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J ournal J. Am. Ceram. Soc., 95 [1] 1–26 (2012) DOI: 10.1111/j.1551-2916.2011.04952.x © 2011 The

J ournal

J. Am. Ceram. Soc., 95 [1] 1–26 (2012) 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 *

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 magnetoresistance

and magnetocapaci-

tance 2 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

1

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

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, T m , 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)].

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 ~ 10 4 10 5 [Ref. 10] observed in a broad temperature range and high piezoelectric coefficients d 33 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.

Several reviews have been devoted to relaxors, most of them to the lead-containing systems. 8,9,13,14 Existing surveys

on lead-free relaxors

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 PbMg 1/3 Nb 2/3 O 3 (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.

8,9

12

15,16

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
Feature

2

Journal of the American Ceramic Society—Shvartsman and Lupascu

Vol. 95, No. 1

Ceramic Society—Shvartsman and Lupascu Vol. 95, No. 1 Fig. 1. The temperature dependence of the real

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(Mg 1/3 Nb 2/3 )O 3 (from Ref. 9).

regions (PNRs) and their response to external stimuli. These regions of locally correlated polarizations appear at the

, which is typically far above the

maximum point of permittivity, T m . 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, P l , are randomly distributed. There- fore, no measurable remanent polarization exists. However,

2 0, the existence of PNRs becomes apparent in

properties depending on P 2 , for example, in the deviation of

temperature dependences of the refractive index 17,18 or the thermal expansion coefficient 13 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

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

(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- ments 20,21 . In PMN single crystals, a significant diffuse scat- tering appears below T D 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

“Burns” temperature,

T D

as P P

l

from linearity.

19

T D = 620 K, which is about 350 K above T m

(a) (b) (c) (d)
(a)
(b)
(c)
(d)

Fig. 2. (a) 180- and 90-degree domains in a ferroelectric PbTiO 3 single crystal at RT (the sample has been provided by Prof. J. Dec, University of Silesia, Katowice, Poland); (b) polar structures in a relaxor Pb 0.9125 La 0.0975 (Zr 0.65 Ti 0.35 ) 0.976 O 3 ceramic below the transition temperature [Ref. 286]; (c) polar nanoregions in a relaxor Sr 0.61 Ba 0.49 Nb 2 O 6 single crystal above the transition temperature [Ref. 240]; (d) polar nanoregions in a BaTi 0.85 Sn 0.15 O 3 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

3

January 2012 Lead-Free Relaxors 3 Fig. 3. Temperature dependences of the linear thermal expansion, D l

Fig. 3. Temperature dependences of the linear thermal expansion, Dl/l, (a) and the refractive index, n, (b) for Pb(Mg 1/3 Nb 2/3 )O 3 showing deviations from linear behavior starting at a temperature (T D ) much higher than the peak (T m ) 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 T D to ~ 10 nm at 10 K upon cooling. The most significant change of their size was observed around the freezing tem- perature T f ~ 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.

The

number of PNRs estimated from the integrated intensity of scattering shows a monotonic increase upon cooling, starting from T D , and then, an abrupt decrease at about T f 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 (Mg 2+ and Nb 5+ ) with different charges and chemical bonding characteristics in the ABO 3 perovskite structure. High-resolution electron microscopy has revealed an inhomogeneous distribution of B-site cations:

nanosized chemically ordered regions (CORs, ~ 25 nm) exist

in a disordered surrounding. 26,27

spectroscopy measurements, Davies and Akbas suggested that

one of the B-sublattices inside the CORs is occupied exclu-

sively by

distribution of B 2+ and B 5+ 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

B 5+ ions, while the other one contains a random

Based on X-ray dispersive

9

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.

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 T D , 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, T f , may be derived from fitting the frequency dependence of the temperature of the dielectric permittivity maximum, T m , to the phenomenological VogelFulcher law:

30

In the case of re-

f ¼ f 0 exp

E

a

kðT m T f Þ

;

(1)

where E a is an activation energy, f 0 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

T f,

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,

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 (1 x)PbMg

PbTiO 3 (PMN-PT) with large Ti 4+

Sr x Ba 1 x Nb 2 O 6

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 T m and evidence of the existence of PNRs far above T m . 42 On the other hand, their low-tempera- ture state exhibits typical ferroelectric properties, such as fer- roelectric hysteresis, pyro-, and piezoelectricity, etc. 9

content (x > 0.35) 40 or

38

or even by thermal annealing stimulating cation

1/3 Nb 2/3 O 3 x

(SBN) with large Ba 2+ content (x 0.5). 41

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.

