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Department of Materials Science and Engineering, University of Florida, Gainesville 32611, Florida
Department of Materials Science and Engineering, North Carolina State University, Raleigh 27695, North Carolina
k
School of Materials Science and Engineering, University of New South Wales, NSW 2052, Australia
Ceramics Laboratory, Swiss Federal Institute of Technology EPFL, Lausanne 1015, Switzerland
Dedicated to Prof. Dr. Marija Kosec, our Maricka, who left us after a long struggle in her tenacious spirit in December 2012.
Bismuth ferrite (BiFeO3), a perovskite material, rich in properties and with wide functionality, has had a marked impact on
the eld of multiferroics, as evidenced by the hundreds of articles published annually over the past 10 years. Studies from
the very early stages and particularly those on polycrystalline
BiFeO3 ceramics have been faced with diculties in the preparation of the perovskite free of secondary phases. In this
review, we begin by summarizing the major processing issues
and clarifying the thermodynamic and kinetic origins of the
formation and stabilization of the frequently observed secondary, nonperovskite phases, such as Bi25FeO39 and Bi2Fe4O9.
The second part then focuses on the electrical and electromechanical properties of BiFeO3, including the electrical conductivity, dielectric permittivity, high-eld polarization, and strain
response, as well as the weak-eld piezoelectric properties. We
attempt to establish a link between these properties and
address, in particular, the macroscopic response of the ceramics under an external eld in terms of the dynamic interaction
between the pinning centers (e.g., charged defects) and the
ferroelectric/ferroelastic domain walls.
I.
Introduction
D. J. Greencontributing editor
Manuscript No. 34489. Received January 30, 2014; approved April 4, 2014.
*Member, The American Ceramic Society.
Feature
1994
BiFeO3 ceramics. Among the most interesting are the BiFeO3PbTiO3 (BFPT)14,16 and BiFeO3BaTiO3 (BFBT)15,17,18
systems, which provide both enhanced piezoelectricity and a
high TC at the MPB, the latter exceeding that of Pb(Zr,Ti)O3
(PZT) (TC ~ 650C for BFPT, TC ~ 600C for BFBT and
TC ~ 350C for PZT at the MPB). In addition, a number of
other BiFeO3-based lead-free compositions are presently the
subject of intensive studies, including BiFeO3REFeO3
(RE = La, Nd, Sm, Gd, Dy),1921 BiFeO3AETiO3
(AE = Mg, Ca, Sr),2226 BiFeO3Bi0.5K0.5TiO327, and BiFeO3Bi(Zn0.5Ti0.5)O3.28 The piezoelectric properties of many
of these ceramic systems have not yet been characterized systematically.
The processing of single-phase BiFeO3 ceramics is dicult; however, signicant progress has been made recently,
particularly in relation to the identication of the origins of
the frequently formed nonperovskite, secondary phases. In
addition, the complex relationship between processing and
defects, on one hand, and the high- and weak-eld electrical
and electromechanical properties, on the other, has been
addressed to some extent. Up to now, a lot of these new
ndings, in particular those relating to processing and
domain-switching behavior, have not been considered suciently or are even ignored in the literature. Along with the
aim of presenting a detailed overview of the past and recent
results on BiFeO3 ceramics, this absence or poor coverage
of some important topics was one of the motivations that
led us to prepare a comprehensive article, which also
includes new data.
The review comprises two topics on BiFeO3 that are the
most controversial and have encountered signicant research
barriers, that is, the processing and the electrical/electromechanical properties. The study does not cover magnetic properties and structural aspects. Whereas the crystal structure of
BiFeO3 has been reviewed in a study by Catalan and Scott,3
and referred to in earlier publications,10,29,30 the data on the
microstructure and the domain structure are only reported
occasionally, without general relations to, for example, the
piezoelectric properties of the undoped BiFeO3 bulk materials and ceramics in particular.
The section on processing covers the major issues
encountered in the synthesis of BiFeO3: (i) the thermodynamic instability and ternary phase diagrams with impurity
oxides; (ii) the reaction kinetics of the Bi2O3Fe2O3 system;
and (iii) the sublimation/evaporation of bismuth oxide during high-temperature treatments. By critically analyzing
these interrelated issues we reveal the multiple origins of the
often-formed secondary phases and their persistence in sintered BiFeO3 ceramics. The processing section ends by illustrating the major problems accompanying the conventional
solid-state processing of BiFeO3, along with general guidelines to be considered when undertaking the synthesis of the
ferrite.
