 The x0 decreases
both by increasing m and by increasing relative Sr content in
the perovskite units.
There are only few reports considering the influence of the
crystallographic anisotropy on relaxor properties in BLSF
compounds. Irie et al. reported on electrical properties of
Ba2Bi4Ti5O18 single crystals.214 Yan et al. have studied the
orientation dependence of the relaxor behavior for grain-ori-
ented BaBi2Nb2O9 ceramics.218 In both cases, the relaxor
parameters, such as DTm(f), the freezing temperature, and
the activation energy of the Vogel–Fulcher fit are isotropic,
in spite of a strong anisotropy of dielectric permittivity and
polarization.
Similar to materials with the perovskite structure, the
relaxor behavior in the Bi-layered compounds is attributed to
a structural disorder, which is either inherent or introduced
by doping. The first situation is realized in BLSF relaxors
with Ba2+ cations on the A-sites. Withers and co-workers
suggested that the major contribution to ferroelectric polari-
zation in BLSFs with m = 2 is due to the displacement of A-
cations in the perovskite units.219,220 Hence, disorder on the
A-sites may significantly affect the polar properties of these
materials. It was originally proposed by Smolenskii et al.
that the relaxor behavior of BaBi2Nb2O9 and BaBi2Ta2O9
originates from anti-site defects, where the Bi3+ ions enter
A-sites, while Ba2+ are incorporated into (Bi2O2)2+ layers
(Fig. 19).198 X-ray and neutron diffraction investigations
have confirmed this assumption221,222. It was shown in calcu-
lations that when Ba2+ occupies the A-site exclusively, the
corresponding valence is larger than two and therefore
“overbonding” of the A-site cation occurs, whereas cation
disordering reduces this overbonding.221
When a bismuth ion enters an A-site, it can easily go off-
center (contrary to Ba2+) leading to local polarization and
stimulating the appearance of PNRs. Concurrently, the cat-
ion redistribution also leaves positive point charges on the
perovskite blocks where Bi3+ replaces Ba2+ and negative
point charges in the fluorite-like layers where Ba2+ replaces
Bi3+. The RFs resulting from these point charges as well as
mechanical stresses due to inhomogeneous cation distribution
effectively break up the long-range interaction and prevent
macroscopic ferroelectric ordering.
Analysis of the frequency dispersion of the dielectric per-
mittivity indicates some substantial differences between
BaBi2Nb2O9 and BaBi2Ta2O9 on the one hand and canonical
relaxors, like PMN, on the other. Namely, the freezing tem-
perature is much below the maximum in e(T) dependences,
Tm(105 Hz)  Tf ~ 350 K in BaBi2Nb2O9 [Ref. 199] against
~80 K in PMN. The activation energy, Ea, is about one
order of magnitude larger in comparison with the typical
value for PMN-based relaxors. On cooling, the relaxation
time distribution shifts to larger times, but without significant
broadening typical of canonical relaxors.199,202 These factors
point out a relatively small size of polar clusters and weak
interaction between them in Bi-layered relaxors with m = 2,
when only two perovskite layers are located between the
(Bi2O2)2+ layers. The growth of PNRs is probably restricted
to two dimensions, in the (a,b) plane. Therefore, they remain
small and the transition to a NR state is delayed. The situa-
tion can be different in BLSF compounds with larger m,
where the larger number of perovskite layers may result in a
crossover from quasi-two-dimensional to three-dimensional
growth of PNRs. Indeed, BaBi4Ti4O15 and Ba2Bi4Ti5O18
show DTm, Tm  Tf, and Ea comparable to values observed
for PMN and related relaxors. Moreover, the polarization
hysteresis loops below Tf indicate that a transition to the fer-
roelectric state occurs at low temperatures. The interactions
between PNRs are substantially enhanced as compared to
BaBi2Nb2O9 and BaBi2Ta2O9.
Structural analysis shows that Bi3+ and Ba2+ ions have
specific anionic environments in BaBi4Ti4O15 and cannot
share identical atomic positions.223 The strong overbonding
observed for the Ba2+ cations on A-sites reflects structural
stresses in the structure.221,223 A certain stress relief can be
assured considering local configurations with compositional
fluctuations, i.e. Ba- and Bi-rich zones.223 Existence of such
regions with different degrees of structural distortion, where
Ba-rich zones are potentially nonpolar, can also be responsi-
ble for the relaxor behavior.
In K0.5La0.5Bi2Nb2O9 and K0.5La0.5Bi2Ta2O9, selected area
electron diffraction reveals a local 1:1 cationic ordering on
A-sites, which is driven by the substantial size and charge
differences between K+ and La3+ (ionic radius RLa3+ =
0.136 nm and RK+ = 0.164 nm).206 It was argued that simi-
lar to PMN and related compounds, where B-site ordering
has been observed, these chemically ordered regions might be
the origin of local RFs promoting the relaxor behavior in
these BLSF compounds.207
January 2012 Lead-Free Relaxors
The mechanism of the transformation from the relaxor
into ferroelectric behavior in the case of substitution of Bi3+
with lanthanides in fluorite-like (Bi2O2)2+ layers yet remains
unclear. Raman spectroscopy revealed a pronounced cation
disorder and related compositional inhomogeneity in the
fluorite-like layers with increasing La3+ content.211,213,224,225
It seems that such type of disorder deteriorates ferroelectric
long-range ordering in BLSF compounds.225 This is likely
related to the fact that in spite of the same charges and very
similar ionic radii of Bi3+ and La3+, the latter ion does not
possess a stereochemically active lone electron pair. Conse-
quently, La3+ would prefer to be more central than the Bi3+
position. Such centralization would result in an additional
need for contraction of the ideal a-parameter of the fluorite-
like unit.226 This destabilizes the perfect [BiLaO2]2+ disorder
resulting in a marked preference of La3+ for the A-site of
the perovskite block instead.226 In such a way, La-doping
enhances the disorder on the A-site, which to a certain extent
even exists in ferroelectric BLSF compounds being related to
anti-site defects, when part of the A-cations enter (Bi2O2)2+
layers, while the Bi3+ ions occupy A-sites.221,222
(3) Uniaxial Relaxors with Tetragonal Tungsten Bronze
Structure
Relaxor behavior has been observed in a number of materials
crystallizing in the tetragonal tungsten bronze (TTB) struc-
ture.15,16 The TTB structure A12A24C4B12B28X30 consists of
layers of BX6 octahedra sharing corners to form three types
of interstitial channels: square A1, pentagonal A2, and trian-
gular C channels (Fig. 20).227 The pentagonal and square
channels are usually occupied by large alkali, alkaline earth,
and rare earth cations (e.g., Na+, K+, Sr2+, Ba2+, La3+,
Bi3+, etc.). The smaller C channels are either empty or filled
by small cations like Li+. The highly charged cations of
transient metals, like Ti4+, Nb5+, and Ta5+, reside on octa-
hedral B-sites. One of the B-site cations in the octahedral site
has to be ferroelectrically active. The presence of crystallo-
graphically nonequivalent A- and B-sites as well as extra C-
sites provides extra degrees of freedom for the manipulation
of the structure offering huge flexibility of composition and
properties.16
The TTB-relaxors display the following properties similar
to other relaxors:
1. Typical Tm(f) shift following the Vogel–Fulcher law.
2. Dynamic PNRs much above Tm.
3. Coexistence of static and dynamic PNRs at Tm.
Fig. 20. Tetragonal tungsten bronze crystal structure,
Sr0.61Ba0.39Nb2O6, A1-sites are occupied by Sr, A2-sites by Sr and
Ba, among six A-sites one is vacant (here the A2-site); triangular C-
channels are empty.
17
However, contrary to the lead-free perovskite relaxors
1. the low-temperature state is rather long-range than
short-range-ordered
2. A-site disorder plays the crucial role in uniaxial TTB
relaxors, while
3. polar behavior is still attributed to the B-site cations
like in the structurally other systems.
Like in materials with the perovskite and Aurivillius-type
structures, a prerequisite of relaxor behavior in TTB com-
pounds is structural disorder related to the occupation of the
same crystallographic site by different ions (Table V). This
may be A-site disorder, like in Sr5xBa5(1-x)(Nb10O30 (x 
0.6)41,228 and Ba2Bi22Nb10O30 (Ref.229) (here  denotes a
vacant site) when Sr and Ba (Bi and Ba) occupy the A2-site,
or B-site disorder, like in Ba6M3+Nb9O30 (M = Ga, Sc, In,
or Co),230–232 Ba2ReTi3Nb2O15 (Re = Bi3+ or La3+),233 and
Sr2K(Nb1xTax)5O15 (0.16  x  1).16 The relaxor behav-
ior was also reported for oxyfluorides with the TTB struc-
ture, where the substitution of F for O2 is coupled with a
cationic substitution to ensure electroneutrality. In this case,
relaxor behavior is provoked either by cationic disorder like
in BaNa2Nb5O14F15 with the A2-site being filled both by Ba2+
and Na+ or by solely anionic disorder like in K3LiNb5O14F
(here K+ and Li+ occupy the A- and C-sites, respectively).16
Among the most studied relaxor TTB systems is Sr5x
Ba5(1x) Nb10O30 or otherwise SrxBa1xNb2O6 (SBN). For
SBN, the A1 positions are occupied by Sr2+ only, the A2-
sites are filled with both Sr2+ and Ba2+, whereas the C chan-
nels remain empty (Fig. 20). As there are only five Sr and Ba
atoms for six A1 and A2 positions, one of the A-sites
remains unoccupied.234
Upon cooling, SBN undergoes an order–disorder phase
transition from a paraelectric 4/mmm to a polar 4mm state
with the spontaneous polarization oriented parallel to the c-
axis.235 The polarization is caused by the off-center displace-
ments of the B-site (Nb5+) cations. For increasing Sr/Ba
molar ratio, a crossover from ferroelectric to relaxor behavior
occurs in compositions with x > 0.6.41,228 Single crystal
SBN40 (x = 0.40) exhibits a relatively sharp peak in the tem-
perature dependence of e(T), whose position, Tm  410 K,
does not shift with probing frequency as is typical of ferroelec-
trics. The Tm coincides with the Curie temperature, TC.228,236
For SBN61 and SBN75 single crystals, the maximum of the
dielectric susceptibility is much broader and the peak position
shifts to lower temperatures when decreasing the frequency of
the probing field as is typical of relaxors.228,237
The crossover to the relaxor behavior in SBN with larger
x is considered to be related to an enhancement of structural
and related charge disorder.41,238 This disorder is primarily
due to randomly distributed vacancies on A-sites. The miss-
ing charges on these vacancies are the most intense sources
of RFs. Occupation of A2-sites by different cations intro-
duces disorder of the oxygen ion positions due to different
Ba–O and Sr–O bonding lengths, whereas the presence of
vacancies on both A1 and A2-sites enhances this disorder.234
Accommodation misfits of the different oxygen octahedra
give rise to local buckling and tilting deformation creating
localized electric multipole moments. These are also sources
of random electric fields. More structural disorder results in
stronger RFs. From statistical considerations, the most
ordered structure is expected in SBN20, where all A2-sites
are occupied solely by Ba2+ cations, while the Sr2+ ions and
vacancies are randomly distributed on the A1-sites. In other
compositions the entropy of the cation distribution, which is
a measure of the structural disorder, increases with increasing
Sr/Ba ratio and reaches a maximum level at x ~ 0.65.238 It
has also been argued that vacancies on A2-sites have a stron-
ger impact on the polar properties of SBN, than those at
A1-sites.238 As the vacancy tends to increasingly occupy the
A2-sublattice as x increases,238,239 the corresponding “active”
charge disorder will be enhanced at large Sr2+ content. The
18 Journal of the American Ceramic Society—Shvartsman and Lupascu Vol. 95, No. 1

Table V. Dielectric and Relaxor Characteristics of Some Relaxors with the Tetragonal Tungsten Bronze Structure. Parameters
Have the Same Meaning as for Table I
Composition Tm, K (103 Hz) DTm, K (102–105 Hz) Tf, K Ea, eV f0, Hz Ref.

A-site K2LaNb5O15 165 22 16

disorder K2BiNb5O15 220 80 15
BaLaNb5O15 203 55 229
BaBiNb5O15 295 75 107 0.33 4.7 9 1011 229
BaLa2/31/3NaNb5O15 210 34 16
Sr3Ba2Nb10O30 320 12 299 0.028 5.8 9 109 237
Sr3.75Ba1.25Nb10O30 361 3 347 0.014 8 9 108 253
B-site Ba2Bi(Nb3Ti2)O15 200 30 229
disorder Ba2La(Nb3Ti2)O15 190 20 233
Sr2La(Nb3Ti2)O15 221 14 190 0.046 2.1 9 1010 283
Sr2Nd(Nb3Ti2)O15 243 35 148 0.17 8.5 9 1011 260
Ba6GaNb9O30 80 20 56 0.077 6.7 9 1011 230, 231
Ba6InNb9O30 280 50 158 0.198 4.1 9 1011 230, 231
Ba6ScNb9O30 230 25 153 0.105 9.1 9 1010 230, 231
Ba6CoNb9O30 135 70 20 0.31 3.6 9 1013 232
Sr2Na(Nb1xTax)5O15 222 (x = 0.4) 20 (x = 0.40) 15
(0.40  x  1) 120 (x = 1) 25 (x = 1)
Sr2K(Nb1xTax)5O15 263 (x = 0.16) 21 (x = 0.16) 16
(0.16  x  1) 80 (x = 1)
Ba2K(Nb1xTax)5O15 268 (x = 0.35) 16 (x = 0.35) 15
(0.35  x  1) 80 (x = 1)
A- and Ba5SmTi3Ta7O30 150 25 117 0.045 4.1 9 109 284
B-site Sr5LaNb7Ti3O30 240 20 184 0.11 5.3 9 1012 261
disorder
X-site K3LiNb5O14F 210 40 16
disorder
A- and Ba4.51.5Nb5O29F 175 30 16
X-site Ba2xNa1+xNb5O15xFx 250 (x = 0.31) 40 (x = 0.31) 285
disorder (0.31  x  1) 140 (x = 1) 17 (x = 1)
Sr2xK1+xNb5O15xFx 290 (x = 0.20) 15 (x = 0.2) 15
(0.20  x  1) 112 (x = 1) 16 (x = 1)
B- and Ba2NaNb5xTixO15xFx 265 (x = 0.31) 15 (x = 0.31) 285
X-site (0.31  x  0.50) 168 (x = 0.50) 30 (x = 0.50)
disorder
 denotes vacant site.