compounds exhibit specific macroscopic phase inhomogene-

43,44 Some

4

Journal of the American Ceramic Society—Shvartsman and Lupascu

Vol. 95, No. 1

ity. Namely, depth-resolved X-ray diffraction experiments

(1 x)PbZn 1/3 Nb 2/3 O 3 xPbTiO 3

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.

performed on single crystal (PZN-PT) 45 and PMN-PT

46

(2) Lead-Free and Lead-Containing Systems

While the relaxor behavior was initially discovered in Ba- TiO 3 BaSnO 3 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)O 3 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

Relaxors: The BaTiO 3 BaSnO 3

was the first system in which relaxor properties were discov-

ered. 6 A number of relaxor compounds based on BaTiO 3

(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 1940s 55,56 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, T C = 393 K (Fig. 4). Below T C ,

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 T C , the dielectric

permittivity follows a CurieWeiss law e = C/(T h) with the CurieWeiss temperature, h < T C , indicating a first-order phase transition.

(A)

BaTiO 3 -Based

a first-order phase transition. (A) BaTiO 3 -Based Fig. 4. The crystallographic structure of BaTiO 3

Fig. 4.

The crystallographic structure of BaTiO 3 .

When solid solutions with other perovskite type com- pounds are formed, BaTiO 3 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 BaTiO 3

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 ABO 3 , for example, in Ba 1 x (Sm

3 (denotes a vacant site), 58 and

BaTiO 3 BiScO 3 5961 or BaTiO 3 La(Mg 0.5 Ti 0.5 )O 3 , 62,63 respec- tively. In the second case, the relaxor behavior appears in compounds with substituted B-site cations, such as BaTiO 3

BaSnO 3

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, T C 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 BaTiO 3 , however, without the frequency shift of T m 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 CurieWeiss law at T > T m [Fig. 6(b)]. This

deviation usually starts at temperatures significantly larger (up to hundreds of degrees) than T m . Several phenomenological approaches have been devel- oped to describe the DPT behavior. One is based on the

0.5 Na 0.5 ) x TiO 3 , 57

Ba 1 x/2

x/2 (Ti 1 x Nb x )O

6

or BaTiO 3 BaZrO 3 . 64

January 2012

Lead-Free Relaxors

5

January 2012 Lead-Free Relaxors 5 Fig. 5. (a) Phase transitions in BaTiO 3 according to the

Fig. 5. (a) Phase transitions in BaTiO 3 according to the displacive scenario with Ti ions shifted from the center. (b) Phase transitions in BaTiO 3 according to the orderdisorder 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).

probabilities from most to less probable (Refs. 117,119). Fig. 6. (a) Temperature dependences of the real

Fig. 6. (a) Temperature dependences of the real part of the dielectric permittivity measured at 10 2 10 6 Hz for heterovalent- substituted (1 x)BaTiO 3 xLa(Mg 1/2 Ti 1/2 )O 3 compounds. (b) Temperature dependences of the reciprocal permittivity for same compositions fitted by the CurieWeiss law. Reprinted with permission from Ref. 63. Copyright Taylor & Francis Group, http:// www.informaworld.com.

model proposed by Kirillov and Isupov. 47 In this model, the DPT is considered to be due to local composition fluctua- tions, resulting in microregions with different local Curie points distributed in a Gaussian fashion around a mean Curie temperature. The following equation was obtained to describe the temperature dependence of the dielectric permit- tivity in the vicinity of T m :

e 0 ¼ e 0 1 þ

e 0 m

1 þ

ð

T

T

m

Þ 2

;

2

d 2

(2)

where em is the maximum of the dielectric permittivity at a given frequency, T m 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 Eiras

65

e 0 ¼

e 0 m

c ; T T m 1 þ d
c ;
T
T m
1 þ
d

(3)