BiFeO3 is known as a perovskite with a high electrical
conductivity, which is probably the major concern for the
applications of the ferrite and its chemical modications. The
rst part of the section on properties is devoted to this issue
where we discuss the impact of the electrical conductivity on
the low-frequency (mHz-to-MHz region) dielectric permittivity of BiFeO3 and address some of the inconsistencies
found in the literature. Based on the available literature data
and our own studies, the character of dielectric relaxation,
the type of conductivity, as well as the nature of point and
electronic defects are discussed.
Considering the unfortunate combination of the high electrical conductivity and the high coercive eld of BiFeO3, it is
not surprising that diculties in studying domain switching
and piezoelectricity persist. We address the switching behavior of the ferrite through an analysis of the polarization(PE) and strain-electric-eld (SE) hysteresis loops, supported
by synchrotron X-ray diraction analysis. In addition, we
review and discuss the direct longitudinal piezoelectric
II.
Processing Issues
! BiFeO3
(1)
July 2014
1995
(b)
(a)
Fig. 1. Thermodynamic instability of BiFeO3. (a) X-ray diraction (XRD) patterns of BiFeO3 at room temperature (25C) and after isothermal
annealing at 700C, 775C, and 850C, showing rstly the decomposition of BiFeO3 into Bi25FeO39 and Bi2Fe4O9 at 700C, followed by the
disappearance of these secondary phases (i.e., the reappearance of BiFeO3) at T 775C. (b) Calculated temperature dependence of the Gibbs
free energy (DrGm) of the equilibrium reaction between BiFeO3 and the Bi- and Fe-rich phases [data are plotted for DrHm = 1.98 kJ/mol and
DrSm = 3.62 J/molK; see Ref. (41)]. Note the slightly positive DrGm in the region 447C< T < 776C, implying that the Bi25FeO39 and
Bi2Fe4O9 are, though weakly, more thermodynamically stable than BiFeO3 in this temperature interval, in agreement with the experimental data
shown in panel (a). Reprinted with permission from Ref. [41] Copyright 2009 American Chemical Society.
(2)
Fig. 2. Inuence of impurities on the phase composition of a reacted Bi2O3Fe2O3 mixture (example of SiO2 as impurity). (a) X-ray diraction
(XRD) patterns of Bi2O3Fe2O3 mixture, annealed at 800C for 5 h, without (0.0%) and with additions of 0.1wt% and 0.5wt% SiO2. (b)
Proposed phase relations in the ternary Bi2O3Fe2O3AOx system, where AOx is SiO2. According to the proposed phase diagram (panel b), a
small amount of SiO2 added to the Bi2O3Fe2O3 mixture should result in a large amount of secondary phases at equilibrium, as conrmed
experimentally (see panel a). Reprinted with permission from Ref. [43] Copyright 2007 American Chemical Society.
1996
calculations that a small amount of introduced SiO2 will generate a large amount of the Bi-rich and Bi-poor secondary
phases upon reacting the mixture. The calculations were conrmed experimentally by deliberately adding 0.1 and 0.5 wt
% of SiO2 to a stoichiometric Bi2O3Fe2O3 mixture; upon
annealing, the additions indeed resulted in large amounts of
the secondary phases, which were easily detected by XRD
[Fig. 2(a)].
In addition to SiO2, ternary phase diagrams were also proposed for other impurities: (i) Al2O3, which, according to
energy-dispersive X-ray spectroscopy analysis (EDXS), incorporates into the Bi2Fe4O9 phase; and (ii) TiO2, which, in
addition to incorporating into the Bi2Fe4O9, partially substitutes for the Fe3+ in BiFeO3.43 Both oxides, added in small
quantities (up to 0.5 wt%), led to the compositional degradation of the BiFeO3 upon annealing, just like in the case of
SiO2 [Fig. 2(a)]. Thus, the strong inuence of impurities on
the equilibrium phase composition has its origin in the
specic phase relations intrinsic to the Bi2O3Fe2O3AOx
ternary systems, where AOx represents an impurity oxide
that is more soluble in either Bi25FeO39 and/or Bi2Fe4O9
than in BiFeO3.