enhancement of structural and charge disorder is reflected in
changes of the polar structure of SBN.238
Even for ferroelectric SBN compositions, the antiparallel
domains are substantially distorted having fractal-shape
boundaries.240 They are strongly anisotropic with a size
along the polar axis of several tens of micrometers, which is
about two orders of magnitude larger than that perpendicu-
lar to the polar axis.240,241 The shape of the domains espe-
cially in the plane normal to the polarization vector is
dictated by the random electric fields, which pin and distort
domain walls, thus forming a complex pattern. The polar dis-
order is enhanced in compositions with larger x correspond-
ing to a strengthening of RFs with increasing Sr content
(Fig. 21). Namely, the domains become smaller; the mean
domain size in SBN75 is only about 75 nm.240 Simulta-
neously, the fractal dimension of domain boundaries
increases, which indicates more pronounced “irregularity” of
the polar structures in relaxor SBN.238
Like in other relaxor systems, the relaxor behavior of SBN
is attributed to the existence of PNRs, which is evidenced
above Tm by the measurements of the optical index of refrac-
tion,242 birefringence,243 and dynamic244 and inelastic Brill-
ouin245 light scattering. The uniaxial character of the order
parameter together with the existence of the quenched RFs
due to the randomly distributed A-site vacancies allows con-
sidering SBN to be a member of the three-dimensional ran-
dom-field Ising model (3D-RFIM) universality class.29,246 In
this case, contrary to the perovskite relaxors, a transition to
a long-range-ordered ground state is predicted below the
Curie temperature, TC. In reality, however, due to extreme
critical slowing-down, the dynamic PNRs are expected to
merely transform into a random field controlled metastable
domain state.247 Indeed, statistics and topology of experi-
mentally observed domain structures in SBN below the tran-
sition temperature corroborate the theoretical predictions for
RFIM systems.240
The evolution of PNRs in the vicinity of the transition
temperature has been probed by piezoresponse force micros-
copy and dielectric spectroscopy.240,247,248 The transition
from the high-temperature ER state to the low-temperature
long-range ferroelectric state does not take place at a fixed
temperature. There is a certain temperature range above TC
where the system contains both small dynamic and large
quasi-static PNRs. The latter ones are precursors of domains
in the low-temperature ferroelectric state. The intermediate
state has a nonergodic character, which was verified by the
observation of aging (via an isothermal decay of the dielec-
tric permittivity) in the same temperature range above TC,
where frozen PNRs were visualized.248,249 This aging is
related to isothermal growth of quasi-static PNRs at the
expense of the dynamic ones.
The appearance of frozen PNRs in the close vicinity above
TC may explain a long time disputed controversy between
the experimentally observed critical behavior in 3D-RFIM
systems and theoretical predictions.247,250 Namely, the values
of critical exponents found in experiments are close to those
theoretically predicted for the two-dimensional Ising model,
but deviate strongly from those of the 3D-RFIM sys-
tems.250,251 Kleemann et al. suggested that the appearance of
quasi-stable PNRs excludes true equilibrium criticality when
January 2012 Lead-Free Relaxors
(a)
(c)
Fig. 21. Piezoresponse force microscopy images taken on c-cut SrxBa1xNb2O6 single crystals below the transition temperatures. Compositions
with x = 0.40 (a) and 0.50 (b) show the ferroelectric behavior, while those with x = 0.61 (c) and 0.75 (d) the relaxor one (Ref. 240).
approaching TC.247 While these large PNRs are frozen on a
finite time scale, the unfrozen interfaces can be considered as
regions with very short-ranged correlation of RFs, which are
not able to select sizable polar clusters via field energy gain.
In these essentially 2D regions forming a percolating network
through the sample, a phase transition may take place under
the constraint of a weakly disordered quasi-staggered field.
At the same time, the 2D Ising model criticality of the inter-
face system is preserved.247
The relaxor properties become more pronounced in SBN
doped by trivalent cations, like rare-earth elements on the A-
site252,253 or by Cr3+ on the B-site254 probably reflecting
stronger RF activity related to heterovalent doping. On the
other hand, the substitution of either Sr2+ or Ba2+ by Na+
in Sr0.6xBa0.4Na2xNb2O6 (x  0.15) and Sr0.6Ba0.4yNa2y
Nb2O6 (y  0.1), respectively, results in the suppression of
relaxor properties and stabilization of the ferroelectric
state.255 In this case, each Sr/Ba substitution by 2Na cations
reduces the disorder in the crystal lattice due to the reduction
of the vacancy concentration.
Recently, increasing interest has reached TTB relaxors with
disorder in the B-sites. It was observed that among the family
of materials with the general formula Ba2MTi2Nb3O15
(M = Bi3+, La3+, Nd3+, Sm3+, Gd3+),233,256,257 the com-
pounds with large M cations, Bi3+ and La3+, exhibit relaxor
properties, whereas those with smaller M = Nd3+, Sm3+,
Gd3+ behave like classical ferroelectrics. X-ray diffraction
confirmed that Ba2+ and M occupy A2 and A1-sites, respec-
tively, while the B-sites are randomly filled with Nb5+ and Ti4
+
cations. Similar to other tungsten bronzes, the polarization
is caused by off-centrality of the B-cations. The ferroelectric
behavior of Ba2MTi2Nb3O15 with smaller M-ions indicates
that the B-site disorder per se is probably not enough to
ensure relaxor behavior in these compounds. The electron dif-
fraction experiments reveal that the ferroelectric and relaxor
Ba2MTi2Nb3O15 have a commensurate and incommensurate
19
(b)
(d)
modulated structure, respectively. While the incommensurate
modulation has been often reported for TTB structures, the
commensurate phase has not been observed before. It was
argued that both the type of the oxygen octahedra tilting and
the periodicity of the tilting modulation (commensurate or
incommensurate) are determined by the competing bonding
requirements of the cations in the pentagonal (Ba) and square
(M) tunnels.256 The commensurate TTB phase is considered
to be more favorable when A1-sites are occupied by ions with
small ionic radii (  1.3 Å).233 The lack of commensurate peri-
odicity in Ba2BiTi2Nb3O15 and Ba2LaTi2Nb3O15 may contrib-
ute to the disruption of long-range dipolar coupling in these
compositions resulting in relaxor rather than classic ferroelec-
tric behavior.233 According to Zhu et al., the polar behavior
in this family of tungsten bronzes is dominated not only by
the ionic radius of the rare-earth elements, but rather by the
radius difference between A1 and A2 cations.258 These argu-
ments were supported by investigation of (BaxSr1x)2Nd-
Ti2Nb3O15 ceramics showing crossover from the ferroelectric
to relaxor behavior as the radius difference between A1 (Nd)
and A2 (Ba/Sr) sites decreases.259
Analysis of the relaxor behavior of the tungsten bronzes
family Ba6MNb9O30 (M = Ga3+, Sc3+, or In3+) reveal that
all characteristic temperatures, including the freezing temper-
ature and temperature of the maximum of the dielectric per-
mittivity, increase with increasing radius of the M cation (see
Table V).230,231 Such a trend correlates with the increased
tetragonality of the unit cell, and hence, with an enhance-
ment of the local polarization. The latter is mainly related to
the displacement of the B1-site cations (M or Nb) along the
c-axis.231 Taking into account that the ratio of B1 to B2 sites
is 1:4 in the TTB unit cell, Rotaru et al. have argued that
these materials have a dilute dipolar structure arising from
“polar” chains of B1 ions spatially separated within a weakly
polar matrix formed by the crystallographic distribution of
the B2-sites.231 Correspondingly, the formation of the low-
20 Journal of the American Ceramic Society—Shvartsman and Lupascu
temperature domain state as in SrxBa1xNb2O6 is considered
to be restricted. Furthermore, it was suggested that the
behavior of the Ba6MNb9O30 compounds is more close to
the dipolar glasses than to the relaxor ferroelectrics.231 The
linear shape of P(E) dependences as well as a presumable
absence of PNRs seem to confirm this supposition.
Some TTB ceramics show rather complex temperature
dependences of the dielectric permittivity with two (some-
times even more) anomalies. Often the low-temperature
anomaly shows relaxor-like frequency dispersion, while the
high-temperature one does not. The origin of these anomalies
is still debated and might be different for different TTB fami-
lies. The anomalies were observed in some ceramics with
compositions intermediate between compounds with ferro-
electric and relaxor behavior, for example, Sr4Nd2Ti4Nb6O30
(Ref. 260) or Ba2Pr0.6Nd0.4FeNb4O16 (Ref. 104) [Fig. 11(b)].
It was supposed that the high-temperature maximum corre-
sponds to the ferroelectric Curie temperature, while the low-
temperature anomaly is associated with the freezing of
PNRs. While Castel et al. have proposed the coexistence of
regions with long and short range orders,104 probably due to
nanoscale compositional segregation, Zhu et al. have sug-
gested that the long-range-ordered state is disrupted into
polar clusters due to a transition to an incommensurate state
on cooling.258 The low-frequency relaxation might also be
related to a freeze-out of the polarizability in the (a,b)-
plane,261 for example, related to concerted rotations of
oxygen octahedra.262 While the ferroelectric properties are
determined by ionic displacements along the polar c-axis,
concerted rotations of oxygen octahedra, which may carry
weaker dipole moments, can give rise to the isotropic dielec-
tric response within the (a,b)-plane.262
The reports on a possible anisotropy of the relaxor prop-
erties in the uniaxial systems are controversial. Simon et al.
have reported that the Sr0.75Ba0.25Nb2O6 single crystals
behave like relaxors along the [001] direction, while exhibit-
ing a ferroelectric transition in the [100] direction in the same
temperature range.263 On the contrary, qualitatively, the
same relaxor behavior was found for the [001] and [100]
directions of Sr0.61Ba0.39Nb2O6 single crystals, (V. V.
Shvartsman, unpublished data) as well as for the textured
Sr0.63Ba0.37Nb2O6 ceramics with the grains-oriented preferen-
tially along and normal to the polar axis, respectively.264
At the end of this section, we would like to point out that
contrary to the lead-free perovskite relaxors, where B-site
disorder is most important for inducing the relaxor behavior,
the A-site disorder plays the crucial role in uniaxial TTB
relaxors, in spite of the fact that the polar behavior in both
cases is attributed to B-site cations.
IV. Technological Perspectives
(1) Dielectric Properties
Large and relatively temperature-insensitive dielectric permit-
tivity makes relaxors obvious candidates for capacitors appli-
cations. Of particular interest are compounds showing a
maximum of the dielectric constant e at room and elevated
temperatures. There is demand for the latter materials, for
example, in automotive and aerospace industry. While most
of BaTiO3-derived relaxors exhibit a peak of the dielectric
permittivity below room temperature, systems based on
KNN or BNT as well as a number of relaxors with the Auri-
villius structure are promising candidates for high-temperature
applications. For example, 0.96K0.5Na0.5NbO3–0.04BiScO3139
and 0.82(0.94Bi1/2Na1/2TiO3–0.06BaTiO3)–0.18K0.5Na0.5NbO3175
relaxor ceramics were shown to have permittivity values of
over 2000 with variation of De/e less than 10% in the tempera-
ture range from 100°C to 300°C (Fig. 22). A large, tempera-
ture stable dielectric constant combined with high electrical
resistivity is necessary for the development of high-energy den-
sity capacitors, which are used in power electronic applica-
tions, such as filtering, voltage smoothing, dc blocking, power
Vol. 95, No. 1
Fig. 22. Temperature dependence of the dielectric permittivity of
the 0.96K0.5Na0.5NbO3–0.04BiScO3 ceramic measured at a frequency
of 10 kHz. Reprinted with permission from Ref. 139. Copyright
2008, American Institute of Physics.
conditioning, electromagnetic interference suppression, com-
mutation in power electronic circuits, etc.51 Usually high-
energy density applications demand high permittivity, low hys-
teresis loss, and high dielectric breakdown strength. Ogihara
et al. have shown that relaxor BaTiO3–BiScO3 ceramics are
feasible for such applications. In particular, they reported that
an energy density of about 6 J/cm3 at a field of 73 kV/cm can
be achieved in single layer 0.7BaTiO3–0.3BiScO3 capacitors,
which is superior to the characteristic of commercial capaci-
tors.51 Moreover, the high-energy density values were con-
firmed up to 300°C making this material an attractive
candidate for applications at elevated temperatures.51
The dc electric-field tuned dielectric materials are candi-
dates for microwave applications, including voltage-con-
trolled oscillators, tunable filters, phase shifters, etc.265–267
Usually the materials have to show a large dielectric tuna-
bilty, =100%·[e(0)e(E)]/e(0), and low dielectric loss. Among
the most studied compounds are presently ferroelectric (Ba,
Sr)TiO3268 and (Pb,Sr)TiO3266. However, recently, the lead-
free relaxor systems Ba(Zr,Ti)O350,269and Ba(Sn,Ti)O3270
have attracted, increased attention due to their excellent
characteristics. The BTZr (x = 0.30) ceramics exhibit tunabil-
ity as high as 45% (at E = 40 kV/cm) and correspondingly
low loss, tgd ~ 0.002 at room temperature.269 The tunability
is even higher at lower temperatures (up to 90% at 230 K).