Here, T m 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 CurieWeiss 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 T m can be fitted maintaining the parameters d and c frequency-indepen-

dent. 65

m ¼

ð T

used to describe the DPT. While it is very similar to the Eq. (3) and yields the same values of the parameter c, the dimen- sionality of the parameter C depends on the value of c, which makes this notation physically difficult to interpret. At higher substitution, T m starts to show frequency disper- sion matching the VogelFulcher law [Eq. (1)]. This is often used as a criterion of a completed crossover to relaxor behavior. Sometimes, especially when data of the frequency dispersion of e(T) are missing, the relaxor state is associated with the condition c = 2 [Eq. (3)]. For example, for the (1 x)BaTiO 3 xLa(Mg 0.5 Ti 0.5 )O 3 system, the parameter c changes from 1.1 to 1.9 when x increases from 0 to 0.075, respectively (Table I). 63 Correspondingly, compounds with x 0.075 show a distinct T m (f) dispersion [Fig. 6(a)]. The degree of the crossover from the ferroelectric to the relaxor state depends on the substitution type. Ravez and Simon systematized the effects of various substitutions on the properties of BaTiO 3 . 15,67 Most experimental data agree well

Þ c =C, proposed by Uchino and Nomura, 66 is often

Instead of Eq. (3), another function, 1=e

0 1=e

0

T m

6

Table I.

Journal of the American Ceramic Society—Shvartsman and Lupascu

Vol. 95, No. 1

Summary of the Dielectric Characteristics for (1 x)BaTiO 3 xLa(Mg 0.5 Ti 0.5 )O 3 Ceramics

x e m (10 5 Hz)

T m , K (10 5 Hz)

D T m , K (10 2 10 6 Hz)

c

T f , K

E a , eV

f 0 , 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

2.310 10

Here, e m is the peak value of the dielectric permittivity at 100 kHz, D T m is the difference between positions of the maximum in the e (T) dependences, T m , mea- sured at 10 6 and 10 2 Hz, the parameter c reflects a degree of diffuseness of the e (T) peaks according to Eq. (3). T f , E a , and f 0 are the VogelFulcher 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 (1 x)BaTiO 3 xLa(Mg 0.5 Ti 0.5 )

O 3 , 63 x = 0.075 for (1 x)BaTiO 3 xNaNbO 3

(1 x)BaTiO 3 xBiScO 3

] or on both B- and oxygen-sites

for Ba(Ti 1 x Li x )O 3 3x F 3x 69 ] (Table II). Heterova-

lent B-site substitution is exemplified by Nb-doped BaTiO 3 , 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 Ba 1 x/2 x/2 (Ti 1 x Nb x )O 3 . 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.,

). In solid solutions with isovalent-

substituted Ti

the relaxor state is only observed at a fairly large substitution

levels x > 0.250.30. 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 BaTiO 3 BaMO 3

(M = Zr, Sn) Solid Solutions: The isovalently substituted BaTiO 3 BaMO 3 (M = Zr, Sn) solid solutions show a more gradual crossover to the relaxor state than heterovalent- substituted compositions. The merger of all polymorph trans-

, x = 0.10 for

68

59

[x = 0.04

x = 0.10

for

TiO 3

Ba 1 x Bi 2x/3 x/3 TiO 3 70 or x = 0.20 for

71

Ba 1 x K x/2 La x/2

4+ ,

like BaTi 1 x Zr x O 3 7274 or BaTi 1 x Sn x O 3 6,7578 ,

Table II.

Critical Concentrations Corresponding to the

Ferroelectric-Relaxor Crossover for Some BaTiO 3 -Derived

Systems

Type of

substitution

Solid solution

x 0

Ref.

Isovalent:

B-site

Heterovalent:

A-site

Heterovalent:

A- and

B-site

Heterovalent:

B- and

anion-site

BaTi 1 x Zr x O 3 BaTi 1 x Sn x O 3 BaTi 1 x Ce x O 3

Ba 1 x Bi 2x/3 x/3 TiO 3 Ba 1 x K x/2 La x/2 TiO 3

Ba 1 x (Sm 0.5 Na 0.5 Ba 1 x/2 x/2 (Ti 1-x

x

) TiO Nb x )O 3 *

3

Ba 1 x La x [Ti 1 x (Mg 0.5 Ti 0.5 ) x ]O 3

Ba 1 x Na x [Ti 1 x Nb x ]O 3

Ba 1 x Bi x [Ti 1 x Sc x ]O 3 Ba 1 x Bi x [Ti 1 x Al x ]O3

Ba 1 x La x [Ti 1 x Fe x ]O 3 Ba[Ti 1 x Li x ]O 3 3x F 3x

0.30

0.25

0.20

0.10

0.25

0.20

0.075

0.055

0.075

0.10

0.10

0.10

0.04

74

76

279

70

71

57

58

63

68

59

280

281

69

denotes vacant site. * While BaTiO 3 doped by Nb 5+ nominally corresponds to B-site substitu- tion, A-site vacancies are needed for charge compensation in this case. Thus, one has actually the situation corresponding to both A- and B-site heterova- lent substitution.

