Temperature-induced local and

average structural changes in

BaTiO3−xBi(Zn1/2Ti1/2)O3 solid solutions:
The origin of high temperature dielectric
permittivity
Cite as: J. Appl. Phys. 122, 064103 (2017); https://doi.org/10.1063/1.4989393
Submitted: 08 June 2017 . Accepted: 27 July 2017 . Published Online: 11 August 2017

Dong Hou , Tedi-Marie Usher , Hanhan Zhou, Natthaphon Raengthon, Narit Triamnak, David P. Cann
, Jennifer S. Forrester , and Jacob L. Jones

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 JOURNAL OF APPLIED PHYSICS 122, 064103 (2017)

Temperature-induced local and average structural changes in

BaTiO32xBi(Zn1/2Ti1/2)O3 solid solutions: The origin of high temperature
dielectric permittivity
Dong Hou,1 Tedi-Marie Usher,1,2 Hanhan Zhou,1 Natthaphon Raengthon,3,4
Narit Triamnak,3,5 David P. Cann,3 Jennifer S. Forrester,6 and Jacob L. Jones1,a)
1
Department of Materials Science and Engineering, North Carolina State University, Raleigh,
North Carolina 27695, USA
2
Chemical and Engineering Materials Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831,
USA
3
Materials Science, School of Mechanical, Industrial, and Manufacturing Engineering, Oregon State
University, Corvallis, Oregon 97331, USA
4
Department of Materials Science, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand
5
Department of Materials Science and Engineering, Faculty of Engineering and Industrial Technology,
Silpakorn University, Nakornpathom 73000, Thailand
6
School of Chemical and Process Engineering, University of Leeds, Leeds, West Yorkshire LS2 9JT,
United Kingdom
(Received 8 June 2017; accepted 27 July 2017; published online 11 August 2017)
The existence of local tetragonal distortions is evidenced in the BaTiO3–xBi(Zn1/2Ti1/2)O3
(BT–xBZT) relaxor dielectric material system at elevated temperatures. The local and average
structures of BT-xBZT with different compositions are characterized using in situ high temperature
total scattering techniques. Using the box-car fitting method, it is inferred that there are tetragonal
polar clusters embedded in a non-polar pseudocubic matrix for BT-xBZT relaxors. The diameter of
these polar clusters is estimated as 2–3 nm at room temperature. Sequential temperature series fit-
ting shows the persistence of the tetragonal distortion on the local scale, while the average structure
transforms to a pseudocubic paraelectric phase at high temperatures. The fundamental origin of
the temperature stable permittivity of BT-xBZT and the relationship with the unique local scale
structures are discussed. This systematic structural study of the BT-xBZT system provides both
insight into the nature of lead-free perovskite relaxors, and advances the development of a wide
range of electronics with reliable high temperature performance. Published by AIP Publishing.
[http://dx.doi.org/10.1063/1.4989393]