For increasing Zr content, the tunability decreases, but still
remains above 20% for BTZr (x = 0.45).50
(2) Electromechanical Properties
While ferroelectric Ba(Ti,Zr)O3 ceramics with a moderate Zr
content (~5%) exhibit excellent piezoelectric properties,
d33 ~ 236 pC/N and field-induced strain ~0.18% (at 40 kV/
cm),271 the relaxor BT-based compounds with larger Zr con-
tent usually show poor electromechanical response. Neverthe-
less, a progressive change of the piezoelectric coefficient with
composition may be used for fabrication of bending actua-
tors based on monolithic ceramics with a gradient of compo-
sition, for example, BaTi1xSnxO3 (0.075  x  0.15).272
The situation is different for bismuth sodium titanate-
based relaxors. The (1x)BNT–xBT solid solutions close to
the morphotropic phase boundary between the rhombohedral
and tetragonal ferroelectric phases (x ~ 0.06–0.08) show good
piezoelectric properties, d33 ~ 150 pC/N.126 The electrome-
chanical response is drastically enhanced by a partial substi-
tution of BNT by KNN. The 0.92Bi0.5Na0.5TiO3–0.06BaTiO3
–0.02K0.5Na0.5NbO3 ceramics can deliver giant strain
~0.45% (at E = 80 kV/cm) under both unipolar and bipolar
electrical loading,53 surpassing the maximum strain values
obtained in commercial ferroelectric Pb(Zr,Ti)O3 ceramics
(Fig. 23). It was suggested that these superior properties are
due to the relaxor character of the BNT–BT–KNN com-
pounds.176 The origin of the giant strain is mostly a conse-
quence of the disappearance of the remnant strain due to the
presence of nonpolar regions in the relaxor phase at zero
electric field. These regions destabilize and randomize an
electrically induced ferroelectric order and bring the system
January 2012 Lead-Free Relaxors
Fig. 23. Unipolar field-induced strain in (1x)Bi0.5Na0.5TiO3–
0.06BaTiO3–xK0.5Na0.5NbO3 ceramics with x = 0, 0.02, and 0.04 in
comparison with a unipolar strain–electric-field curve of commercial
soft PZT. Reprinted with permission from Ref. 53. Copyright 2007,
American Institute of Physics.
back to its unpoled state once the applied electric field is
removed.176
(3) Optical Properties
Some relaxors with TTB structure, like Sr1xBaxNb2O6 show
excellent electrooptic properties. Large linear electro-optic
coefficients, r33 = 1340 9 1012 m/V for composition with
x = 0.75, make them potential materials for light modulation
and laser frequency multiplication required for optical com-
munication systems.227 The SBN single crystals furthermore
exhibit a substantial photorefractive effect, optically induced
change of refractive index, which can be used in holographic
memory, phase conjugation, image amplification, optical
resonators, and other nonlinear optical applications.54
V. Conclusions
Lead-free relaxor ferroelectrics offer all property features one
can possibly think of in a ferroelectric relaxor system. Their
basic features are summarized in Fig. 24. Here, we assume
that the inherent symmetry of the local order parameter, i.e.
polarization, results in a corresponding shape anisotropy of
the polar nanoregions. Indeed, strongly anisotropic needle-
like nano-domains have been observed in the one-dimen-
sional relaxors like (Sr,Ba)Nb2O6 with tetragonal tungsten
bronze structure.273 It was suggested that in 2D relaxors with
Aurivillius structure growth of PNRs is restricted to the
plane of the perovskite layer, but no experimental proves
have been given so far. It is often accepted that PNRs in 3D
relaxor, for example, in PbMg1/3Nb2/3O3, are of ellipsoidal
shape.9,274 However, there are evidences of planar-type corre-
lation of local polarization in some relaxors with the perov-
skite structure.275–277 For example, results of three-
dimensional mapping of diffuse X-ray scattering intensities
performed for PbZn1/3Nb2/3O3–PbTiO3 single crystals indi-
cate that PNRs have a pancake-like shape resulting from
{110} planar correlations of <1–10> polarizations.275 It was
suggested that <111>-polarized PNRs could be a result of
the overlap of three different {110}-type pancakes.275 Local
symmetry of PNRs may be different for different relaxor sys-
tems, for example, rhombohedral or tetragonal for BaTiO3
and Bi1/2Na1/2TiO3-based relaxors, respectively. It is interest-
ing, however, that one, two, and three dimensional systems
offer surprisingly similar material behavior at least at the
macroscopic scale.
The relaxor state in all systems relies on some atomic and
field disorder. For each of the systems, the structural or
atomic origin may be different: site disorder, substitutional
21
Fig. 24. The three families of relaxor ferroelectrics with different
dimensionality of the order parameter (polarization) and different
anisotropy of the respective polar nanoregions. For relaxors with the
perovskite structure PNRs with rhombohedral or tetragonal
symmetry of polarization may exist depending on the individual
compound.
charge disorder, size disorder, or even at nominally the same
effective ionic charge a difference in the existence of a lone
electron pair at an ion or not may be sufficient sources of
disordering. Polar nanoregions generated from such disorder
are found in all relaxors. Strong anisotropy of macroscopic
material properties does not translate into comparable
anisotropy of the relaxor properties. Thus, all forms of
longer range structural ordering do not directly correlate
with the polar nanostate. It is thus inherently restricted to
atomic scale processes irrespective of the overall crystal sym-
metry. The large variety of lead-free relaxor systems has
allowed us to arrive at such a clear statement.
Large and potentially “giant” material parameters have
been found and device technology is waiting for the final sur-
passing of the output thresholds set by the lead-containing
compositions. Fundamentally, there is no reason why the lat-
ter should continue to dominate device technology on the
long run.
References
1
Y. Murakami, H. Kasai, J. J. Kim, S. Mamishin, D. Shindo, S. Mori, and
A. Tonomura, “Ferromagnetic Domain Nucleation and Growth in Colossal
Magnetoresistive Manganite,” Nature Nanotechnol., 5, 37–41 (2010).
2
R. P. Rairigh, G. Singh-Bhalla, S. Tongay, T. Dhakal, A. Biswas, and A.
F. Hebard, “Colossal Magnetocapacitance and scale-Invariant Dielectric
Response in Phase-Separated Manganites,” Nat. Phys., 3, 551–5 (2007).
3
J. Lee, K. Fujita, K. McElroy, J. A. Slezak, M. Wang, Y. Aiura, H.
Bando, M. Ishikado, T. Masui, J.-X. Zhu, A. V. Balatsky, H. Eisaki, S. Uch-
ida, and J. C. Davis, “Interplay of Electron–Lattice Interactions and Super-
conductivity in Bi2Sr2CaCu2O8+8” Nature, 442, 546 (2006).
4
Z. Kutnjak, J. Petzelt, and R. Blinc, “The Giant Electromechanical
Response in Ferroelectric Relaxors as a Critical Phenomenon,” Nature, 441,
956–9 (2006).
5
E. Dagotto, “Complexity in Strongly Correlated Electronic Systems,”
Science, 309, 257–62 (2005).
6
G. A. Smolenskii and V. A. Isupov, “Segnetoelektricheskie svoistva tver-
dykh rastvorov stannata bariya v titanate bariya,” Zh. Tekh. Fiz., 24, 1375–86
(1954).
7
G. A. Smolenskii, V. A. Isupov, A. I. Agranovskaya, and S. N. Popov,
“Ferroelectrics with Diffuse Phase Transitions,” Sov. Phys. Solid State, 2,
2584–94 (1961).
8
L. E. Cross, “Relaxor Ferroelectrics,” Ferroelectrics, 76, 241–67 (1987).
9
A. A. Bokov and Z. –G. Ye, “Recent Progress in Relaxor Ferroelectrics
with Perovskite Structure,” J. Mater. Sci., 41, 31–52 (2006).
22 Journal of the American Ceramic Society—Shvartsman and Lupascu
10
A. J. Bell, “Calculations of Dielectric Properties from the Superparaelec-
tric Model of Relaxors,” J. Phys. Condens. Matter, 5, 8773–92 (1993).
11
S. -E. Park and T. R. Shrout, “Ultrahigh Strain and Piezoelectric Behavior
in Relaxor Based Ferroelectric Single Crystals,” J. Appl. Phys., 82, 1804–11
(1997).
12
K. Uchino, Piezoelectric Actuators and Ultrasonic Motors. Kluwer
Academic, Boston, 1996.
13
G. A. Samara, “The Relaxational Properties of Compositionally Disor-
dered ABO3 Perovskites,” J. Phys.: Condens. Matter, 15, R367–411 (2003).
14
R. A. Cowley, S. N. Gvasaliya, S. G. Lushnikov, B. Roessli, and G. M.
Rotaru, “Relaxing with Relaxors: A Review of Relaxor Ferroelectrics,” Adv.
Mater., 60, 29–327 (2011).
15
J. Ravez and A. Simon, “Some Solid State Chemistry Aspects of Lead-
Free Relaxor Ferroelectrics,” J. Sol. State Chem., 162, 260–5 (2001).
16
J. Ravez and A. Simon, “Lead-Free Relaxor Ferroelectrics with “TTB”
Structure,” C. R. Chimie, 5, 143–8 (2002).
17
G. Burns and F. H. Dacol, “Glassy Polarization Behavior in Ferroelectric
Compounds Pb(Mg1/3Nb2/3)O3 and Pb(Zn1/3Nb2/3)O3,” Solid State Commun.,
48, 853–6 (1983).
18
V. Westphal, W. Kleemann, and M. Glinchuk, “Diffuse Phase Transitions
and Random-Field-Induced Domain States of the “relaxor” Ferroelectric
PbMg1/3Nb2/3O3,” Phys. Rev. Lett., 68, 847–50 (1992).
19
M. E. Lines and A. M. Glass, Principles and Applications of Ferroelectrics
and Related Materials. Clarendon Press, Oxford, 1979.
20
S. B. Vakhrushev, B. E. Kvyatkovsky, A. A. Naberezhnov, N. M. Okuneva,
and B. P. Toperverg, “Glassy Phenomena in Disordered Perovskite-Like Single
Crystals,” Ferroelectrics, 90, 173–6 (1989).
21
A. Naberezhnov, S. Vakhrushev, B. Dorner, D. Strauch, and H. Moud-
den, “Inelastic Neutron Scattering Study of the Relaxor Ferroelectric PbMg1/3
Nb2/3O3 at High Temperatures,” Eur. Phys. J. B, 11, 13–20 (1999).
22
K. Hirota, S. Wakimoto, and D. E. Cox, “Neutron and X-Ray Scattering
Studies of Relaxors,” J. Phys. Soc. Jpn., 75, 111006 (2006).
23
G. Xu, G. Shirane, J. R. D. Copley, and P. M. Gehring, “Neutron Elastic
Diffuse Scattering Study of PbMg1/3Nb2/3O3,” Phys. Rev. B, 69, 064112 (2004).
24
D. La-Orauttapong, J. Toulouse, J. L. Robertson, and Z.-G. Ye, “Diffuse
Neutron Scattering Study of a Disordered Complex Perovskite PbZn1/3
Nb2/3O3 Crystal,” Phys. Rev. B, 64, 212101 (2001).
25
C. Stock, R. J. Birgeneau, S. Wakimoto, J. S. Gardner, W. Chen, Z.-G.
Ye, and G. Shirane, “Universal Static and Dynamic Properties of the Struc-
tural Transition in PbZn1/3Nb2/3O3,” Phys. Rev. B, 69, 094104 (2004).
26
M. Yoshida, S. Mori, N. Yamamoto, Y. Uesu, and J. M. Kiat, “TEM
Observation of Polar Domains in Relaxor Ferroelectric Pb(Mg1/3Nb2/3)O3,”
Ferroelectrics, 217, 327–33 (1998).
27
P. K. Davies and M. A. Akbas, “Chemical Order in PMN-Related Relax-
ors: Structure, Stability, Modification, and Impact on Properties,” J. Phys.
Chem. Solids, 61, 159 (2000).
28
W. Kleemann, “Random-Field Induced Antiferromagnetic, Ferroelectric
and Structural Domain States,” Int. J. Mod. Phys. B, 7, 2469–507 (1993).
29
W. Kleemann, “The Relaxor Enigma - Charge Disorder and Random
Fields in Ferroelectrics,” J. Mater. Sci., 41, 129–36 (2006).
30
I. Imry and S. K. Ma, “Random Field Instability of the Ordered State of
Continious Symmetry,” Phys. Rev. Lett., 35, 1399–401 (1975).
31
D. Viehland, S. J. Jang, L. E. Cross, and M. Wuttig, “Freezing of the
Polarization Fluctuations in Lead Magnesium Niobate Relaxors,” J. Appl.
Phys., 68, 2916–21 (1990).
32
A. E. Glazounov and A. K. Tagantsev, “Direct Evidence for Vögel–Ful-
cher Freezing in Relaxor Ferroelectrics,” Appl. Phys. Lett., 73, 856–8 (1998).
33
A. Levstik, Z. Kutnjak, C. Filipic, and R. Pirc, “Glassy Freezing in Relax-
or Ferroelectric Lead Magnesium Niobate,” Phys. Rev. B, 57, 11204–11 (1998).
34
E. V. Colla, Yu. E. Koroleva, N. M. Okuneva, and S. B. Vakhrushev,
“Long-Time Relaxation of the Dielectric Response in Lead Magnoniobate,”
Phys. Rev. Lett., 74, 1681–4 (1995).
35
E. V. Colla, L. K. Chao, M. B. Weissman, and D. Viehland, “Aging
in a Relaxor Ferroelctric: Scaling and Memory Effects,” Phys. Rev. Lett., 85,
3033–6 (2000).