Though not directly discussed, the eect of impurities on
BiFeO3 should be considered with care, taking into account
the long list of oxides, including SiO2, ZnO, GeO2, PbO,
Ga2O3, ZrO2, Nb2O5, and MnO, that can form the sillenite
phase by reacting with Bi2O3,4447 possibly resulting in the
compositional degradation of the ferrite (analogous to the
case of SiO2, Fig. 2). Therefore, monitoring the type and
amount of impurities present in the starting Bi2O3 and Fe2O3
powders is extremely important; as a matter of fact, phasepure BiFeO3 can be successfully synthesized using starting
oxides with ultrahigh purity, that is, >99.999%.43 Another
source of contamination during the processing of BiFeO3,
which is rarely considered in the literature, is the milling procedure. For example, prolonged milling (>10 h) using conventional yttria-stabilized zirconia (YSZ) milling media and
vials may cause substantial wearing of the milling balls and
contamination of the powder with ZrO2;48 the ZrO2 may
then react upon annealing the contaminated powder to form
the sillenite phase.46
Even though all the impurity oxides may not necessarily
have such a strong eect as SiO2 or Al2O3, the sensitivity of
BiFeO3 to impurities should also be considered in view of
the doping. Namely, several authors report on the persistence
of the secondary phases in the ceramics even at low doping
levels (1 mol%).4951 For example, the study on TiO2,43 one
of the often-reported dopants for BiFeO3,5256 suggests that
once the maximum solubility of TiO2 in BiFeO3 is exceeded,
which may happen even locally in the ceramics due to an
inhomogeneous distribution of the dopant, the composition
of the system will fall within the narrow three-phase eld
[see, as an example, Fig. 2(b)], resulting in the appearance of
secondary phases in large quantities. Therefore, when choosing a dopant for BiFeO3, one has to be careful particularly
when the dopant tends to be incorporated into the Bi25FeO39
and/or Bi2Fe4O9 since this may stabilize these secondary
phases. Extended discussions on this topic were presented by
Bernardo et al.55 for the case of the B-site W6+, Nb5+, and
Ti4+ doping cations. Other problems related to doping BiFeO3 involve the segregation of the dopant at the grain boundaries and the suppression of grain growth by doping.56
Another problem that is the direct result of the eect of
impurities on the equilibrium phase composition is the chemical incompatibility between the BiFeO3 and substrates. SiO2
and Al2O3 are the main constituents of refractory materials
that are commonly in contact with the ferrite during sintering. This may lead to a compositional degradation of the
BiFeO3 at such contacts. In fact, it was proposed that the
often-observed decomposition of BiFeO3 in its paraelectric
phase is due to the chemical incompatibility between the ferrite and the materials in contact with the sample during
(a)
(b)
(b1)
(b2)
July 2014
1997
(b)
Fig. 4. Reaction kinetics in the Bi2O3Fe2O3 system. (a) Scanning electron microscopy (SEM) image of a characteristic distribution of phases
with dierent Bi/Fe molar ratios observed in the sintered ceramics, that is, a BiFeO3 grain (light-gray phase) with the Bi-rich sillenite phase at
the BiFeO3 grain boundary (bright phase) and an Fe-rich phase (Bi2Fe4O9 or Fe2O3; dark-gray phase) in the interior of the BiFeO3 grain. The
sample was prepared by a conventional mixed-oxide route at 750C for 2 h. (b) Proposed reaction pathway mechanism for the solid-state
synthesis of BiFeO3 from Bi2O3 and Fe2O3, based upon diusion-couple studies and experimental observations (see panel a). Reprinted with
permission from Ref. [60] Copyright 2011 Elsevier Ltd.