formations of parent BaTiO 3

occurs at x ~ 0.10 79 and x ~ 0.08 80 for (1 x)BaTiO 3 xBaZrO 3 (BTZr) and (1 x)BaTiO 3 xBaSnO 3 (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 T m both in BTSn 82,83 and BTZr 74 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-

(pinched phase transition)

7 4 , 8 3 This relaxa- (pinched phase transition) Fig. 7. Temperature dependences of the

Fig. 7. Temperature dependences of the real part of the dielectric permittivity measured at different frequencies for isovalent- substituted (1 x)BaTiO 3 xBaSnO 3 compounds [Ref. 76].

(1 x )BaTiO 3 – x BaSnO 3 compounds [Ref. 76]. Fig. 8. Frequency spectra of

Fig. 8. Frequency spectra of the imaginary part of the dielectric permittivity for (1 x)BaTiO 3 -xBaSnO 3 ceramics with DPT (15% of Sn) and relaxor (30% of Sn) behavior (Ref. 76).

January 2012

Table III.

Lead-Free Relaxors

Summary of the Dielectric and Relaxor Characteristics for (1 x)BaTiO 3 x BaZrO 3 Ceramics. Parameters are the Same as for Table I [Ref. 74]

7

x

e m (10 5 Hz)

T m , K (10 5 Hz)

D T m , K (10 2 10 6 Hz)

c

T f , K

E a , eV

f 0 , Hz

0.15

31900

344.5

0.5

1.29

0.20

30200

317

0.6

1.46

0.25

13500

279.5

3

1.93

278

5 9 10 4

8.9 9 10 7

0.30

11900

233

6

1.86

228

0.001

1.2 9 10 7

0.35

9960

198

25

1.96

165

0.02

10 8

0.40

4600

161

42

1.9

70

0.13

1.5 9 10 12

tion already appears above T m , 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 T m has also been reported for the heterovalent-substituted solid solution (BaTiO 3 ) 0.975 (LaMg 1/2 Ti 1/2 O 3 ) 0.025 also show- ing DPT behavior. In compositions with larger content of Sn (or Zr), a shift of T m with frequency following the VogelFulcher 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 10 6 and 10 9 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 110130 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 VogelFulcher

fits of T m (f) differ for these compositions. 74,76 For BTSn with

20% and 25% of Sn 4+ , for example, T f is substantially

higher than the temperature corresponding to complete freez- ing of PNRs relaxation. An explanation is that T f estimated from the VogelFulcher fit corresponds to the appearance of an infinite percolated cluster with frozen polarization, while some re-orientable PNRs continue to exist below T f . Bokov et al. similarly suggested that in BTZr (x = 0.35), two inter-

penetrating sets of PNRs exist below T f : static (large) PNRs

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 T m . 73 In compositions with relatively high substitution rate, x 0.30 (BTSn), x 0.40 (BTZr) T f 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

In compounds with Zr content

0.80 x 0.95, the relaxation peak in the dielectric per-

mittivity, T m , follows the Arrhenius law, f = f 0 exp( E a /kT m ). The authors attributed this relaxation to PNRs appearing around the ferroelectrically active Ti 4+ cations introduced into the nonpolar matrix of BaZrO 3 . As the Ti content

84

and

the Zr-rich side. 64,87

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 (1 x)BaTiO 3 xBaZrO 3 solid solutions based on experimental data by several authors. After a pinched transition at x ~ 0.10, the low-tem- perature state below T m 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

, but regions with dynamic PNRs simultaneously exist

below the transition temperature. 74

0.35 < x < 0.80, canonical behavior is found transiting into

the NR state with macroscopic cubic symmetry below T f . 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 T D ~ 440 K, a deviation from linear behavior was observed indicating an electrostric- tive strain due to formation of the local spontaneous polari-

In the range

T f

zation. Thus, T D 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 paraelectricergodic 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

compounds. Some authors argue that it is qualita-

BaTiO 3

tively different from canonical PMN-type relaxors 64,89 based,

for example, on results of heat capacity measurements, 89

for example, on results of heat capacity measurements, 8 9 Fig. 9. Phase diagram of the

Fig. 9. Phase diagram of the (1 x)BaTiO 3 xBaZrO 3 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 T m (at 100 kHz) and T f , 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,

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 250350 and 150200 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 BaZr 0.35 Ti 0.65 O 3 by X-ray diffraction measure-

ments under electric field. 91

Bokov et al. have argued that

the presence of nanometer-size nonpolar Zr-rich regions 90,95 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 T f

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 T m (f). The authors attributed this depolarization to a transition from the field-induced ferroelectric state back to a NR state.