36
Z. Kutnjak, C. Filipic, R. Pirc, A. Levstik, R. Farhi, and M. El Marssi,
“Slow Dynamics and Ergodicity Breaking in a Lanthanum-Modified Lead
Zirconate Titanate Relaxor System,” Phys. Rev. B, 59, 294–301 (1999).
37
Z. -G. Ye and H. Schmid, “Optical, Dielectric and Polarization Studies of
the Electric Field-Induced Phase Transition in Pb(Mg1/3Nb2/3)O3 [PMN],”
Ferroelectrics, 145, 83–108 (1993).
38
T. Kim, J. N. Hanson, A. Gruverman, A. I. Kingon, and S. K. Streiffer,
“Ferroelectric Behavior in Nominally Relaxor Lead Lanthanum Zirconate
Titanate Thin Films Prepared by Chemical Solution Deposition on Copper
Foil,” Appl. Phys. Lett., 88, 262907 (2006).
39
F. Chu, I. M. Reaney, and N. Setter, “Spontaneous (Zero-Field) Relaxor-
to-Ferroelectric-Phase Transition in Disordered Pb(Sc1/2Nb1/2)O3,” J. Appl.
Phys., 77, 1671–6 (1995).
40
O. Noblanc, P. Gaucher, and G. Calvarin, “Structural and Dielectric
Studies of Pb(Mg1/3Nb2/3)O3-PbTiO3 Ferroelectric Solid Solutions Around the
Morphotropic Boundary,” J. Appl. Phys., 79, 4291–7 (1996).
41
A. M. Glass, “Investigation of the Electrical Properties of Sr1-xBaxNb2O6
with Special Reference to Pyroelectric Detection,” J. Appl. Phys., 40, 4699–713
(1969).
42
B. Dkhil, J. M. Kiat, G. Calvarin, G. Baldinozzi, S. B. Vakhrushev, and
E. Suard, “Local and Long Range Polar Order in the Relaxor-Ferroelectric
Compounds PbMg1/3Nb2/3O3 and PbMg0.3Nb0.6Ti0.1O3,” Phys. Rev. B, 65,
024104 (2002).
Vol. 95, No. 1
43
F. M. Jiang and S. Kojima, “Relaxation Mode in 0.65Pb(Mg1/3Nb2/3)O3-
0.35PbTiO3 Relaxor Single Crystals Studied by Micro-Brillouin Scattering,”
Phys. Rev. B, 62, 8572–5 (2000).
44
V. V. Shvartsman and A. L. Kholkin, “Domain Structure of 0.8PbMg1/3
Nb2/3O3-0.2PbTiO3 Studied by Piezoresponse Force Microscopy,” Phys. Rev.
B, 69, 014102 (2004).
45
G. Xu, H. Hiraka, G. Shirane, and K. Ohwada, “Dual Structures in (1-x)
Pb(Zn1/3Nb2/3)O3-xPbTiO3 Ferroelectric Relaxors,” Appl. Phys. Lett., 84, 3975
–7 (2004).
46
G. Xu, D. Viehland, J. F. Li, P. M. Gehring, and G. Shirane, “Evidence
of Decoupled Lattice Distortion and Ferroelectric Polarization in the Relaxor
System PMN-xPT,” Phys. Rev. B, 68, 212410 (2003).
47
V. V. Kirillov and V. A. Isupov, “Relaxation Polarization of PbMg1/3Nb2/3
O3 (PMN) – a Ferroelectric with a Diffused Phase Transition,” Ferroelectrics,
5, 3–9 (1973).
48
R. Blinc and R. Pirc, “Spherical Random-Bond–Random-Field Model of
Relaxor Ferroelectrics,” Phys. Rev. B, 60, 13470–8 (1999).
49
EU-Directive 2002/95/EC, “Restriction of the Use of Certain Hazardous
Substances in Electrical and Electronic Equipment (RoHS),” Off. J. Eur.
Union, 46 [L37] 19–23 (2003).
50
T. Maiti, R. Guo, and A. S. Bhalla, “Enhanced Electric Field Tunable
Dielectric Properties of BaZrxTi1-xO3 Relaxor Ferroelectrics,” Appl. Phys.
Lett., 90, 182901 (2007).
51
H. Ogihara, C. A. Randall, and S. Trolier-McKinstry, “High-Energy
Density Capacitors Utilizing 0.7BaTiO3–0.3BiScO3 Ceramics,” J. Am. Ceram.
Soc., 92, 1719–24 (2009).
52
J. R. Gomah-Pettry, S. Said, P. Marchet, and J. –P. Mercurio, “Sodium-
Bismuth Titanate Based Lead-Free Ferroelectric Materials,” J. Eur. Ceram.
Soc., 24, 1165–9 (2004).
53
S. –T. Zhang, A. B. Kounga, E. Aulbach, H. Ehrenberg, and J. Rödel,
“Giant Strain in Lead-Free Piezoceramics Bi0.5Na0.5TiO3-BaTiO3-
K0.5Na0.5NbO3,” Appl. Phys. Lett., 91, 112906 (2007).
54
M. D. Ewbank, R. R. Neurgaonkar, W. K. Gory, and J. Feinberg,
“Photorefractive Properties of Strontium-Barium Niobate,” J. Appl. Phys., 62,
374–80 (1987).
55
B. Wul, “Barium Titanate – A New Ferroelectric,” Nature, 157, 808 (1946).
56
A. von Hippel, “Ferroelectricity, Domain Structure, and Phase Transitions
of Barium Titanate,” Rev. Mod. Phys., 22, 221–37 (1950).
57
N. Abdelmoula, H. Chaabane, H. Khemakem, R. von der Muhll, and A.
Simon, “Relaxor or Classical Ferroelectric Behavior in A-Site Substituted
Perovskite Type Ba1-x(Sm0.5Na0.5) xTiO3,” Solid State Sci., 8, 880–7 (2006).
58
R. Farhi, M. El Marssi, A. Simon, and J. Ravez, “Relaxor-Like and Spec-
troscopic Properties of Niobium Modified Barium Titanate,” Eur. Phys. J. B,
18, 605–10 (1999).
59
H. Ogihara, C. A. Randall, and S. Trolier-McKinstry, “Weakly Coupled
Relaxor Behavior of BaTiO3–BiScO3 Ceramics,” J. Am. Ceram. Soc., 92, 110–
8 (2009).
60
S. Tinberg and S. Troiler-McKinstry, “Structural and Electrical Character-
ization of xBiScO3 -(1-x)BaTiO3 Thin Films,” J. Appl. Phys., 101, 024112
(2007).
61
S. S. N. Bharadwaja, J. R. Kim, H. Ogihara, L. E. Cross, S. Trolier-
McKinstry, and C. A. Randall, “Critical Slowing Down Mechanism and
Reentrant Dipole Glass Phenomena in (1-x)BaTiO3-xBiScO3 (0.1 
x  0.4): The High Energy Density Dielectrics,” Phys. Rev. B, 83, 024106
(2011).
62
A. N. Salak, M. P. Seabra, and V. M. Ferreira, “Relaxor Behavior of the
0.9BaTiO3–0.1La(Mg1/2Ti1/2)O3 Solid Solution,” J. Am. Ceram. Soc., 87, 216–
20 (2004).
63
A. N. Salak, M. P. Seabra, and V. M. Ferreira, “Evolution from
Ferroelectric to Relaxor Behavior in the (1  x)BaTiO3  xLa(Mg1/2Ti1/2)O3
System,” Ferroelectrics, 318, 185–92 (2005).
64
T. Maiti, R. Guo, and A. S. Bhalla, “Structure-Property Phase Diagram
of BaZrxTi1-xO3 System,” J. Am. Ceram. Soc., 91, 1769–80 (2008).
65
I. A. Santos and J. A. Eiras, “Phenomenological Description of the
Diffuse Phase Transition in Ferroelectrics,” J. Phys.: Condens. Matter, 13,
11733–40 (2001).
66
K. Uchino and S. Nomura, “Critical Exponents of the Dielectric Con-
stants in Diffused-Phase-Transition Crystals,” Ferroelectric Lett., 44, 55–61
(1982).
67
J. Ravez and A. Simon, “Lead-Free Ferroelectric Relaxor Ceramics
Derived from BaTiO3,” Eur. Phys. J. AP, 11, 9–13 (2000).
68
H. Khemakhem, A. Simon, R. von der Mühll, and J. Ravez, “Relaxor
or Classical Ferroelectric Behavior in Ceramics with Composition Ba1-x
NaxTi1-xNbxO3,” J. Phys.: Condens. Matter, 12, 5951–9 (2000).
69
J. Ravez and A. Simon, “Le premier relaxeur ferroélectrique oxyfluoré,”
Phys. Status Solidi A, 159, 517–22 (1997).
70
F. Bahri, A. Simon, H. Khemakem, and J. Ravez, “Classical or Relaxor
Ferroelectric Behavior of Ceramics with Composition Ba1-xBi2x/3TiO3,” Phys.
Status Solidi A, 184, 459–64 (2001).
71
J. Ravez and A. Simon, “New Lead-Free Relaxor Ceramics Derived from
BaTiO3 by Cationic Heterovalent Substitutions in the 12 C.N. Crystallo-
graphic Site,” Solid State Sci., 2, 525–9 (2000).
72
A. Simon, J. Ravez, and M. Maglione, “The Crossover from a Ferroelec-
tric to a Relaxor State in Lead-Free Solid Solutions,” J. Phys.: Condens.
Matter, 16, 963–70 (2004).
73
A. A. Bokov, M. Maglione, and Z. G. Ye, “Quasi-Ferroelectric State in
Ba(Ti1-xZrx)O3 Relaxor: Dielectric Spectroscopy Evidence,” J. Phys.: Condens.
Matter, 19, 092001 (2007).
January 2012 Lead-Free Relaxors
74
V. V. Shvartsman, J. Zhai, and W. Kleemann, “The Dielectric Relaxation
in Solid Solutions BaTi1-xZrxO3,” Ferroelectrics, 379, 77–85 (2009).
75
V. Mueller, H. Beige, and H. -P. Abicht, “Non-Debye Dielectric Disper-
sion of Barium Titanate Stannate in the Relaxor and Diffuse Phase-Transition
State,” Appl. Phys. Lett., 84, 1341–3 (2004).
76
V. V. Shvartsman, J. Dec, Z. K. Xu, J. Banys, P. Keburis, and W. Klee-
mann, “Crossover from Ferroelectric to Relaxor Behavior in BaTi1-xSnxO3
Solid Solutions,” Phase Transitions, 81, 1013–21 (2008).
77
C. Lei, A. A. Bokov, and Z. -G. Ye, “Ferroelectric to Relaxor Crossover
and the Dielectric Phase Diagram in BaTiO3-BaSnO3 System,” J. Appl. Phys.,
101, 084105 (2007).
78
S. G. Lu, Z. K. Xu, and H. Chen, “Tunability and Relaxor Properties of
Ferroelectric Barium Stannate Titanate Ceramics,” Appl. Phys. Lett., 85, 5319
–21 (2004).
79
D. Hennings, A. Schnell, and G. Simon, “Diffuse Ferroelectric Phase
Transitions in Ba(Ti1-yZry)O3 Ceramics,” J. Am. Ceram. Soc., 65, 539–44
(1982).
80
L. Geske, H. Beige, H. –P. Abicht, and V. Mueller, “Electromechanical
Resonance Study of the Diffuse Ferroelectric Phase Transition in BaTi1-x
SnxO3 Ceramics,” Ferroelectrics, 314, 97–104 (2005).
81
X. Y. Wei, Y. Feng, and X. Yao, “Dielectric Relaxation Behavior in Bar-
ium Stannate Titanate Ferroelectric Ceramics with Diffused Phase Transition,”
Appl. Phys. Lett., 83, 2031–3 (2003).
82
K. -Y. Oh, K. Uchino, and L. E. Cross, “Optical Study of Domains in Ba
(Ti,Sn)O3 Ceramics,” J. Am. Ceram. Soc., 77, 2809–16 (1994).
83
V. V. Shvartsman, W. Kleemann, J. Dec, Z. K. Xu, and S. G. Lu, “Dif-
fuse Phase Transition in BaTi1-xSnxO3 Ceramics: An Intermediate State
Between Ferroelectric and Relaxor Behavior,” J. Appl. Phys., 99, 124111
(2006).
84
A. N. Salak, V. V. Shvartsman, M. P. Seabra, A. L. Kholkin, and V.
M. Ferreira, “Ferroelectric-To-Relaxor Transition Behavior of BaTiO3
Ceramics Doped with La(Mg1/2Ti1/2)O3,” J. Phys. Condens. Matter, 16,
2785–94 (2004).
85
S. Kamba, M. Kempa, V. Bovtun, J. Petzelt, K. Brinkman, and N. Setter,
“Soft and Central Mode Behavior in PbMg1/3Nb2/3O3 Relaxor Ferroelectric,”
J. Phys.: Condens. Matter, 17, 3965–74 (2005).
86
A. K. Tagantsev, “Vogel-Fulcher Relationship for the Dielectric Permittiv-
ity of Relaxor Ferroelectrics,” Phys. Rev. Lett., 72, 1100–3 (1994).
87
T. Maiti, R. Guo, and A. S. Bhalla, “The Evolution of Relaxor Behavior
in Ti4+ Doped BaZrO3 Ceramics,” J. Appl. Phys., 100, 114109 (2006).
88
A. Kumar, I. Rivera, and R. S. Katiyar, “Investigation of Local Structure
of Lead-Free Relaxor Ba(Ti0.70Sn0.30)O3 by Raman Spectroscopy,” J. Raman
Spectrosc., 40, 459–62 (2009).
89
M. Nagasawa, H. Kawaji, T. Tojo, and T. Atake, “Absence of The Heat
Capacity Anomaly in the Pb-Free Relaxor BaTi0.65Zr0.35O3,” Phys. Rev. B, 74,
132101 (2006).