(3)
1998
(b)
(c)
(d)
Fig. 5. Segregation of Bi-rich liquid phase and Bi2O3 sublimation/evaporation. Scanning electron microscopy (SEM) backscattered-electron
(BE) images of BiFeO3 ceramics sintered at (a) 760C for 6 h and (b, c, d) at 820C for 10 h with an additional 10 h of postannealing at (b)
820C with the sample immersed in the packing powder, (c) 820C in open air and (d) 880C in open air (both (c) and (d) are denoted as
nonimmersed). The inset of (b) shows the segregation of a Bi-rich liquid phase at 820C as a result of the melting of the Bi25FeO39 phase with
the onset at the peritectic temperature (Tp~790C). The large, regularly shaped Bi2Fe4O9 crystals, identied after annealing at 880C (panel d),
are consistent with the Bi2O3 sublimation loss (see text for details). Reprinted with permission from Ref. [68] Copyright 2010 American Institute
of Physics.
Fig. 6. (a) Sintering curve of Bi2O3Fe2O3 mixture before (mixture) and after calcination at 700C for 5 h with additional planetary milling
(calcined + milled). The sintering curve of the mechanochemically activated Bi2O3Fe2O3 mixture (mixture (activated)) is added for
comparison. (b) X-ray diraction (XRD) patterns of Bi2O3Fe2O3 mixture calcined at 650C (6 h), 680C (4 h), and 700C (4 h). The pattern of
the mechanochemically activated mixture, which was reactive sintered at 760C for 6 h (A+RS), is also added.
July 2014
resulting powders contained a signicant amount of secondary phases, which were easily detected by XRD [Fig. 6(b)].
The result is not surprising, taking into account that the
reaction is driven within the temperature region of the thermodynamic instability of BiFeO3, that is, between 447C and
767C [see Fig. 1(b)].
To achieve a higher reaction yield with a given powder
mixture, one of the common approaches is to increase the
diusion rate of the reacting species by increasing the calcination temperature. In the case of BiFeO3, temperatures
higher than 767C would be required to enter the temperature region in which BiFeO3 is stable [see Fig. 1(b)]. There
are, however, two key problems related to this approach.
Firstly, the Bi25FeO39 phase starts to melt at Tp ~ 790C,
which may cause the uncontrolled loss of Bi2O3 through
evaporation and/or segregation of the resulting liquid phase,
as discussed in the previous section. In fact, the slight expansion of the pellet at ~790C, observed on the sintering curve
of the Bi2O3Fe2O3 mixture [Fig. 6(a), mixture], coincides
with the peritectic point of the Bi25FeO39. Secondly, as seen
from the sintering curve [Fig. 6(a), mixture], the densication of the powder mixture sets in at 800C. In principle, this
limits the calcination to below this temperature if we intend
to avoid particle coarsening and, consequently, additional
milling steps, which may increase the possibility of the contamination and stabilization of secondary phases by impurities. We also note that the onset of the densication of the
powder after the rst calcination and milling appears at even
lower temperatures, that is, 600C [Fig. 6(a), calcined +
milled]. Thus, by considering these two arguments, the rst
and subsequent calcination steps would necessarily require
temperatures that fall within the range of the thermodynamic
instability of BiFeO3 or are close to the top-end of this
temperature interval.
To overcome the apparent incompatibility between the
reaction and the densication of conventionally processed BiFeO3, we recently proposed the use of mechanochemical activation (high-energy milling). This method is capable of
providing highly sinterable and reactive precursors, allowing
us to merge the two processes into a single step, known as
reactive sintering.70 We believe that reducing the number of
processing steps, including milling, is indeed important for
the synthesis of BiFeO3, considering the degrading eect of
impurities. The mechanochemical activation of the Bi2O3
Fe2O3 powder mixture resulted in an increased sinterability,
that is, the sintering curve of the activated mixture [Fig. 6(a),
mixture (activated)] is comparable to that of the calcined
and milled powder [Fig. 6(a), calcined + milled]; at the
same time, it also provided increased reactivity between the
Bi2O3 and the Fe2O3. By applying reactive sintering, we were
able to obtain BiFeO3 ceramics in one processing step with a
minimum content of secondary phases [<1%; Fig. 6(b),
A+RS] and a low level of impurities, originating from the
milling media (W: 130 ppm, Co: 390 ppm). Figure 6(b)
(A+RS) shows the case of 760C, however, similar results
were obtained for higher sintering temperatures.68 The
obtained ceramics were able to withstand electric elds as
high as 180 kV/cm, allowing us to study the domain-switching behavior and piezoelectricity of BiFeO3. Those results
are presented in Sections IV and V, while studies on the
dielectric permittivity are presented in the following section.