A pecu-

89

(C) BaTiO 3 BiScO 3 , A Re-Entrant Relaxor:

liar behavior has been observed in (1 x)BaTiO 3 xBiScO 3

relaxors. The BiScO 3 is a paraelectric with a monoclinic dis- torted perovskite structure characterized by both oxygen octahedra tilting and antiparallel displacement of B-cations. Solid solution (1 x)BaTiO 3 xBiScO 3 shows a fast crossover from the ferroelectric to the relaxor behavior typical of heterovalent substitutions. 59,61 At x 0.10, the samples show VF-type behavior with an activation energy E a ~ 0.10.2 eV, a value about one order of magnitude larger than in PMN. 59 Such values of E a imply a weak interaction between PNRs classifying this system as a “weakly coupled relaxor,” where the PNRs are isolated and frustrated in a matrix that provides only weak coupling between neighboring polar regions. Contrary to most BT-derived relaxors, an increase of both T m and T f was observed in compounds with higher BiScO 3 content starting from x = 0.10 [Fig. 10(a)]. 59 Such enhance- ment of the transition temperature at relatively small amount of the second component is unusual in BT-based solid solu- tions. It was reported only when Ba was partially substituted

either by Pb 97

bonding due to its partially covalent nature 99 induces a dif- ferent component of polarization in the structure pushing the

transition temperature to higher values. 98 A similar type of T m (x) dependence with a minimum has been reported for

some other systems, for example, (1 x)BTxKNbO

(1 x)BTxNaNbO 3 101 solid solutions. However, in these cases, the increase of T m starts at rather high concentrations of the second component, x = 0.7 and 0.5, respectively, reflecting a dilution of the high T C KNbO 3 and NaNbO 3 compounds by BaTiO 3 . Another marked phenomenon reported for the BaTiO 3 BiScO 3 system is re-entrant relaxor behavior called so analo- gously to re-entrant magnetic spin glass systems. 61,102 A more ordered state first develops at higher temperatures before going back to a more disordered state at low temperature. Taking the remanent polarization, for example, it first increases as the temperature is lowered, but drops again on further cooling essentially vanishing at low T [Fig. 10(b)]. 61 Another manifestation of re-entrant behavior is a relaxation peak related to the freezing of PNRs occurring below another frequency-independent transition attributed to the ferroelectric phase transition [Fig. 11(a)]. 102 This was inter-

3 100 and

96

59

or by Bi 98 . It was assumed that the BiO

96 59 or by Bi 9 8 . It was assumed that the Bi – O

Fig. 10. (a) The peak (T m ) and freezing temperature (T f ) as a function of BiScO 3 concentration for (1 x)BaTiO 3 xBiScO 3 ceramics (from Ref. 59). (b) Remanent polarization as a function of temperature in (1 x)BaTiO 3 xBiScO 3 ceramics showing re-entrant relaxor behavior. Reprinted with permission form Ref. 61. Copyright 2011, The American Physical Society.

preted as a long-range-ordered state with a remanent polar- ization developing below T m between the ER and the NR states in (1 x)BaTiO 3 xBiScO 3 (0.10 x 0.45). Bharad- waja et al. assumed that re-entrant features in this system are due to a competitive dipole interaction between local ferro- electric and AFE order and/or local stresses. 61 Guo et al. observed by piezoresponse force microscopy that the disor- dered state with presence of PNRs grows within the normally ordered ferroelectric phase. 102 They concluded that polar clusters develop from a ferroelectric state and re-enter the frozen disordered phase, instead of emerging from a para- electric state as in most other relaxor ferroelectrics. 102 Similar re-entrant relaxor behavior has also been reported for some other lead-free systems, like 0.99BaTiO 3 0.01 AgNbO 3 103 and Ba 2 Nd 1 x Pr x FeNb 4 O 15 104 [Fig. 11(b)].