90
J. Kreisel, P. Bouvier, M. Maglione, B. Dkhil, and A. Simon, “High-Pres-
sure Raman Investigation of the Pb-Free Relaxor BaTi0.65Zr0.35O3,” Phys.
Rev. B, 69, 092104 (2004).
91
Ph. Sciau, G. Calvarin, and J. Ravez, “X-ray Diffraction Study of
BaTi0.65Zr0.35O3 and Ba0.92Ca0.08Ti0.75Zr0.25O3 Compositions: Influence of
Electric Field,” Solid State Commun., 113, 77–82 (2000).
92
Y. Moriya, H. Kawaji, T. Tojo, and T. Atake, “Specific-Heat Anomaly
Caused by Ferroelectric Nanoregions in Pb(Mg1/3Nb2/3)O3 and Pb(Mg1/3Ta2/3)
O3 Relaxors,” Phys. Rev. Lett., 90, 205901 (2003).
93
M. V. Gorev, V. S. Bondarev, I. N. Flerov, Ph. Sciau, and J. -M. Savariault,
“Heat Capacity Study of Double Perovskite-Like Compounds BaTi1-xZrxO3,”
Phys. Solid St., 47, 2304–8 (2005).
94
N. de Mathan, E. Husson, G. Calvarin, and A. Morell, “Structural Study
of a Poled PbMg1/3Nb2/3O3 Ceramic at Low Temperature,” Mater. Res. Bull.,
26, 1197–1172 (1991).
95
C. Laulhé, F. Hippert, J. Kreisel, M. Maglione, A. Simon, J. L. Haze-
mann, and V. Nassif, “EXAFS Study of Lead-Free Relaxor Ferroelectric
BaTi1-xZrxO3 at the Zr K Edge,” Phys. Rev. B, 74, 014106 (2006).
96
A. A. Belik, S. Iikubo, K. Kodama, N. Igawa, S. Shamoto, M. Maie, T.
Nagai, Y. Matsui, S. Y. Stefanovich, B. I. Lazoryak, and E. Takayama-Muro-
machi, “BiScO3: Centrosymmetric BiMnO3-Type Oxide,” J. Am. Chem. Soc.,
128, 706–7 (2006).
97
G. Shirane, and K. Suzuki, “On The Phase Transition in Barium-Lead
Titanate,” J. Phys. Soc. Jpn., 6, 274–8 (1951).
98
K. Datta, P. A. Thomas, and K. Roleder, “Anomalous Phase Transi-
tions of Lead-Free Piezoelectric xNa0.5Bi0.5TiO3 - (1-x)BaTiO3 Solid Solutions
with Enhanced Phase Transition Temperatures,” Phys. Rev. B, 82, 224105
(2010).
99
R. Seshadri and N. A. Hill, “Visualizing the Role of Bi 6s “lone pairs”
in the Off-Center Distortion in Ferromagnetic BiMnO3,” Chem. Mater., 13,
2892–9 (2001).
100
R. J. Bratton and T. Y. Tien, “Phase Transitions in the System BaTiO3-
KNbO3,” J. Am. Cream. Soc., 50, 90–3 (1967).
101
I. P. Raevskii, L. M. Proskuryakova, L. A. Reznichenko, E. K.
Zvorykina, and L. A. Shilkina, “Obtaining Solid Solutions in the NaNbO3-
BaTiO3 System and Investigation of its Properties,” Rus. Phys. J., 21, 259–
61 (1978).
102
H. Y. Guo, C. Lei, and Z. –G. Ye, “Re-Entrant Type Relaxor Behav-
ior in (1-x)BaTiO3-xBiScO3 Solid Solution,” Appl. Phys. Lett., 92, 172901
(2008).
103
C. Lei, and Z. –G. Ye, “Re-Entrant-Like Relaxor Behavior in the New
0.99BaTiO3–0.01AgNbO3 Solid Solution,” J. Phys.: Condenc. Matter, 20,
232201 (2008).
23
104
E. Castel, M. Josse, D. Michau, and M. Maglione, “Flexible Relaxor
Materials: Ba2PrxNd1xFeNb4O15 Tetragonal Tungsten Bronze Solid Solu-
tion,” J. Phys.: Condens. Matter, 21, 452201 (2009).
105
R. Farhi, M. El Marssi, A. Simon, and J. Ravez, “A Raman and Dielec-
tric Study of Ferroelectric Ba(Ti1-xZrx)O3 Ceramics,” Eur. Phys. J. B, 9, 599–
604 (1999).
106
N. K. Karan, R. S. Katiyar, T. Maiti, R. Guo, and A. S. Bhalla, “Raman
Spectra of Zr4+-rich BaZrxTi1-xO3 (0.5  x  1.00) Phase Diagram,”
J. Raman Spectrosc., 40, 370–5 (2009).
107
M. P. Fontana and M. Lambert, “Linear Disorder and Temperature
Dependence of Raman Scattering in BaTiO3,” Solid State Commun., 10, 1–4
(1972).
108
G. A. Barbosa, A. Chaves, and S. P. S. Porto, “Temperature Dependence
of the Raman Cross Sections in BaTiO3 and SrTiO3,” Solid State Commun.,
11, 1053–5 (1972).
109
S. Miao, J. Pokorny, U. M. Pasha, O. P. Thakur, D. C. Sinclair, and
I. M. Reaney, “Polar Order and Diffuse Scatter in Ba(Ti1-xZrx)O3 Ceramics,”
J. Appl. Phys., 106, 114111 (2009).
110
C. Laulhé, F. Hippert, R. Bellissent, A. Simon, and G. J. Cuello, “Local
Structure in BaTi1-xZrxO3 Relaxors from Neutron Pair Distribution Function
Analysis,” Phys. Rev. B, 79, 064104 (2009).
111
C. Laulhé, A. Pasturel, F. Hippert, and J. Kreisel, “Random Local Strain
Effects in Homovalent-Substituted Relaxor Ferroelectrics: A First-Principles
Study of BaTi0.74Zr0.26O3,” Phys. Rev. B, 82, 132102 (2010).
112
I.-K. Jeong, C. Y. Park, J. S. Ahn, S. Park, and D. J. Kim, “Ferroelec-
tric-Relaxor Crossover in Ba(Ti1-xZrx)O3 Studied Using Neutron Total Scat-
tering Measurements and Reverse Monte Carlo Modelling,” Phys. Rev. B, 81,
214119 (2010).
113
Y. Liu, R. L. Whiters, X. Y. Wei, and J. D. F. Gerald, “Structure
Diffused Scattering and Polar Nano-Regions in the Ba(Ti1-xSnx)O3 Relaxor
Ferroelectric System,” J. Sol. St. Chem., 180, 858–65 (2007).
114
Y. Liu, R. L. Whiters, B. Nguyen, and K. Elliot, “Structurally Frustrated
Polar Nanoregions in BaTiO3-Based Relaxor Ferroelectric Systems,” Appl.
Phys. Lett., 91, 152907 (2007).
115
R. Gomes, M. Lambert, and A. Guinier, “The Chain Structure of
BaTiO3 and KNbO3,” Solid State Commun., 6, 715–9 (1968).
116
J. Harada, M. Watanabe, S. Kodera, and G. Honjo, “Diffuse Streak Dif-
fraction Pattern of Electron and X-Rays Due to Low Frequency Optical Mode
in Tetragonal BaTiO3,” J. Phys. Soc. Jpn., 20, 630–1 (1965).
117
A. S. Chaves, F. C. S. Barreto, R. A. Nogueira, and B. Zeks, “Thermo-
dynamic of an Eight-Sight Order-Disorder Model for Ferroelectrics,” Phys.
Rev. B, 13, 207–12 (1976).
118
K. A. Müller and W. Berlinger, “Microscopic Probing of Order-Disorder
Versus Displacive Behavior in BaTiO3 by Fe3+ EPR,” Phys. Rev. B, 34, 6130–
6 (1986).
119
B. Zalar, A. Lebar, J. Seliger, R. Blins, V. V. Laguta, and M. Itoh, “NMR
Studies of Disorder in BaTiO3 and SrTiO3,” Phys. Rev. B, 71, 064107 (2005).
120
J. Hlinka, T. Ostapchuk, D. Nuzhnyy, J. Petzelt, P. Kuzel, C. Kadlec,
P. Vanek, I. Ponomareva, and L. Bellaiche, “Coexistence of the Phonon
and Relaxation Soft Modes in the Terahertz Dielectric Response of Tetragonal
BaTiO3,” Phys. Rev. Lett., 101, 167402 (2008).
121
H. Ko, S. Kojima, T.-Y. Koo, J. H. Jung, C. J. Won, and N. J. Hur,
“Elastic Softening and Central Peaks in BaTiO3 Single Crystals Above the
Cubic-Tetragonal Phase-Transition Temperature,” Appl. Phys. Lett., 93,
102905 (2008).
122
M. Maglione, R. Böhmer, A. Loidl, and U. T. Höchli, “Polar Relaxation
Mode in Pure and Iron-Doped Barium Titanate,” Phys. Rev. B, 40, 11441–4 (1989).
123
R. Yan, Z. Guo, R. Tai, H. Xu, X. Zhao, D. Lin, X. Li, and H. Luo,
“Observation of Long Range Correlation Dynamics in BaTiO3 Near TC by
Photon Correlation Spectroscopy,” Appl. Phys. Lett., 93, 192908 (2008).
124
G. Burns and F. H. Dacol, “Polarization in the Cubic Phase of BaTiO3,”
Solid State Commun., 42, 9–12 (1982).
125
E. Dul’kin, J. Petzelt, S. Kamba, E. Mojaev, and M. Roth, “Relaxor-like
Behavior of BaTiO3 Crystals from Acoustic Emission Study,” Appl. Phys.
Lett., 97, 032903 (2010).
126
J. Rödel, W. Jo, K. T. P. Seifert, E.-M. Anton, T. Granzow, and D.
Damjanovic, “Perspective on the Development of Lead-Free Piezoceramics,”
J. Am. Ceram. Soc., 92, 1153–77 (2009).
127
M. D. Maeder, D. Damjanovic, and N. Setter, “Lead Free Piezoelectric
Materials,” J. Electroceram., 13, 385–92 (2004).
128
T. Takenaka, H. Nagata, and Y. Hiruma, “Current Developments
and Prospective of Lead-Free Piezoelectric Ceramics,” Jpn. J. Appl. Phys., 47,
3787–801 (2008).
129
M. Ahtee and A. M. Glazer, “Lattice Parameters and Tilted Octahedra
in Sodium-Potassium Niobate Solid Solutions,” Acta Crystallogr., Sect. A, 32,
434–46 (1976).
130
L. Egerton and D. M. Dillon, “Piezoelectric and Dielectric Properties of
Ceramics in the System Potassium Sodium Niobate,” J. Am. Ceram. Soc., 42,
438–42 (1959).
131
Y. Saito, H. Takao, I. Tani, T. Nonoyama, K. Takatori, T. Homma, T.
Nagaya, and M. Nakamura, “Lead-Free Piezoceramics,” Nature, 432, 84–7 (2004).
132
K. Wang and J. F. Li, “Domain Engineering of Lead-Free Li-Modified
(K,Na)NbO3 Polycrystals with Highly Enhanced Piezoelectricity,” Adv. Funct.
Mater., 20, 1924–9 (2010).
133
H. Birol, D. Damjanovic, and N. Setter, “Preparation and Characteriza-
tion of (K0.5Na0.5)NbO3 Ceramics,” J. Eur. Ceram. Soc., 26, 861–6 (2006).
134
Y. Guo, K. Kakimoto, and H. Ohsato, “Structure and Electrical Proper-
ties of Lead-Free (Na0.5K0.5)NbO3-BaTiO3 Ceramics,” Jpn. J. Appl. Phys., 43,
6662–6 (2004).
24 Journal of the American Ceramic Society—Shvartsman and Lupascu
135
Y. Guo, K. Kakimoto, and H. Ohsato, “Dielectric and Piezoelectric
Properties of Lead-Free (Na0.5K0.5)NbO3–SrTiO3 Ceramics,” Solid State
Commun., 129, 279–84 (2004).
136
V. Bobnar, J. Bernard, and M. Kosec, “Relaxorlike Dielectric Properties
and History-Dependent Effects in the Lead-Free K0.5Na0.5NbO3–SrTiO3 Cera-
mic System,” Appl. Phys. Lett., 85, 994–6 (2004).
137
M. Kosec, V. Bobnar, M. Hrovat, J. Bernard, B. Malic, and J. Holc,
“New Lead-Free Relaxors Based on the K0.5Na0.5NbO3–SrTiO3 Solid Solu-
tion,” J. Mat Res., 19, 1849–54 (2004).
138
V. Bobnar, J. Holc, M. Hrovat, and M. Kosec, “Relaxorlike Dielectric
Dynamics in the Lead-Free K0.5Na0.5NbO3-SrZrO3 Ceramic System,” J. Appl.
Phys., 101, 074103 (2007).
139
H. Du, W. Zhou, F. Luo, D. Zhu, S. Qu, Y. Li, and Z. Pei, “High
Tm Lead-Free Relaxor Ferroelectrics with Broad Temperature Usage
Range: 0.04BiScO30.96(K0.5Na0.5)NbO3,” J. Appl. Phys., 104, 044104
(2008).
140
H. Du, W. Zhou, F. Luo, D. Zhu, S. Qu, and Z. Pei, “Phase Structure,
Dielectric Properties, and Relaxor Behavior of (K0.5Na0.5)NbO3–(Ba0.5Sr0.5)
TiO3 Lead-Free Solid Solution for High Temperature Applications,” J. Appl.
Phys., 105, 124104 (2009).
141
Z. Kutnjak, C. Filipic, A. Levstik, and R. Pirc, “Glassy Dynamics of
Rb0.40(ND4)0.60D2PO4,” Phys. Rev. Lett., 70, 4015–8 (1993).