III.
A comprehensive review, including the most important references on the dielectric permittivity of BiFeO3 across a wide
frequency range, has recently been published by Catalan and
Scott.3 The intrinsic GHz dielectric permittivity of BiFeO3 is
actually small, that is, er~30, however, room-temperature
values as high as er~10000 were reported in the Hz-to-MHz
frequency range, both in ceramics71 and single crystals.72
1999
2000
(c)
(b)
(d)
Fig. 7. Dielectric permittivity (e ) and dielectric losses (tand) versus eld frequency for three types of BiFeO3 ceramics prepared by the reactive
sintering of a mechanochemically activated Bi2O3Fe2O3 mixture. The three batches dier in the conditions of premilling of the initial Bi2O3 and
Fe2O3 powders: (a) no premilling and (b,c) premilling in a planetary mill at 200 min1 of rotational frequency for 4 h using (b) isopropanol and
(c) acetone. (d) e and tand of the three BiFeO3 ceramics plotted on a logarithmic scale. The median particle sizes (d50) of the starting Bi2O3/
Fe2O3 powders were 14.6/11.3 lm (no premilling), 1.6/0.6 lm (isopropanol milling) and 0.8/0.5 lm (acetone milling). All three ceramics were
reactively sintered at 760C for 6 h [details are given in Ref. (68)], resulting in relative densities in the range 92%95%. e in panel (c) is plotted
in the frequency range 2000.6 Hz; below 0.6 Hz, e decreases and approaches zero as the phase angle reaches ~90 (not shown on the plot). The
real part of the permittivity coecient (e ) can be expressed as e = (Q0/V0)(L/Ae0)cos(d) where Q0, V0, L, A, e0, and d indicate the charge
amplitude, voltage amplitude, sample thickness, sample area, vacuum permittivity, and phase angle, respectively. According to this equation, if
d = 90, e becomes zero, while tand diverges (pure DC conductive behavior).
July 2014
It appears, from recent studies, that the conductivity in BiFeO3-related systems can be signicantly reduced by thermal
treatments in an oxygen-poor atmosphere; however, this
leaves an open question as to whether the Bi2O3 loss through
sublimation and/or evaporation may be controlled under
such conditions. In fact, a lack of oxygen during annealing
may enhance the Bi2O3 loss [see Section II(2) and reaction
(3)], an issue that has been initiated,69,104 but so far not
studied in detail. A related problem found in argon-annealed
BiFeO3 is a poor microstructure with a high level of porosity, which has its origin, apparently, in the loss of Bi2O3.67
IV.
(a)
2001
(b)
(c)
Fig. 9. Selected polarizationelectric-eld (PE) hysteresis loops of BiFeO3 ceramics from the literature. The ceramics were prepared using (a)
solgel powder processing [sintered at 800C in O2 with high heating (30C/min) and cooling rate (not specied)],90 (b) rapid liquid-phase
sintering [sintered at 855C with high heating (100C/min) and cooling rate (~170C/min)],85 and (c) solid-state reaction method [sintered at
860C with high cooling rate (quenching medium not reported)].107 Arrows in panels (a) and (b) indicate the pinched state of the loops.
Reprinted with permission from Ref. [90] (Copyright 2006 American Institute of Physics), Ref. [85] (Copyright 2006 Elsevier Ltd) and Ref. [107]
(Copyright 2005 American Institute of Physics).
2002
Fig. 10. Inuence of quenching temperature and cooling rate on the domain-switching behavior of BiFeO3. (a) Polarizationelectric-eld (PE)
hysteresis loops of as-sintered (nonquenched) ceramics (non-Q) and after rapid quenching in water from 450C, 760C, and 900C.68 The holding
time at each temperature was 5 min. (b) PE loops of ceramics annealed at 900C for 5 min, followed by quenching in water (Q-water) and air
(Q-air), and by slow cooling within the furnace with 1C/min of cooling rate (slow). Reprinted with permission from Ref. [68] Copyright 2010
American Institute of Physics.