There

are many evidences that at the microscopic scale, BaTiO 3 - based relaxors behave similar to pure barium titanate. The Raman spectra of BT-derived relaxors, for example, look very much like those recorded in the paraelectric phase of BaTiO 3 with broad bands centered at ~ 285 and 520 cm 1 (Fig. 12). 58,88,90,105,106 Even though a perfect cubic symmetry forbids any Raman modes, the Raman spectrum in the para- electric phase of pure BaTiO 3 has been reported at tempera- tures up to 570 K. It is considered as an indication of a strong local disorder due to random displacement of Ti 4+ ions at high temperatures. 107,108 Presence of these bands in BT-derived relaxors implies that the local structure around the BO 6 octahedra deviates from the perfect cubic symmetry. It was conjectured that the local structure of BTZr relaxors is rhombohedral. 105 A high-frequency mode at ~ 780 cm 1 (BTZr), not existing in pure BT is often considered as a sig- nature of the relaxor phase. 88,105,106 In contrast to ferroelec-

(D)

BaTiO 3 -Based Relaxors: Microscopic Properties:

January 2012

Lead-Free Relaxors

9

January 2012 Lead-Free Relaxors 9 Fig. 11. Temperature dependence of the real part of the dielectric

Fig. 11. Temperature dependence of the real part of the dielectric permittivity measured between 10 2 and 10 6 Hz for (a) (1 x)BaTiO 3 x BiScO 3 , x = 0.05 (Reprinted with permission from Ref. 102. Copyright 2008, American Institute of Physics) and (b) Ba 2 Pr x Nd 1 x FeNb 4 O 15 , 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-

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

width. 58,105,106,109

(for the 520 cm 1 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 Ti 4+ displacements present in the ferroelectric BaTiO 3

persist in BTZr relaxors.

moments associated with the Ti 4+ 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 Ti 4+ and Zr 4+ 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.

A ran-

dom distribution of the Ti displacement symmetries among the TiO 6 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.

Off-centering of Ti 4+ ions in BTZr solid solutions was

confirmed by the analysis of neutron total scattering mea-

while the

surements by a reverse Monte Carlo approach,

Zr 4+ ions remain in centers of the oxygen octahedra. The correlation of the Ti 4+ 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

Moreover, the local dipole

110

111

111

112

0.35). 1 1 2 Moreover, the local dipole 110 111 111 112 Fig. 12. Ref. 109.

Fig. 12.

Ref. 109. Copyright 2009, American Institute of Physics.

Temperature evolution of Raman spectra for (1 x)BaTiO 3 xBaZrO 3 ceramics with x = 0.00 and 0.35. Reprinted with permission from

10

Journal of the American Ceramic Society—Shvartsman and Lupascu

Vol. 95, No. 1

Electron diffraction experiments on both isovalent and heterovalent-substituted BaTiO 3 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 BaTiO 3 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 BaTiO 3 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-

This interpretation of the diffuse electron

electric order. 114

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 BaTiO 3 and

BaTiO 3 -based relaxors (at least in systems where the second component is paraelectric) are substantially related to

ions from the center position in the

displacements of Ti oxygen octahedra.

4+

(E)

Origin of the Relaxor Behavior in BaTiO 3 -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 T m .

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. It is natural to assume that the development of the relaxor state in hetero-substituted BaTiO 3 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)O 3 . 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 BaTiO 3 results mainly from cooperative off-center shifts

of the Ti 4+ (B-site) cations in the oxygen cages. This is con- trary to the lead-containing ferroelectrics, where off-centrality

of Pb 2+

cations on the A-site plays a major role. In BaTiO 3 ,

substitution of Ti 4+ 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 BaTiO 3 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, T C . When the concentration of substituted cations is below a critical thresh- old, the number of the perturbed clusters is small, but each

29,48

28

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 T f . 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, Sn 4+ 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 BaTiO 3 , 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 TiO 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:

T D , T C , and T f . 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, T D , 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 T f , may lie below T C 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 T C lies below T f , 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-

ing

cate that the Ti 4+ ions randomly occupy one of the eight equivalent off-center sites along the [111] cubic directions [Fig. 5(b)]. Nuclear magnetic resonance experiments 119 and terahertz dielectric spectroscopy 120 point out a coexistence of