I. INTRODUCTION exceeds 200  C. Considering the growing demands of elec-

tronic devices that operate in harsh environments, efforts
Many emerging technologies such as micro-flight sys-
have been made to discover new materials with properties
tems, electric-powered vehicles, and renewable energy
that persist at higher temperatures.
generation devices have electrical energy storage require-
The concept of complex solid solutions with the perov-
ments that are not met by existing materials and devices.1,2
skite ABO3 structure has been a mainstay of the capacitor
Existing energy storage technologies require a tradeoff
between power density and energy density. For example, community and new materials with a relatively high permit-
fuel cell and battery technologies provide high energy densi- tivity, temperature insensitivity, and frequency dependent
ties, but have limited power densities because of the sluggish character have been reported.8–10 The in-service temperature
nature of their charge storage mechanism.1,3 Therefore, there can be extended to above 200  C, which is an improvement in
is a demand to develop new energy storage materials that conventional BT-based dielectric materials. These materials
exhibit both high power density and high energy density. are referred to as temperature-stable relaxor dielectrics due to
One promising class of materials for the new generation of the broad frequency-dependent permittivity. In general, two
energy storage materials is ceramic capacitors. The most types of lead-free perovskite systems have been widely exam-
common currently used material in this class is the BaTiO3 ined for high temperature performance: BT-based11–14 and
(BT)-based multilayer ceramic capacitors, which can reach Na1/2Bi1/2TiO3(NBT)-based15–18 solid solutions. Zeb and
the X9R level of the Electronic Industries Association stand- Milne provided a systematic performance study of the differ-
ards by chemical modification, in which X9R represents ent temperature-stable relaxor dielectrics.19 To obtain BT-
615% variability of capacitance over the 55 to 175  C based relaxor dielectrics, the general method is to modify the
temperature range.4–7 However, traditional ferroelectric- normal ferroelectric BT with Bi(M)O3, where M indicates the
based dielectric materials suffer a significant permittivity trivalent equivalent cations on the B-site of the perovskite struc-
drop and an increase of dielectric loss when the temperature ture, such as Fe3þ, Sc3þ, (Zn1/2Ti1/2)3þ, and (Mg2/3Nb1/3)3þ.
The performance of various BT-Bi(M)O3 relaxor dielectrics has
a)
Author to whom correspondence should be addressed: [email protected] been reported and summarized by others.19–22

0021-8979/2017/122(6)/064103/10/$30.00 122, 064103-1 Published by AIP Publishing.

064103-2 Hou et al. J. Appl. Phys. 122, 064103 (2017)