July 2014
(a)
Fig. 11. Inuence of Bi2O3 loss upon annealing on the domainswitching behavior of BiFeO3. Polarizationelectric-eld (PE)
hysteresis loops of BiFeO3 sintered at 820C for 10 h with an
additional 10 h of postannealing at 820C or 840C with the ceramic
sample (a) immersed in a BiFeO3 packing powder or (b) treated in
air (without the packing powder). Note that the loops shown in
panels (a) and (b) were measured at dierent electric-eld amplitudes
(140 and 90 kV/cm, respectively). To allow a comparison under the
same electric-eld conditions, the PE loop of the sample annealed
in the packing powder and measured at 90 kV/cm is added in panel
(a) (see dashed line).
(a)
2003
(b)
Fig. 12. (a) Strainelectric-eld (SE) hysteresis loops of BiFeO3 ceramics measured with increasing eld amplitudes at 0.1 Hz (the inset shows
the loop at 160 kV/cm). (b) Peak-to-peak strain as a function of driving-eld frequency for 110, 120, and 130 kV/cm. The data shown in panel
(b) were compiled from measurements reported in Ref. [86]. As indicated with arrows in panel (a), the SE loops evolve from a pinched-like
state with little remanent strain at low driving-eld amplitudes (110 kV/cm) to a de-pinched state at high amplitudes (160 kV/cm).
2004
Fig. 13. (a) Portion of X-ray diraction (XRD) pattern and (b) calculated degree of domain alignment in poled BiFeO3 as a function of the
angle to the applied electric eld. Before XRD analysis, the BiFeO3 ceramic sample was poled with electric elds of increasing amplitude from 10
to 160 kV/cm in steps of 10 kV/cm. The corresponding SE loops of this sample are shown in Fig. 12(a). The degree of domain alignment can
be represented as either multiples of random distribution (MRD) for the polar [111]pc direction (f111) or the domain switching fraction (g111);
both of these values are shown as separate y-axes in panel b. An initially unpoled state would be represented as f111 = 1 MRD and g111=0 in all
directions of the polycrystalline ceramic; such a state is shown on panel b as a dashed line.
July 2014
V.
2005
2006
(b)
(c)
(d)
Fig. 15. Direct piezoelectric response of BiFeO3 ceramics. (a) Piezoelectric d33 coecient and piezoelectric losses (tand) as a function of the
frequency of the driving stress (measured at 1.1 MPa of peak-to-peak stress amplitude); (b) relative piezoelectric coecient (d33 relative) versus
amplitude of the driving stress, measured at 10, 1, 0.1, and 0.01 Hz;138 (c, d) charge densitystress loops measured with increasing (c) frequency
and (d) amplitude of driving stress. Note the considerable increase of the slope and the hysteresis of the loops as the frequency of the driving
eld is reduced (panel c) or the amplitude is increased (panel d). The static stress was set to either 2.7 MPa (panel a) or 3.7 MPa (panels b, c,
and d).
VI.
Summary
1. spontaneous decomposition of the BiFeO3 in the temperature range 447C767C according to the reaction
[see Eq. (1)]:.
BiFeO3 ! 1=49Bi25 FeO39 12=49Bi2 Fe4 O9
(4)
July 2014
Acknowledgments
This work was supported by the Slovenian Research Agency (programme P20105 and project J2-5483). TR would like to thank Prof. Dr. Nava Setter for
her nancial and technical support related to parts of this work. DD acknowledges the nancial support of FNS-PNR62. JJ and GT acknowledge the U.S.
Department of the Army for support under contract number W911NF-09-10435. JD acknowledges nancial support from an AINSE research fellowship
and ARC DP120103968. Use of the Advanced Photon Source was supported
by the US Department of Energy, Oce of Science, Oce of Basic Energy
Sciences, under Contract No. DE-AC02-06CH11357.
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h
thin lms, tunable ferroelectric thin lms and solutionderived materials for transparent electronics. She is also
involved in studies related to chemical solution deposition of
thin lms, inkjet printing of solutions and particle dispersions. She is author or co-author of more than 130 papers,
10 book-chapters, more than 110 technical reports and 4 Slovenian patents.
July 2014
2011