115,117

and electron paramagnetic resonance 118 data indi-

January 2012

Lead-Free Relaxors

11

displacive and orderdisorder features for the ferroelectric

phase transition of BaTiO 3 . Brillouin scattering, 121 wide band

dielectric spectroscopy,

and photon correlation spectros-

copy 123 give evidence that “jumps” of Ti 4+ ions in between different positions are correlated in neighboring unit cells resulting in polar clusters with a size of a few nanometers far from T C and up to 200 nm 123 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 T C are related to PNRs in BaTiO 3 -related relaxors. A high-frequency (f ~ 10 8 10 9 Hz) dielectric relaxation similar to the one in pure BaTiO 3 has been reported for BTSn composition relaxors with DPT behavior. 76 One can assume that polar clusters in pure BaTiO 3 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 Ti 4+ 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 TiO 6 octahedra and impede a perfect alignment of all Ti displace- ments as in ferroelectric BaTiO 3 . 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, (1 x)BTx(Na 0.5 Bi 0.5 )TiO 3 , T C 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 NbO 3 (KNN) and (Bi 0.5 Na 0.5 )TiO 3 (BNT). 126128

Search for

(K 0.5 Na 0.5 )

122

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. VogelFulcher behavior of T m (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)NbO 3 between ferroelectric KNbO 3 and antiferroelectric NaNbO 3 are their relatively high Curie temperatures, several polymorphic phase transitions (PPT), and the existence of morphotropic phase boundaries (MPBs). 126130 The compositions around 50% of

NaNbO 3 lie in the vicinity of a MPB between two ortho- rhombic phases and show the best piezoelectric properties, a longitudinal piezoelectric coefficient, d 33 ~ 160 pC/N, and an

electro-mechanical coupling factor k

up to 40%, as well as a

high Curie temperature (693 K). 131133 Besides the paraelec-

tric (cubic) to ferroelectric (tetragonal) phase transition at T C , other transitions between ferroelectric phases with tetrag- onal to orthorhombic and orthorhombic to rhombohedral symmetry change occur at T to = 473 K and T or = 80 K,

Due to the high T C , KNN is a promising

respectively.

candidate for high-temperature applications. Relaxor behav- ior has been observed in systems, like (1 x)KNNxBT

(x > 0.10), 134

KNNxSrZrO 3

(x > 0.04), 139 etc.

p

129,130

(1 x)KNNxSrTiO 3

(x > 0.15),

138

(x > 0.15), 135137

(1 x)

(1 x)KNNxBiScO 3

1 3 5 – 1 3 7 (1 x ) (1 x )KNN – x BiScO

Fig. 13. Temperature dependences of the dielectric permittivity measured at frequencies from 10 kHz to 1 MHz for (1 x)KNNx SrTiO 3 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, T C (or T m ) 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 CurieWeiss behavior above T m and the parameter c describing the degree of diffuseness of the transition [Eq. (3)] increases. The T to 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 KNNBaTiO 3 (x = 0.06) 134 and KNNSrTiO 3

(x = 0.04)

. At a high enough degree of substitution, for

example, x 0.15 and x 0.10 for KNNSrTiO 3 135 and KNNBa 0.5 Sr 0.5 TiO 3 140 , respectively, the peak position, T m , shows relaxor-like frequency dispersion (Fig. 13). The macro- scopic symmetry below T m 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 KNNBiScO 3 to x ~ 0.15 in KNNSrTiO 3 . Some compounds, for example, 0.96KNN0.04BiScO 3 and

0.85KNN0.15SrZrO 3 show an extremely broad plateau-like maximum in e (T), for which, the large dielectric permittivity ( ~ 5000) remains almost constant in intervals of 100150 K width at temperatures above 300400 K, respectively. 138,139 Based on the similarity between this behavior and that of

dipolar glasses,

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 KNNBiScO 3 , to

maintain large dielectric permittivity in a broad temperature range makes them quite attractive for high-temperature capacitors. 139

135

141

Bobnar et al. have argued that the compo-

Sim-

ilar to KNN, bismuth sodium titanate Bi 0.5 Na 0.5 TiO 3 (BNT) is considered as a promising lead-free piezoelectric mate- rial. 126128 Of particular interest are solid solutions (1 x) BNTxBT, 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

(G) Bi 0.5 Na 0.5 TiO 3 “Antiferroelectric” Relaxors:

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: d 33 ~ 155 pC/N, and k p ~ 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 ferroelectrics 52,144,145

like:

1.

A broad peak of the dielectric permittivity.

2.

Absence of a structural transformation at T m .

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

a transition from a tetragonal to a cubic phase at 813 K.