142
T. Takenaka, K. Maruyama, and K. Sakata, “(Bi1/2Na1/2)TiO3-BaTiO3
System for Lead-Free Piezoelectric Ceramics,” Jpn. J. Appl. Phys., 30, 2236–9
(1991).
143
C. Xu, D. Lin, and K. W. Kwok, “Structure, Electrical Properties and
Depolarization Temperature of (Bi0.5Na0.5)TiO3-BaTiO3 Lead-Free Piezoelec-
tric Ceramics,” Solid State Sci., 10, 934–40 (2008).
144
C. Ma, X. Tan, E. Dul’kin, and M. Roth, “Domain Structure-Dielectric
Property Relationship in Lead-Free (1-x)(Bi1/2Na1/2)TiO3-xBaTiO3 Ceramics,”
J. Appl. Phys., 108, 104105 (2010).
145
F. Cordero, F. Craciun, F. Trequattrini, E. Mercadelli, and C. Galassi,
“Phase Transitions and Phase Diagram of the Ferroelectric Perovskite
(Na0.5Bi0.5)1-xBaxTiO3 by Anelastic and Dielectric Measurements,” Phys. Rev.
B, 81, 144124 (2010).
146
V. Dorcet, G. Trolliard, and P. Boullay, “Reinvestigation of Phase Tran-
sitions in Na0.5Bi0.5TiO3 by TEM. Part I: First Order Rhombohedral to
Orthorhombic Phase Transition,” Chem. Mater., 20, 5061–73 (2008).
147
V. A. Isupov, “Ferroelectric Na0.5Bi0.5TiO3 and K0.5Bi0.5TiO3 and Their
Solid Solutions,” Ferroelectrics, 315, 123–47 (2005).
148
G. A. Smolenskii, V. A. Isupov, A. I. Agranovskaya, and N. N. Krainik,
“New Ferroelectrics of Complex Composition IV,” Sov. Phys. Solid State, 2,
2651–4 (1961).
149
G. O. Jones and P. A. Thomas, “Investigation of the Structure and Phase
Transitions in the Novel A-Site Substituted Distorted Perovskite Compound
Na0.5Bi0.5TiO3,” Acta Crystallogr., Sect. B, 58, 168–78 (2002).
150
S. B. Vakhrushev, V. A. Isupov, B. E. Kvyatkovsky, N. M. Okuneva, I.
P. Pronin, G. A. Smolensky, and P. P. Syrnikov, “Phase Transitions and Soft
Modes in Sodium Bismuth Titanate,” Ferroelectrics, 63, 153–60 (1985).
151
C. –S. Tu, I. G. Siny, and V. H. Schmidt, “Sequence of Dielectric Anom-
alies and High-Temperature Relaxation Behavior in Na1/2Bi1/2TiO3,” Phys.
Rev. B, 49, 11550–9 (1994).
152
K. Sakata and Y. Masuda, “Ferroelectric and Antiferroelectric Properties
of (Na0.5Bi0.5)TiO3-SrTiO3 Solid Solution Ceramics,” Ferroelectrics, 7, 347–9
(1974).
153
J. Suchanicz, “The Low-Frequency Dielectric Relaxation Na0.5Bi0.5TiO3
Ceramics,” Mater. Sci. Eng. B, 55, 114–8 (1998).
154
A. M. Balagurov, E. Yu. Koroleva, A. A. Naberezhnov, V. P. Sak-
hnenko, B. N. Savenko, N. V. Ter-Oganessian, and S. B. Vakhrushev, “The
Rhombohderal Phase with Incommensurate Modulation in Na1/2Bi1/2TiO3,”
Phase Trans., 79, 163–73 (2006).
155
J. Suchanicz, K. Roleder, A. Kania, and J. Hanaderek, “Electrostrictive
Strain and Pyroeffect in the Region of Phase Coexistence in Na0.5Bi0.5TiO3,”
Ferroelectrics, 77, 107–10 (1988).
156
J. Kreisel, A. M. Glazer, P. Bouvier, and G. Lucazeau, “High-Pressure
Raman Study of a Relaxor Ferroelectric: The Na0.5Bi0.5TiO3 Perovskite,”
Phys. Rev. B, 63, 174106 (2001).
157
J. Hlinka, J. Petzelt, S. Kamba, D. Noujni, and T. Ostapchuk, “Infrared
Dielectric Response Of Relaxor Ferroelectrics,” Phase Transitions, 79, 41–78
(2006).
158
I. P. Aleksandrova, A. A. Sokhovsky, Yu. N. Ivanov, Yu. E. Yablons-
kaya, and S. B. Vakhrushev, “Local and Average Structure of Relaxor
Na1/2Bi1/2TiO3 from the Point of View of NMR,” Ferroelectrics, 378, 6–22
(2009).
159
S. A. Sheets, A. N. Soukhojak, N. Ohashi, and Y.-M. Chiang, “Relaxor
Single Crystals in the (Bi1/2Na1/2)1-xBaxZryTi1-yO3 System Exhibiting High
Electrostrictive Strain,” J. Appl. Phys., 90, 5287–95 (2001).
160
I. W. Chen, “Structural Origin of Relaxor Ferroelectrics – Revisited,”
J. Phys. Chem. Solids, 61, 197–208 (2000).
161
J. Suchanicz, J. Kusz, H. Böhm, H. Duda, J. P. Mercurio, and K. Kon-
ieczny, “Structural and Dielectric Properties of (Na0.5Bi0.5)0.70Ba0.30TiO3
Ceramics,” J. Eur. Ceram. Soc., 23, 1559–64 (2003).
162
J. Suchanicz, J. Kusz, and H. Böhm, “Structural and Electric Characteris-
tics of (Na0.5Bi0.5)0.50Ba0.50TiO3 and (Na0.5Bi0.5)0.20Ba0.80TiO3 Ceramics,”
Mater. Sci. Eng. B, 97, 154–9 (2003).
163
D. Rout, K.-S. Moon, S.-J. L. Kang, and I. W. Kim, “Dielectric
and Raman Scattering Studies of Phase Transitions in the (100-x)Na0.5Bi0.5
TiO3-xSrTiO3 System,” J. Appl. Phys., 108, 084102 (2010).
Vol. 95, No. 1
164
Y. Hiruma, Y. Imai, Y. Watanabe, H. Nagata, and T. Takenaka, “Large
Electrostrain Near The Phase Transition Temperature of (Bi0.5Na0.5)
TiO3–SrTiO3 Ferroelectric Ceramics,” Appl. Phys. Lett., 92, 262904 (2008).
165
S. I. Raevskaya, L. A. Reznitchenko, I. P. Raevski, V. V. Titov, S. V.
Titova, and J.- L. Dellis, “Lead Free Niobate Ceramics with Relaxor-Like
Properties,” Ferroelectrics, 340, 107–12 (2006).
166
V. Dorcet, P. Marchet, O. Peña, and G. Trolliard, “Properties of the
Solid Solutions (1-x)Na0.5Bi0.5TiO3-xBiFeO3,” J. Magn. Magn. Mater., 321,
1762–6 (2009).
167
D. Lin, C. Xu, Q. Zheng, Y. Wei, and D. Gao, “Piezoelectric and Dielec-
tric Properties of Bi0.5Na0.5TiO3–Bi0.5Li0.5TiO3 Lead-Free Ceramics,”
J. Mater. Sci. - Mater. Electron., 20, 393–7 (2009).
168
Y. Hiruma, H. Nagata, and T. Takenaka, “Formation of Morphotropic
Phase Boundary and Electrical Properties of (Bi1/2Na1/2)TiO3–Ba(Al1/2Nb1/2)
O3 Solid Solution Ceramics,” J. Jpn. Appl. Phys., 48, 09KC08 (2009).
169
S. Said and J. –P. Mercurio, “Relaxor Behavior of Low Lead and Lead
Free Ferroelectric Ceramics of the Na0.5Bi0.5TiO3–PbTiO3 and Na0.5Bi0.5TiO3–
K0.5Bi0.5TiO3 Systems,” J. Eur. Ceram. Soc., 21, 1333–6 (2001).
170
Y. Hiruma, H. Nagata, and T. Takenaka, “Phase Diagrams and Electri-
cal Properties of (Bi1/2Na1/2)TiO3 - Based Solid Solutions,” J. Appl. Phys.,
104, 124106 (2008).
171
Y. Li, W. Chen, Q. Xu, J. Zhou, X. Gu, and S. Fang, “Electromechanical
and Dielectric Properties of Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3–BaTiO3 Lead-Free
Ceramics,” Mat Chem. Phys., 94, 328–32 (2005).
172
Y. Wu, H. Zhang, Y. Zhnag, J. Ma, and D. Xie, “Lead-Free Piezoelectric
Ceramics with Composition of (0.97x)Na1/2Bi1/2TiO3-0.03NaNbO3-x
BaTiO3,” J. Mater. Sci., 38, 987–94 (2003).
173
Y. -M. Li, W. Chen, Q. Xu, J. Zhou, H. –J. Sun, and M. –S. Liao,
“Dielectric and Piezoelectric Properties of Na0.5Bi0.5TiO3-K0.5Bi0.5TiO3-NaN-
bO3 Lead-Free Ceramics,” J. Electroceram., 14, 53–8 (2005).
174
C. Zhou, X. Liu, W. Li, C. Yuan, and G. Chen, “Structure and Electrical
Properties of Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3-BiCoO3 Lead-Free Piezoelectric
Ceramics,” J. Mater. Sci., 44, 3833–40 (2009).
175
R. Dittmer, W. Jo, D. Damjanovic, and J. Rödel, “Lead-Free High-Tem-
perature Dielectrics with Wide Operational Range,” J. Appl. Phys., 109,
034107 (2011).
176
W. Jo, T. Granzow, E. Aulbach, J. Rödel, and D. Damjanovic, “Origin
of the Large Strain Response in (K0.5Na0.5)NbO3-Modified (Bi0.5Na0.5)
TiO3-BaTiO3 Lead-Free Piezoceramics,” J. Appl. Phys., 105, 094102 (2009).
177
A. Aydi, H. Khemakhem, C. Boudaya, R. von der Muhll, and A. Simon,
“New Ferroelectric and Relaxor Ceramics in the Mixed Oxide System NaN-
bO3-BaSnO3,” Solid State Sci., 6, 333–7 (2004).
178
R Jimenez, M. L. Sanjuan, and B. Jimenez, “Stabilization of the Ferro-
electric Phase and Relaxor-Like Behavior in Low Li Content Sodium
Niobates,” J. Phys. Condens. Matter, 16, 7493–510 (2004).
179
S. I. Raevskaya, V. V. Titov, M. A. Malitskaya, L. A. Reznitchenko, M.
A. Seredkina, I. P. Raevski, and J. -L- Dellis, “Some Properties of the Relax-
or-Like Behavior in Sodium Niobate-Based Binary Solid Solutions,” Ferroelec-
trics, 374, 122–7 (2008).
180
I. P. Raevski and S. A. Prosandeev, “A New, Lead Free, Family of
Perovskites with a Diffuse Phase Transition: NaNbO3 Based Solid Solutions,”
J. Phys. Chem. Solids, 63, 1939–50 (2002).
181
H. D. Megaw, “The Seven Phases of Sodium Niobate,” Ferroelectrics, 7,
87–9 (1974).
182
L. E. Cross and B. J. Nicholson, “The Optical and Electrical Properties
of Single Crystals of Sodium Niobate,” Phil. Mag., 46, 453–66 (1955).
183
C. N. W. Darlington and K. S. Knight, “High Temperature Phases of
NaNbO3 and NaTaO3,” Acta Crystallogr., Sect. B, 55, 24–30 (1999).
184
A. Molak, “The Influence of Reduction in Valency of Nb Ions on the
Antiferroelectric Phase Transition in NaNbO3,” Solid State Commun., 62, 413
–7 (1987).
185
I. P. Raevskii, L. A. Reznichenko, V. G. Smotrakov, V. V. Eremkin, M.
A. Malitskaya, E. M. Kuznetsova, and L. A. Shilkina, “A New Phase Transi-
tion in Sodium Niobate,” Tech. Phys. Lett., 26, 744–6 (2000).
186
S. K. Mishra, N. Choudhury, S. L. Chaplot, P. S. R. Krishna, and
R. Mittal, “Competing Antiferroelectric and Ferroelectric Interactions in
NaNbO3: Neutron Diffraction and Theoretical Studies,” Phys. Rev. B, 76,
024110 (2007).
187
Z. X. Shen, X. B. Wang, M. H. Kuok, and S. H. Tang, “Raman Scatter-
ing Investigations of the Antiferroelectric-Ferroelectric Phase Transition of
NaNbO3,” J. Raman Spectrosc., 29, 379–84 (1998).
188
S. Lanfredi, M. H. Lente, and A. J. Eiras, “Phase Transition at Low
Temperature in NaNbO3 Ceramic,” Appl. Phys. Lett., 80, 2731–3 (2002).
189
J. Cheng, and D. Feng, “TEM Studies of Phase and Domains in NaN-
bO3 at Room Temperature,” Phys. Status Solidi A, 109, 171–85 (1988).
190
S. O. Lisitsyna, I. P. Raevskii, and G. A. Geguzina, “Classification of
Binary Sodium Niobate Solid Solutions According to the Properties of Their
Second Component,” Sov. Phys. – Tech. Phys., 31, 673–5 (1986).
191
M. P. Ivliev, I. P. Raevskii, L. A. Reznichenko, S. I. Raevskaya, and
V. P. Sakhnenko, “Phase States and Dielectric Properties of Sodium–Potassium
Niobate Solid Solutions,” Phys. Sol. St., 45, 1984–9 (2003).
192
B. Aurivillius, “Mixed Bismuth Oxides with Layer Lattices. 1. The Struc-
ture Type of CaNb2Bi2O9,” Ark. Kemi, 1, 463 (1950).