Traditional ferroelectric-based dielectrics with high tem- by Triamnak et al. and Usher et al.28,34 Ceramic pellets were
perature properties may be strongly contributed by composi- obtained after sintering at 1200  C for 2 h. The bulk samples
tional segregation in a core-shell microstructure.4,21 However, were polished, painted with silver paste, and then examined
this core-shell type of microstructure has not been compre- by using a LCR meter (Agilent 4284A model, Agilent
hensively reported in the new generation of temperature- Technologies, Inc., Santa Clara, CA). The permittivity and
stable relaxor dielectrics. Even though the compositions of dielectric loss of the BT-xBZT samples were recorded upon
relaxor dielectrics are similar to those of normal ferroelectric cooling over a wide temperature range of 150 to 200  C
compounds, in which the high permittivity arises from with frequencies of 25–250 kHz. The sintered pellets were
domain interactions, the lack of hysteresis and the negligible crushed into powders and then annealed at 400  C for 3 h to
saturation indicate the absence of domain interactions in reduce the induced stress for the following X-ray investiga-
relaxor dielectrics.23,24 Therefore, relaxor dielectrics are fun- tion. In addition, the bulk ceramic samples were polished
damentally different from traditional ferroelectric-based and thermally etched at 800  C for 30 min, and then cooled
dielectrics although they exhibit similar high temperature to room temperature with a 5  C/min cooling rate. The
properties. It has been hypothesized that the mixed site occu- microstructures were investigated with a field-emission scan-
pancy, lattice scale heterogeneity, and subtle compositional ning electron microscope (FE-SEM) (Verios XHR model,
variations might be the chemical and structural origins of FEI, Corp., Hillsboro, OR). The grain size was determined
these unique properties. Due to the lack of fundamental stud- from stereological analyses of the FE-SEM images using the
ies of the structure-property relationships in this class of mate- ImageJ program.35
rials, the mechanism underlying these anomalous dielectric In situ X-ray total scattering measurements were per-
properties is not entirely known. formed at beamline 11-ID-B of the Advanced Photon Source
In this study, one BT-Bi(M)O3 solid solution that has at Argonne National Laboratory, with an X-ray wavelength
been reported to have desirable high temperature stable of 0.13702 Å (90.49 keV). The powder samples were loaded
performance, (1–x)BT-xBi(Zn1/2Ti1/2)O3 (BT-xBZT), is in quartz capillaries, and heated from room temperature to
examined.23–26 Previous dielectric measurements show a 500  C with a ramp rate of 5  C/min using resistive heating
crossover from normal ferroelectric-like behavior to relaxor- coils in the sample environment. Total scattering patterns
like behavior when the BZT concentration is increased were recorded on a Perkin Elmer flat-panel amorphous-sili-
to x ¼ 9% and above. Laboratory X-ray diffraction (XRD) con 2-D detector with a collection rate of 20 s per pattern.
suggests a phase transition from a tetragonal to This method can capture structure changes in a temperature
‘rhombohedral-like’ (or pseudocubic) structure with increas- increment as small as 1.67  C during the in situ heating pro-
ing BZT concentration in this solid solution, and a critical cedure. The 2-D total scattering images were integrated and
composition for this transition is around x ¼ 0.09.23,24,27 Usher reduced to 1-D patterns using Fit2D.36 Within the PDFgetX3
et al. presented a detailed structural description for the BT- package,37 background subtraction, normalization, and
xBZT system at room temperature using high resolution XRD, Fourier transform were performed on each 1-D total scatter-
neutron diffraction, and neutron pair distribution function ing structure function SðQÞ, converting the data to a GðrÞ
(PDF).28 However, in situ crystal structure studies at elevated PDF pattern. The maximum scattering vector (Qmax) used
temperatures of BT-xBZT and other BT-Bi(M)O3 material sys- for Fourier transform is above 23 Å1, which is suitable for
tems are yet unavailable. In situ XRD and total scattering tech- PDF analysis.38–40 Peak fitting of selected PDF peaks was
niques enable the crystallographic study of various materials conducted using a Gaussian profile. Real-space refinements
under different stimuli (temperature, pressure, stress, electric of the in situ PDF patterns were carried out in PDFgui using
field, etc.), which can offer valuable information to interpret the least-squares minimization method.41
structure-property relationships.29–33 Here, we conducted in
III. RESULTS AND DISCUSSION
situ high-temperature synchrotron total scattering experiments
on the BT-xBZT material system with selected compositions. A. Dielectric measurements
The purpose of this study is to examine the local environment
The dielectric properties of BT-xBZT were character-
on the A-site, to study the distortions at the local scale, and fur-
ized as a function of temperature and frequency. Figure 1
thermore, to elucidate the average and local structure for com-
shows the real part of dielectric relative permittivity (e0 ) and
positions across the BT-xBZT phase diagram, both at room
dielectric loss (tan d) for BT-xBZT samples at various fre-
temperature and at elevated temperatures. The average and
quencies (f ) and temperatures (T). BT-0.06BZT exhibits
local structural changes with increasing temperature and vary-
classic ferroelectric-like behaviors: a sharp peak of permit-
ing composition can give insight into the mechanism of high
tivity as a function of temperature, the temperature of maxi-
temperature relaxor dielectrics, which may help to interpret
mum permittivity (T m) is frequency independent, and the e0
and to engineer the properties.
versus T curves do not exhibit obvious frequency dispersion.
With a BZT concentration of 0.08, the permittivity peak
II. EXPERIMENTAL
becomes broad as a function of temperature, T m decreases
Bulk polycrystalline ceramics of BT-xBZT with compo- with increasing frequency, and a strong frequency dispersion
sitions of x ¼ 0.06, 0.08, 0.10, and 0.20 were prepared using of e0 and tan d is observed. These behaviors suggest relaxor-
a conventional solid state synthesis technique. The details of like dielectric behavior for BT-0.08BZT. With a BZT con-
reactants and synthesis procedures are described elsewhere tent of 0.10, the frequency dispersion of e0 and tand is
064103-3 Hou et al. J. Appl. Phys. 122, 064103 (2017)

FIG. 1. Temperature dependent dielec-

tric permittivity (e0 ) and dielectric loss
( tan d) at various frequencies for BT-
xBZT, where x ¼ 0.06, 0.08, 0.10, and
0.20, respectively (arrows indicate the
direction of increasing frequency).