The temperature dependence of the dielectric permittivity shows several anomalies [Fig. 14(a)]: a broad maximum at T m ~ 593 K corresponds to a transition from a paraelectric (according some reports ferroelastic 147,150 ) 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, T d . 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 T d and T m . 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 do not reveal any structural transition at T m , 150,154 but indi- cate coexistence of rhombohedral and tetragonal phases in this temperature range. 150 Weak pyroelectricity and a finite bottleneck of the double hysteresis loops indicate the exis- 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 orthorhombic AFE phase proceeds via an intermediate AFE modulated phase consisting of orthorhombic sheets in a rhombohedral matrix in the range between 473 and

573 K. 146 The orthorhombic phase is then formed at 573 K

and immediately turns into the tetragonal one. 146 The inter-

mediate state is characterized by polar disorder which becomes apparent in relaxor-like behavior of the low-temper- ature dielectric anomaly. 146,150 The NBT is considered to be

a relaxor due to a substantial frequency dispersion at T d ,

absence of a structural transformation at T m , and indications of phase coexistence at the nanoscale. 150,151,156158 The relax- or behavior was attributed to the presence of ferroelectric rhombohedral clusters embedded in a nonpolar tetragonal

or polar Na + TiO 3 and Bi 3+ TiO 3 clusters in an

AFE matrix. 156

matrix 150

and 673 K, 146,150 where these phases coexist, and finally,

149

The structural complexity is intimately related to cation

disorder in the Na/Bi sublattice.

solutions with other perovskites, for example, in BNTBT. Indeed, a strong frequency dispersion of the dielectric permit-

tivity around T d has been reported for (1 x)BNTxBT solid

solutions with 0.06 x 0.09 (Fig. 15).

shows a phase diagram of the BNTBT

the BNT side, T m corresponding to the transition to a para- electric phase decreases from 593 K in pure BNT to ~ 550 K

On

Figure 16

It is enhanced in solid

146

144

system. 52,142,145

enhanced in solid 146 144 s y s t e m . 52,142,145 Fig. 14. Temperature

Fig. 14. Temperature dependences of the dielectric permittivity measured at frequencies from 10 2 to 10 6 Hz for (a) Bi 0.5 Na 0.5 TiO 3 . (Reprinted with permission from Ref. 153. Copyright 1998), with permission from Elsevier), (b) 0.5Bi 0.5 Na 0.5 TiO 3 0.5BaTiO 3 , and (c) 0.3Bi 0.5 Na 0.5 TiO 3 0.7BaTiO 3 ceramics (Reprinted from Ref. 52. Copyright 2004, Elsevier).

in compositions with x = 0.05 and then only weakly depends on the BT content. The temperature corresponding to the transition to the AFE tetragonal state, T 2 , rapidly drops down and merges with the depolarization temperature, T d , at

x = 0.02-0.03. At x 0.06, T d (x) starts to rise, while T 2 (x) continues to decrease, determining the morphotropic phase boundary (Fig. 16). The transition between paraelectric phases with tetragonal and cubic symmetry also shifts to

lower temperatures approaching T m

at x ~ 0.05. 145 It

remains unclear whether this transition merges with the

(x) line at x > 0.05 or dissolves into an average cubic

phase with local tetragonal distortion. 145 The nature of the region of the phase diagram, defined by 0.05 < x < 0.11 and T d < T < T m is not clear yet. Based on the analysis of the elastic compliance, Cordero et al. suggested that for x > 0.05

and T < T d , the phase is pseudocubic with local tetragonal distortions. 145 The compositions from this range show relaxor- like frequency dispersion near T d , which is substantially stron- ger than that in the parent BNT. Sheets et al. considered the state between T m and T d , as a “region of frustration where multiple domain states are simultaneously available.” 159 By analogy with other relaxor systems, the frequency dispersion of the dielectric permittivity might be related to the existence of the polar nanoregions, which probably form much above

Indeed, room temperature TEM studies reveal that

T m . 150,151

T m

January 2012

Lead-Free Relaxors

13

January 2012 Lead-Free Relaxors 13 Fig. 15. Temperature dependences of the dielectric characteristics for (1 x

Fig. 15. Temperature dependences of the dielectric characteristics for (1 x)Bi 0.5 Na 0.5 TiO 3 xBaTiO 3 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 BaTiO 3 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 (Bi 3+ ,

Na + , Ba

) are antiparallel to the displacements of the

B-site cation (Ti 4+ ) 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 Bi 3+ /Na + and Ti 4+ along the [001] direction. 149 However, the AFE ordering in BNTBT is only short-ranged

2+

the AFE ordering in BNT – BT is only short-ranged 2+ Fig. 16. Phase diagram of

Fig. 16. Phase diagram of (1 x)Bi 0.5 Na 0.5 TiO 3 xBaTiO 3 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