193
S. E. Cummins and L. E. Cross, “Electrical an Optical Properties of
Ferroelectric Bi4Ti8O12 Single Crystals,” J. Appl. Phys., 39, 2268–74 (1968).
194
H. Amorı́n, V. V. Shvartsman, A. L. Kholkin, and M. E. V. Costa,
“Ferroelectric and Dielectric Anisotropy in High-Quality SrBi2Ta2O9 Single
Crystals,” Appl. Phys. Lett., 85, 5667–9 (2004).
January 2012 Lead-Free Relaxors
195
E. C. Subbarao, “A Family of Ferroelectric Bismuth Compounds,”
J. Phys. Chem. Solids, 23, 665–76 (1962).
196
C. A. Paz de Araujo, J. D. Cuchiaro, L. D. McMillan, M. C. Scott, and
J. F. Scott, “Fatigue-Free Ferroelectric Capacitors with Platinum Electrodes,”
Nature, 374, 627–9 (1995).
197
J. F. Scott, Ferroelectric memories. Springer, Berlin-Heidelberg, 2000.
198
G. A. Smolenskii, V. A. Isupov, and A. I. Agranovskaya, “Ferroelectrics
of the Oxygen-Octahedral Type with Layered Structure,” Sov. Phys. Solid
State, 3, 651–5 (1961).
199
A. L. Kholkin, M. Avdeev, M. E. V. Costa, J. L. Baptista, and S. N.
Dorogovtsev, “Dielectric Relaxation in Ba-Based Layered Perovskites,” Appl.
Phys. Lett., 79, 662–4 (2001).
200
M. Adamczyk, Z. Ujma, and M. Paweczyk, “Dielectric Properties of
BaBi2Nb2O9 Ceramics,” J. Mater. Sci., 41, 5317–22 (2006).
201
D. Nuzhnyy, S. Kamba, P. Kužel, S. Veljko, V. Bovtun, M. Savinov,
J. Petzelt, H. Amorı́n, M. E. V. Costa, A. L. Kholkin, Ph. Boullay, and M.
Adamczyk, “Dynamics of the Phase Transitions in Bi-Layered Ferroelectrics
with Aurivillius Structure: Dielectric Response in the Terahertz Spectral
Range,” Phys. Rev. B, 74, 134105 (2006).
202
V. V. Shvartsman, M. E. V. Costa, M. Avdeev, and A. L. Kholkin,
“Relaxor Behavior of BaBi2Ta2O9 and BaBi2Nb2O9 Ceramics,” Feroelectrics,
296, 187–97 (2003).
203
D. Ben Jannet, M. El Maaoui, and J. P. Mercurio, “Ferroelectric Versus
Relaxor Behavior in Na0.5Bi4.5Ti4O15-BaBi4Ti4O15 Solid Solutions,” J. Electro-
ceram., 11, 101–6 (2003).
204
S. K. Rout, E. Sinha, A. Hussian, J. S. Lee, C. W. Ahn, I. W. Kim, and
S. I. Woo, “Phase Transition in ABi4Ti4O15 (A=Ca, Sr, Ba) Aurivillius Oxides
Prepared Through a Soft Chemical Route,” J. Appl. Phys., 105, 024105 (2009).
205
H. Irie, M. Miyayama, and T. Kudo, “Electrical Properties of a Bismuth
Layer-Structured Ba2Bi4Ti5O18 Single Crystal,” J. Am. Ceram. Soc., 83, 2699–
704 (2000).
206
C. Karthik, N. Ravishankar, K. B. R. Varma, M. Maglione, R.
Vondermuhll, and J. Etourneau, “Relaxor Behavior of K0.5La0.5Bi2Nb2O9
Ceramics,” Appl. Phys. Lett., 89, 042905 (2006).
207
C. Karthik, N. Ravishankar, M. Maglione, R. Vondermuhll, J. Etour-
neau, and K.B.R. Varma, “Relaxor Behavior of K0.5La0.5Bi2Ta2O9 Ceramics,”
Solid State Commun., 139, 268–72 (2006).
208
L. Sun, C. Feng, L. Chen, and S. Huang, “Effect of Substitution of
Nd3+ for Bi3+ on the Dielectric Properties and Structures of
SrBi2xNdxNb2O9 Bismuth Layer-Structured Ceramics,” J. Appl. Phys., 101,
084102 (2007).
209
S. Huang, L. Sun, C. Feng, and L. Chen, “Relaxor Behavior of Layer
Structured SrBi1.65La0.35Nb2O9,” J. Appl. Phys., 99, 076104 (2006).
210
Z. Zhou, X. Dong, S. Huang, and H. Yan, “Dielectric Relaxation of La3+
-Modified Bi3TiNbO9 Aurivillius Phase Ceramics,” J. Am. Ceram. Soc., 89,
2939–42 (2006).
211
X. –B. Chen, R. Hui, J. Zhu, W. –P. Lu, and X. –Y. Mao, “Relaxor
Properties of Lanthanum-Doped Bismuth Layer-Structured Ferroelectrics,”
J. Appl. Phys., 96, 5697–700 (2004).
212
Y. Shimakawa, Y. Kubo, Y. Nakagawa, S. Goto, T. Kamiyama, H.
Asano, and F. Izumi, “Crystal Structure and Ferroelectric Properties of
ABi2Ta2O9 (A= Ca, Sr, and Ba),” Phys. Rev. B, 61, 6559–64 (2000).
213
P. Fang, H. Fan, J. Li, and F. Liang, “Lanthanum Induced Larger
Polarization and Dielectric Relaxation in Aurivillius Phase SrBi2-xLaxNb2O9
Ferroelectric Ceramics,” J. Appl. Phys., 107, 064104 (2010).
214
H. Irie, M. Miyayama, and T. Kudo, “Structure Dependence of Ferro-
electric Properties of Bismuth Layer-Structured Ferroelectric Single Crystals,”
J. Appl. Phys., 90, 4089–94 (2001).
215
S. Huang, C. Feng, L. Chen, and Q. Wang, “Relaxor Behavior of
Sr1-xBaxBi2Nb2O9 Ceramics,” J. Am. Ceram. Soc., 89, 328–31 (2006).
216
B. Behera, E. B. Araújo, and A. F. Junior, “Structural and Dielectric
Properties of Relaxor Sr0.5Ba0.5Bi2Nb2O9 Ceramic,” Adv. Appl. Ceram., 109,
1–5 (2010).
217
H. Zhang, H. Yan, and M. J. Reece, “Microstructure and Electrical
Properties of Aurivillius Phase (CaBi2Nb2O9)1-x(BaBi2Nb2O9)x Solid Solu-
tion,” J. Appl. Phys., 108, 014109 (2010).
218
H. Yan, H. Zhang, R. Ubic, M. Reece, J. Liu, and Z. Shen, “Orientation
Dependence of Dielectric and Relaxor Behavior in Aurivillius Phase
BaBi2Nb2O9 Ceramics Prepared by Spark Plasma Sintering,” J. Mater. Sci:
Mater. Electron., 17, 657–61 (2006).
219
R. L. Withers, J. G. Thompson, and A. D. Rae, “The Crystal Chemistry
Underlying Ferroelectricity in Bi4Ti3O12, Bi3TiNbO9, and Bi2WO6,” J. Solid
State Chem., 94, 404–17 (1991).
220
A. D. Rae, J. G. Thompson, and R. L. Withers, “Structure Refinement
of Commensurately Modulated Bismuth Strontium Tantalite,” Bi2SrTa2O9,
Acta Crystallogr., Sect. B, 48, 818 (1992).
221
A. M. Blake, M. J. Falconer, M. McCreedy, and P. Lightfoot, “Cation
Disorder in Ferroelectric Aurivillius Phases of the Type Bi2ANb2O9 (A=Ba,
Sr, Ca),” J. Mater. Chem., 7, 1609–13 (1997).
222
Ismunandar and B. J. Kennedy, “Effect of Temperature on Cation Disor-
der in ABi2Nb2O9 (A=Sr, Ba),” J. Mater. Chem., 9, 541–4 (1999).
223
J. Tellier, Ph. Boullay, M. Manier, and D. Mercurio, “A Comparative
Study of the Aurivillius Phase Ferroelectrics CaBi4Ti4O15 and BaBi4Ti4O15,”
J. Sol. St. Chem., 177, 1829–37 (2004).
224
S. Huang, C. Feng, L. Chen, and X. Wen, “Dielectric Properties of SrBi2-x
PrxNb2O9 Ceramics (x = 0, 0.04 and 0.2),” Solid State Commun., 133, 375–9
(2005).
25
225
M. Osada, M. Tada, M. Kakihana, T. Watanabe, and H. Fubakubo,
“Cation Distribution and Structural Instability in Bi4-xLaxTi3O12,” Jpn.
J. Appl. Phys., 40, 5572–5 (2001).
226
C. H. Hervoches and P. Lightfoot, “Cation Disorder in Three-Layer Au-
rivillius Phases: Structural Studies of Bi2-xSr2+xTi1-xNb2+xO12 (0 < x < 0.8)
and Bi4-xLaxTi3O12 (x = 1 and 2),” J. Sol. St. Chem., 153, 66–73 (2000).
227
Y. Xu, Ferroelectric materials and their applications. Elsevier, North-
Holland, Amsterdam, 1999.
228
T. Łukasiewicz, M. A. Swirkowicz, J. Dec, W. Hofman, and W. Szyrski,
“Strontium-Barium Niobate Single Crystals, Growth and Ferroelectric Proper-
ties,” J. Cryst. Growth, 310, 1464–9 (2008).
229
A. Simon and J. Ravez, “Lead Free Relaxors with “TTB” Structure Con-
taining Either Lanthanum or Bismuth,” Phys. Status Solidi A, 199, 541–5 (2001).
230
D. C. Arnold and F. D. Morrison, “B-Cation Effects in Relaxor and Fer-
roelectric Tetragonal Tungsten Bronzes,” J. Mat. Chem., 19, 6485–8 (2009).
231
A. Rotaru, D. C. Arnold, A. Daoud-Aladine, and F. D. Morrison, “Ori-
gin and Stability of the Dipolar Response in a Family of Tetragonal Tungsten
Bronze Relaxors,” Phys. Rev. B, 83, 184302 (2011).
232
P. P. Liu, X. L. Zhu, and X. M. Chen, “Relaxor Ferroelectric and Mag-
netic Properties of Ba6CoNb9O30 Ceramics with Tungsten Bronze Structure,”
J. Appl. Phys., 106, 074111 (2009).
233
M. C. Stennett, I. M. Reaney, G. C. Miles, D. I. Woodward, A. R. West,
C. A. Kirk, and I. Levin, “Dielectric and Structural Studies of Ba2M-
Ti2Nb3O15 (BMTNO15, M = Bi3+, La3+, Nd3+, Sm3+, Gd3+) Tetragonal
Tungsten Bronze-Structured Ceramics,” J. Appl. Phys., 101, 104114 (2007).
234
P. B. Jamieson, S. C. Abrahams, and J. L. Bernstein, “Ferroelectric
Tungsten Bronze-Type Crystal Structures. I. Barium Strontium Niobate
Ba0.27Sr0.75Nb2O5.78,” J. Chem. Phys., 48, 5048–57 (1968).
235
J. R. Oliver, R. R. Neurgaonkar, and L. E. Cross, “A Thermodynamic
Phenomenology for Ferroelectric Tungsten Bronze Sr0.6Ba0.4Nb2O6 (SBN:60),”
J. Appl. Phys., 64, 37–47 (1988).
236
S. Miga, W. Kleemann, J. Dec, and T. Łukaciewicz, “Three-Dimensional
Random-Field Ising Model Phase Transition in Virgin Sr0.4Ba0.6Nb2O6: Over-
coming Aging,” Phys. Rev. B, 80, 220103 (2009).
237
J. Dec, W. Kleemann, and T. Łukasiewicz, “Critical Slowing Down in the
Single Crystalline Relaxor SBN75,” Phase Transit., 79, 505–11 (2006).
238
V. V. Shvartsman, J. Dec, S. Miga, T. Łukaciewicz, and W. Kleemann,
“Ferroelectric Domains in SrxBa1-xNb2O6 Single Crystals (0.4  x  0.75),”
Ferroelectrics, 376, 197–204 (2008).
239
T. S. Chernaya, B. A. Maksimov, I. V. Verin, L. I. Ivleva, and V. I. Si-
monov, “Crystal Structure of Ba0.39Sr0.61Nb2O6,” Crystallogr. Rep., 42, 375–80
(1997).
240
V. V. Shvartsman, W. Kleemann, T. Łukasiewicz, and J. Dec, “Polar
Structure in SrxBa1-xNb2O6 Single Crystals Studied by Piezoelectric Force
Microscopy,” Phys. Rev. B, 77, 054105 (2008).
241
U. Voelker and K. Betzler, “Domain Morphology from k-space Spectros-
copy of Ferroelectric Crystals,” Phys. Rev. B, 74, 132104 (2006).
242
A. S. Bhalla, R. Guo, L. E. Cross, G. Burns, F. H. Dacol, and R. R.
Neurgaonkar, “Measurements of Strain and the Optical Indices in the Ferro-
electric Ba0.4Sr0.6Nb2O6: Polarization Effects,” Phys. Rev. B, 36, 2030–5
(1987).
243
P. Lehnen, W. Kleemann, Th. Woike, and P. Pankrath, “Phase Transi-
tions in Sr0.61Ba0.39Nb2O6:Ce3+: II. Linear Birefringence Studies of Spontane-
ous and Precursor Polarization,” Eur. Phys. J. B, 14, 633–7 (2000).
244
W. Kleemann, P. Licinio, Th. Woike, and P. Pankrath, “Dynamic Light
Scattering at Domains and Nanoclusters in a Relaxor Ferroelectric,” Phys.
Rev. Lett., 86, 6014–7 (2001).