enhanced and the permittivity peak is broader still. For BT- Therefore, for BT-0.20BZT, the maximum measurement
0.20BZT, the diffusive permittivity peak is further broad- temperature was extended to 500  C, and the new (1/e0 ) ver-
ened, and a temperature-insensitive plateau develops. The sus T curve is presented in Fig. S2 (supplementary material),
relative permittivity of BT-0.20BZT remains around 1500 in which the permittivity begins to follow the CW law at
for temperatures up to 200  C, while the dielectric loss is rel- above 405  C. It is worthwhile to note that other composi-
atively small, confirming that BT-0.20BZT belongs to the tions with relaxor behavior (e.g., x ¼ 0.08, 0.10) may also
class of temperature-stable relaxor dielectrics. not strictly follow the fitted line in Fig. S1 (supplementary
For a normal ferroelectric material, the permittivity fol- material) with further increase in the dielectric measurement
lows the Curie-Weiss (CW) law above the Curie temperature temperatures. This is because the CW law was originally
(T C), as shown by the linear response of inverse permittivity used to describe a ferroelectric in the paraelectric phase, and
(1/e0 ) versus T.42 The (1/e0 ) as a function of T for BT-xBZT the pseudocubic phases in relaxors are fundamentally differ-
measured at 100 kHz is shown in Fig. S1 in the supplemen- ent from the paraelectric phase of traditional ferroelectrics.
tary material. Deviation from the CW law is observed for all To better describe the dielectric behaviors in the high tem-
the compositions above T m. For example, BT-0.06BZT has a perature region, a modified CW law was proposed and
T m of 71  C, while the linear fitting of (1/e0 ) versus T shows employed for the dielectric relaxors.10,25,43 Further extension
that the deviation temperature (T dev) is 136  C, which is well of the dielectric measurement temperature for x ¼ 0.06 to
above T m. The deviation from CW law in BT-0.06BZT 0.10 was not successful due to the significant decrease in
reveals the minor relaxor character in this ferroelectric-like resistivity and increase in dielectric loss. Nonetheless, Fig.
material. With increasing BZT concentration from 0.06 to S2 (supplementary material) demonstrates excellent high
0.10, the deviation from the CW law becomes larger, and temperature stable permittivity in BT-0.20BZT compared to
T dev decreases from 136  C to 131  C. In addition, the T C other compositions. The grain size for all compositions is
obtained by fitting the CW law (x-intercept of the fit line) about 1–2 lm, and the representative SEM images are shown
decreases significantly with a small amount of BZT modifi- in Fig. S3 in the supplementary material. The samples with
cation: T C decreases from 20  C to 123  C when BZT con- x ¼ 0.08, 0.10, and 0.20BT show clear microstructures and
tent changes from 0.06 to 0.10. Notably, the linear fitting of grain boundaries, while for x ¼ 0.06, segregation is observed
BT-0.20BZT (1/e0 ) versus T curve gives a line nearly parallel at the grain boundaries. According to the study of Triamnak
to the x-axis, with a slope of 2.38  107 and x-intercept of et al.,34 the sintering temperature increases with decreasing
2505  C as shown in Fig. S1 (supplementary material). BZT concentration, suggesting that the thermal etching tem-
Clearly, these physically impossible values indicate the perature for low-BZT compositions should also be a little
strong temperature stable character in BT-0.20BZT composi- higher than that for the high-BZT compositions. However, in
tion. Due to the high resistivity in BT-0.20BZT, the dielec- this study the thermal etching temperature was fixed to
tric measurement can be performed at higher temperatures. 800  C for all compositions. The segregation in BT-0.06BZT
064103-4 Hou et al. J. Appl. Phys. 122, 064103 (2017)