245
J. –H. Ko and S. Kojima, “Intrinsic and Extrinsic Central Peaks in the
Brillouin Light Scattering Spectrum of the Uniaxial Ferroelectric Relaxor
Sr0.61Ba0.39Nb2O6,” Appl. Phys. Lett., 91, 082903 (2007).
246
W. Kleemann, J. Dec, P. Lehnen, R. Blinc, B. Zalar, and R. Pankrath,
“Uniaxial Relaxor Ferroelectrics: The Ferroic Random-Field Ising Model
Materialized at Last,” Europhys. Lett., 57, 14–9 (2002).
247
W. Kleemann, J. Dec, V. V. Shvartsman, S. Kutnjak, and T.h. Braun,
“Two-Dimensional Ising Model Criticality in a Three-Dimensional Uniaxial
Relaxor Ferroelectric with Frozen Polar Nanoregions,” Phys. Rev. Lett., 97,
065702 (2006).
248
J. Dec, V. V. Shvartsman, and W. Kleemann, “Domainlike Precursor
Clusters in the Paraelectric Phase of the Uniaxial Relaxor Sr0.61Ba0.39Nb2O6,”
Appl. Phys. Lett., 89, 212901 (2006).
249
J. Dec, W. Kleemann, S. Miga, V. V. Shvartsman, T. Łukasiewicz, and
M. Swirkowicz, “Aging, Rejuvenation, and Memory Effects in the Domain
State of Sr0.75Ba0.25Nb2O6, Phase,” Transit., 80, 131–40 (2007).
250
W. Kleemann, “Absence of True Critical Exponents in Relaxor Ferroelec-
trics: The Case for Nanodomain Freezing,” J. Phys.: Condens. Matter, 18,
L523–6 (2006).
251
J. F. Scott, “Absence of True Critical Exponents in Relaxor Ferroelectrics:
The Case for Defect Dynamics,” J. Phys.: Condens. Matter, 18, 7123–34 (2006).
252
T. R. Volk, V. Y. Salobutin, L. I. Ivleva, N. M. Polozkov, R. Pankrath,
and M. Woehlecke, “Ferroelectric Properties of Strontium Barium Niobate
Crystals Doped with Rare-Earth Metals,” Phys. Sol. State, 42, 2129–36 (2000).
253
J. Dec, W. Kleemann, Th. Woike, and R. Pankrath, “Phase Transitions
in Sr0.61Ba0.39Nb2O6:Ce3+: I. Susceptibility of Clusters and Domains,” Eur.
Phys. J. B, 14, 627–32 (2000).
254
P. Lehnen, E. Beckers, W. Kleemann, T. Woike, and R. Pankrath, “Fer-
roelectric Domains in the Uniaxial Relaxor System SBN: Ce, Cr, and Co,”
Ferroelectrics, 253, 567–75 (2001).
26 Journal of the American Ceramic Society—Shvartsman and Lupascu
255
A. Belous, O. V’yunov, D. Mishchuk, S. Kamba, and D. Nuzhnyy,
“Effect of Vacancies on the Structural and Relaxor Properties of (Sr,Ba,Na)
Nb2O6,” J. Appl. Phys., 102, 014111 (2007).
256
I. Levin, M. C. Stennet, G. C. Miles, D. I. Woodward, A. R. West, and
I. M. Reaney, “Coupling Between Octahedral Tilting and Ferroelectric Order
in Tetragonal Tungsten Bronze-Structured Dielectrics,” Appl. Phys. Lett., 89,
122908 (2006).
257
X. L. Zhu, X. M. Chen, X. Q. Liu, and X. G. Li, “Ferroelectric Phase
Transition and Low-Temperature Structure Fluctuations in Ba4Nd2Ti4Nb6O30
Tungsten Bronze Ceramics,” J. Appl. Phys., 105, 124110 (2009).
258
X. L. Zhu, X. M. Chen, X. Q. Liu, and X. G. Li, “Dielectric Relaxations,
Ultrasonic Attenuation, and their Structure Dependence in Sr4(LaxNd1-x)2
Ti4Nb6O30 Tungsten Bronze Ceramics,” J. Mater. Res., 23, 3112–21 (2008).
259
X. L. Zhu, S. Y. Wu, and X. M. Chen, “Dielectric Anomalies in (BaxSr1-x)4
Nd2Ti4Nb6O30 Ceramics with Various Radius Differences Between A1- and A2-
Site Ions,” Appl. Phys. Lett., 91, 162906 (2007).
260
X. L. Zhu, X. M. Chen, and X. Q. Liu, “Dielectric Abnormity of
Sr4Nd2Ti4Nb6O30 Tungsten Bronze Ceramics Over a Broad Temperature
Range,” J. Mater. Res., 22, 2217–22 (2007).
261
X. L. Zhu, X. Q. Liu, and X. M. Chen, “Crystal Structure and Dielectric
Properties of Sr5RTi3Nb7O30 (R = La, Nd, Sm, and Eu) Tungsten Bronze
Ceramics,” J. Am. Ceram. Soc., 94, 1829–36 (2011).
262
J. -H. Ko, S. Kojima, S. G. Lushnikov, R. S. Katiyar, T. –H. Kim, and
J. –H. Ro, “Low-Temperature Transverse Dielectric and Pyroelectric Anoma-
lies of Uniaxial Tungsten Bronze Crystals,” J. Appl. Phys., 92, 1536–43 (2002).
263
A. Simon, G. T. Joo, M. Maglione, and J. Ravez, “Anisotropic Polar
State of Sr0.75Ba0.25Nb2O6 Single Crystal,” Solid State Sci., 9, 52–6 (2007).
264
M. Venet, J. de Los, S. Guerra, I. A. Santos, J. A. Eiras, and D. Garcia,
“Diffuse Phase Transition and Relaxor Behavior of Textured
Sr0.63Ba0.37Nb2O6 Ceramics,” J. Phys.: Condens. Matter, 19, 026207 (2007).
265
X. X. Xi, H. –C. Li, W. Si, A. A. Sirenko, I. A. Akimov, J. R. Fox, A.
M. Clark, and J. Hao, “Oxide Thin Films for Tunable Microwave Devices,”
J. Electroceram., 4, 393–405 (2000).
266
Y. Somiya, A. S. Bhalla, and L. E. Cross, “Study of (Sr, Pb)TiO3 Ceram-
ics on Dielectric and Physical Properties,” Int. J. Inorg. Mat., 3, 709–14
(2001).
267
C. M. Jackson, J. H. Kobayashi, A. Lee, C. Pettiette-Hall, J. F. Burch,
R. Hu, R. Hilton, and J. McDade, “Novel Monolithic Phys Shifter Combining
Ferroelectrics and High Temperature Superconductors,” Microwave Opt. Tech-
nol. Lett., 5, 722–6 (1992).
268
J. -W. Liou and B. -S. Chiou, “Effect of Direct-Current Biasing on the
Dielectric Properties of Barium Strontium Titanate,” J. Am. Ceram. Soc., 80,
3093–9 (1997).
269
Z. Yu, C. Ang, R. Guo, and A. S. Bhalla, “Dielectric Properties and
High Tunability of Ba(Ti0.7Zr0.3)O3 Ceramics under dc Electric Field,” Appl.
Phys. Lett., 81, 1285–7 (2002).
270
T. Wang, X. M. Chen, and X. H. Zheng, “Dielectric Characteristics and
Tunability of Barium Stannate Titanate Ceramics,” J. Electroceram., 11, 173–8
(2003).
Vol. 95, No. 1
271
Z. Yu, C. Ang, R. Guo, and A. S. Bhalla, “Piezoelectric and Strain Prop-
erties of Ba(Ti1-xZrx)O3 Ceramics,” J. Appl. Phys., 92, 1489–93 (2002).
272
R. Steinhausen, H. Th. Langhammer, A. Z. Kouvatov, C. Pientschke, H.
Beige, and H.-P. Abicht, “Bending Actuators Based on Monolithic Barium
Titanate-Stannate Ceramics as Functional Gradient Materials,” Mat. Sci.
Forum, 494, 167–74 (2005).
273
D. Viehland, Z. Xu, and W.-H. Huang, “Structure-Property Relation-
ships in Strontium Barium Niobate: I. Needle-Like Nanopolar Domains and
Metastably-Locked Incommensurate Structure,” Philos. Mag. A, 71, 205–17
(1995).
274
N. Takesue, Y. Fujii, and H. You, “X-Ray Diffuse Scattering Study on
Ionic-Pair Displacement Correlations in Relaxor Lead Magnesium Niobate,”
Phys. Rev. B, 64, 184112 (2001).
275
G. Xu, Z. Zhong, H. Hiraka, and G. Shirane, “Three-Dimensional Map-
ping of Diffuse Scattering in Pb(Zn1/3Nb2/3)O3-xPbTiO3,” Phys. Rev. B, 70,
174109 (2004).
276
J. Kreisel, P. Bouvier, B. Dkhil, P. A. Tomas, A. M. Glazer, T. R. Wel-
berry, B. Chaabane, and M. Mezouar, “High-Pressure X-Ray Scattering of
Oxides wih a Nanosclae Local Structure: Application to Na1/2Bi1/2TiO3,”
Phys. Rev. B, 68, 014113 (2003).
277
G. Young, J. Toulouse, R. Erwin, S. M. Shapiro, and B. Hennion,
“Pretransitional Diffuse Neutron Scattering in the Mixed Perovskite Relaxor
K1-xLixTaO3,” Phys. Rev. B, 62, 14736 (2000).
278
Z. Yu, C. Ang, Z. Jing, P. M. Vilarinho, and J. L. Baptista, “Dielectric
Properties of Ba(Ti,Ce)O3 from 102 to 105 Hz in the Temperature Range
85–700 K,” J. Phys.: Condens. Matter, 9, 3081–8 (1997).
279
L. Cui, Y.-D. Hou, S. Wang, C. Wang, and M. -K. Zhu, “Relaxor
Behavior of (Ba,Bi)(Ti,Al)O3 Ferroelectric Ceramic,” J. Appl. Phys., 107,
054105 (2010).
280
H. Chaabane, N. Abdelmoula, H. Khemakhem, A. Simon, D. Michau,
and M. Maglione, “Dielectric And Ferroelectric Properties of Lead-Free Ba1-x
LaxTi1-xFexO3 Ceramics,” Phys. Status Solidi A, 208, 180–5 (2011).
281
S. Kumar and K. B. R. Varma, “Relaxor Behavior of BaBi4Ti3-
Fe0.5Nb0.5O15 Ceramics,” Solid State Commun., 147, 457–60 (2008).
282
X. L. Zhu, X. M. Chen, X. Q. Liu, and Y. Yuan, “Dielectric Characteris-
tics and Diffuse Ferroelectric Phase Transition in Sr4La2Ti4Nb6O30 Tungsten
Bronze Ceramics,” J. Mater. Res., 21, 1787–92 (2006).
283
M. X. Cao, X. L. Zhu, X. Q. Liu, and X. M. Cheng, “Crystal Structure
and Ferroelectric Behaviors of Ba5SmTi3Ta7O30 and Ba4Sm2Ti4Ta6O30 Tung-
sten Bronze Ceramics,” J. Am. Ceram. Soc., 93, 782–6 (2010).
284
H. El Alaoui-Belghiti, A. Simon, M. Elaatmani, J. M. Reau, and
J. Ravez, “TKWB-Type Lead-Free Oxyfluoride Relaxors Derived from
Ba2NaNb5O15,” Phys. Status Solidi A, 187, 549–56 (2001).
285
V. V. Shvartsman, A. L. Kholkin, A. Orlova, D. Kiselev, A. A. Bogomo-
lov, and A. Sternberg, “Polar Nanodomains and Local Ferroelectric Phenom-
ena in Relaxor Lead Lanthanum Zirconate Titanate Ceramics,” Appl. Phys.
Lett., 86, 202907 (2005). h

Vladimir V. Shvartsman studied solid state physics at Moscow State Engineering Physics Institute and
obtained a PhD in physical chemistry from Karpov Institute of Physical Chemistry in Moscow in
2000. His PhD thesis was devoted to sintering and investigations of ferroelectric and relaxor ceramics
for electrocaloric applications. Thereafter he joined the group of Dr. Andrei Kholkin at the Depart-
ment of Ceramic and Glass Engineering at Aveiro University, Portugal, where he has specialized in
piezoresponse force microscopy (PFM) studies of polar dielectrics, especially relaxors. These studies he
continued at the group of Prof. Wolfgang Kleemann at the Physical Faculty of University Duisburg-
Essen, where he moved in the year 2005. Since 2007 he has been involved in investigations of multi-
ferroic and magnetoelectric materials. In 2009 he joined the Institute for Materials Science in Civil
Engineering at University of Duisburg-Essen, where he leads several research projects including devel-
opment of new lead-free piezoelectrics and composite multiferroic materials with a core-shell structure.

Doru C. Lupascu studied physics at Braunschweig and Paris and obtained a PhD in nuclear solid state
physics from University of Göttingen. Already at this time, oxides were his major research field: NMR
studies on high-Tc superconductors and gg angular correlation spectroscopy on rare earth oxides. He
joined the Department of Materials Science at Darmstadt University of Technology in 1996 and found
his research field of passion there, namely ferroelectrics, their fatigue characteristics and their mechan-
ics. His habilitation for Materials Science in 2003 lead to a first tenured professorship at the Institute
of Materials Science at Dresden University of Technology in 2006. Already in 2008, his journey con-
tinued to the Institute for Materials Science in Civil Engineering at University of Duisburg-Essen. The
institute intends to foster the research on functional materials and their incorporation into classical
building materials and structures. Present research fields of the institute span ferroelectrics, magneto-
electrics, organic solar cells, thermal insulation, and durability of concrete.
Copyright of Journal of the American Ceramic Society is the property of Wiley-Blackwell and its content may
not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written
permission. However, users may print, download, or email articles for individual use.