grain boundaries might come from insufficient diffusion and A-A and B-B pairs at r  4.0 Å. The peak representing the
redistribution of atoms, and a cleaner boundary is expected shortest B-O pairs should be at r  2 Å, but is obscured by
for BT-0.06BZT with a slight increase in the thermal etching the intrinsically weak scattering of Ti/Zn-O when using
temperature, prolonging the annealing time, or decreasing X-ray radiation and the presence of termination ripples (a
the cooling rate. normal artifact due to the Fourier transform) at low-r.
To summarize, with increasing BZT concentration in The room temperature PDF patterns for all the BT-xBZT
BT, a transition from a classic ferroelectric-like to relaxor- compositions are shown in Fig. S4 in the supplementary
like material then to temperature stable relaxor is observed material. At the local scale, i.e., r range of 2–6 Å as shown in
according to the dielectric measurements. The incorporation Fig. S4(a), the peaks overlay each other for different compo-
of BZT into BT may involve compositional and site disorder sitions with almost no peak position difference, suggesting
on the A- and B-sites of the perovskite structure. the local structure has no obvious changes as a function of
Considering that the properties of a ferroelectric or dielectric composition. Peak fitting of the first three PDF peaks con-
material are strongly correlated with the crystal structure, the firmed this statement: as shown in Fig. S4(b) (supplementary
study of the local and long-range structure as a function of material), the position difference for a specific set of low-r
temperature is necessary and important. PDF peaks is within the error bars. The peaks in a high-r
range shift to the right side, suggesting that the addition of
BZT into BT expands the lattice, and the expansion of the
B. Local and average structures at room temperature
unit cell accumulates at a longer length scale, resulting in
The experimental PDF, GðrÞ, is obtained by a direct obvious peak shifts at high-r. This observation agrees well
Fourier transform of the total scattering structure function, with other reported average structure studies of BT-xBZT at
SðQÞ, as room temperature.23,24,28 Another interesting observation is
ð the increase in peak width and decrease in height with
2 1 increasing BZT concentration. A previous PDF study sug-
G ðr Þ ¼ QðSðQÞ  1ÞsinðQr ÞdQ;
p 0 gested that this decrease in peak height is partially due to the
change in scattering factors as a function of composition.28
where Q is the scattering vector or momentum transfer, and r To test this theory, an ABO3 model with a pseudocubic struc-
is the atom-atom distances.44 Figure 2(a) shows the reduced ture was created, in which the composition is allowed to vary
structure function, QðSðQÞ  1Þ, of BT-0.06BZT at room but the structure remains unchanged. The corresponding PDF
temperature. The inset is a magnification of the high-Q patterns were then calculated to investigate the effect of scat-
region, indicating a good signal-to-noise ratio. The signal tering factors on the peak shape. Figure S4(c) shows that the
only begins to decay at Q  23 Å1, which is suitable for X-ray scattering factor difference between Ba2þ and Bi3þ or
PDF analysis. Figure 2(b) shows a representative GðrÞ pat- between Ti4þ and Zn2þ has negligible impact on the PDF
tern covering the range from sub-ångstr€om up to 50 Å, show- peak heights (supplementary material). Instead, it is likely
ing the connection from the local structure to long-range that static disorder induced by BZT modification dominates
structure. The inset of Fig. 2(b) shows the magnification of this broadening effect.
the local PDF peaks: the first characteristic peak (at To determine the structure of BT-xBZT at room temper-
r  2.8 Å) represents the A-sites to oxygen (A-O) pairs, fol- ature, PDF refinements were conducted for all compositions
lowed by the nearest A-B pairs at r  3.4 Å and the nearest at two different length scales: 2–10 Å for the local scale, and
10–30 Å for the intermediate scale. Four plausible phases
were used for refinements: cubic Pm3m, rhombohedral R3m,
orthorhombic Amm2, and tetragonal P4mm. These four
phases were selected because these structures are widely
reported in BT-based perovskite structure studies, e.g., BT
has a Pm3m ! P4mm ! Amm2 ! R3m phase transforma-
tion with decreasing temperature,45,46 the local structure of
Sn-doped (Ba,Ca)TiO3 is reported to be R3m at high temper-
ature and P4mm at lower temperature,47 Zr-doped BT has a
R3m local structure,48 Nb-doped BT is reminiscent of a local
R3m phase at all temperatures,49 and pure BZT assumes a
highly distorted perovskite P4mm structure.50 Therefore, it is
reasonable that BZT-modified BT will inherit part of the BT
or BZT crystallographic character for local and long-range
structures. The fits of each phase to the BT-0.06BZT room
temperature PDF pattern are shown in Fig. 3 in the two
FIG. 2. (a) Reduced structure function, QðSðQÞ  1Þ, of BT-0.06BZT at respective ranges. At the intermediate length scale, tetrago-
room temperature. The inset is a magnification of the high-Q region, indicat- nal P4mm gives the best fit indicated by the minimized dif-
ing a good signal-to-noise ratio. (b) PDF of BT-0.06BZT at room tempera-
ture after Fourier transform, the inset shows the magnified area of low-r
ference curve and best goodness of fit (GoF) value. The
PDF data, and the major atom pairs which contribute to the local PDF peaks structure represented by the intermediate range PDF data
are indicated. agrees with the average structure XRD studies. This suggests
064103-5 Hou et al. J. Appl. Phys. 122, 064103 (2017)

FIG. 3. The fits of the BT-0.06BZT

room temperature PDF pattern over a
range of 2–10 Å and 10–30 Å using
four plausible phases: P4mm, R3m,
Amm2, and Pm3m. The goodness of fit
value for each fit is listed.

that the intermediate scale structure from PDF approximates parameters (a and c for P4mm), atomic positions, and atomic
to the average structure obtained from XRD refinements. At displacement parameters (ADP). Figure 4 summarizes the
the local scale, P4mm also gives the best fit compared to box-car fitting results of the lattice parameters for BT-xBZT.
other models. The Amm2 model also results in a reasonable The black and red shaded regions in each subplot represent
GoF, but by examining the actual fit at the local scale, it is the a and c lattice parameters with standard deviation obtained
clear that the low GoF is a result of the better fit of the termi- from whole profile fitting of PDF data (1–50 Å), which can
nation ripples at around 2 Å, while the fit of PDF peaks is be approximated to the average structure of this material.
inferior to P4mm, e.g., the fit of the peak at r  9 Å is poor. With increasing BZT concentration, the tetragonality (c/a)
The same refinement routine was conducted for all composi- decreases, and for BT-0.20BZT, the tetragonality is nearly
tions, and P4mm is the best model in the local and intermedi- unity, meaning a cubic-like average structure. Interestingly,
ate scale with all BZT additions. Figure S5 (supplementary all compositions show a structure evolution with increasing
material) shows the fit of the BT-0.20BZT PDF data using length scale: an enhancement of tetragonality is observed for
different models as a representative example of fitting other the local scale structure, while the structure in the high-r
compositions. It was found that at the intermediate scale, region is closer to the average structure. This transition is
either P4mm or Pm3m gives a good fit of the PDF data, but demonstrated in Fig. 4.
P4mm has a lower GoF value, indicating that a subtle and
not negligible tetragonal distortion may exist in the BT-
0.20BZT relaxor, corresponding to the “pseudocubic” aver-
age structure reported from previous diffraction studies.23,25
At the local scale of the BT-0.20BZT PDF pattern, P4mm is
a better fit than Pm3m and the GoF difference between these
two models is larger than that at the intermediate scale, sug-
gesting that at the local scale, it is more likely tetragonal
than cubic.
To characterize the length scale dependence of the crys-
tal structure in BT-xBZT at room temperature, a sequential
fitting of increasing r-ranges (box-car method) was per-
formed on each PDF dataset. This approach is beneficial
when studying how the structure evolves at different length
scales, and has been applied to various material sys-
tems.28,51–53 In this study, the r-window was fixed to 10 Å,
with an increment of 5 Å for the starting and end position of
the r-window: 1–10 Å, 5–15 Å, 10–20 Å, etc. The tetragonal
P4mm model was adopted for this box-car sequential fitting
of all BT-xBZT compositions. The initial parameter values
FIG. 4. The box-car fitting results of the lattice parameters a and c for
for each individual fitting were input from the refinement
BT-xBZT using P4mm model. The black and red shade lines in each subplot
results of whole profile fitting (1–50 Å), and the parameters represent the a and c values with standard deviation obtained from whole
refined during the sequential fitting were: scale factor, lattice profile fitting of PDF data (1–50 Å).
064103-6 Hou et al. J. Appl. Phys. 122, 064103 (2017)

It is interesting to note that the lattice parameters of size is an estimation based on the total scattering from the
local structures have similar values for different composi- bulk sample. It is likely that there is a distribution of the
tions (a  3.995 Å and c  4.040 Å), indicating that the local polar cluster size across the sample. The box-car fitting
structure across the BT-xBZT system is similar, and the method was used with an interval (r-window) of 10 Å and a
addition of BZT affects the structure only at a longer length step increment of 5 Å; a better estimation of the PNR size
scale. The lattice parameters of the BT-xBZT local structure might be achieved by decreasing the r-window and the step
at RT are also in excellent agreement with the long-range increment in the box-car fitting, but at the cost of fewer data
structure of undoped BT (a ¼ 3.966 Å and c ¼ 4.035 Å from points for each sequential fitting and larger uncertainty of the
Ref. 54 by first-principles calculations, and a ¼ 3.992 Å and fitting results. Confidence in the PNR size estimate could
c ¼ 4.036 Å from Ref. 46 by Rietveld refinement of neutron also be improved by utilizing an instrument with finer resolu-
diffraction data). This suggests that the local structure of tion, which would result in observable pair correlations at
BT-xBZT (or more generally, the BT-xBi(M)O3 solid solu- higher r, although likely at the cost of rapid in situ measure-
tions) is inherently inherited from the major BT end-member, ments. Another point to note: it is expected that the tetragon-
while addition of other elements on A/B-sites only disrupts ality inside a PNR is not uniform due to the inhomogeneity
the long-range order and not the local atom pair correlations. from charge and compositional disorder in BT-xBZT, but the
Similar box-car fitting of PDFs of classic ferroelectrics, e.g., PDF cannot readily detect the tetragonality distribution
BT or PbTiO3, would likely yield significantly less deviation within the PNR due to the averaging effect. As the model
of the local structure from the long-range structure compared length scale increases, the longer correlation lengths will
to the chemically modified solid solutions. contain more atom-atom pairs from matrix-matrix or matrix-
We hypothesize that the observed significantly enhanced PNR correlations than those from the PNR itself, thus result-
tetragonal distortion at the local scale for BT-0.10BZT and ing in the decreasing tetragonality with increasing r. In addi-
BT-0.20BZT correlates with the polar nano-region (PNR) tion, inherently local probes, e.g., transmission electron
theory in the relaxor ferroelectrics literature. According to microscopy and scanning probe microscopy, could offer
the PNR theory, nanoscale clusters with a polar phase are complementary information on the structure and structural
embedded in the non-polar matrix and contribute to the fluctuation within the PNRs.
anomalous dielectric and ferroelectric behaviors for relaxor The room temperature X-ray PDF result is consistent
ferroelectrics.8,10 The PDF results in this study support the with a similar study by Usher et al. using neutron PDF, in
fact that the polar phase of the clusters exists as regions char- which the polar clusters were also shown.28 In the present
acterized by tetragonal distortions, while at a longer length work, the use of a synchrotron source has the advantage of
scale the distortions average out as the matrix. The tetragonal rapid acquisition time58 compared to a neutron source, which
distortion and permittivity are found to be positively corre- allows parametric in situ studies under external stimuli, such
lated. Based on first-principles calculations and experimental as increasing temperature. The local structural changes with
measurements of a variety of ferroelectric solid solutions, increasing temperature can be captured and studied, as
the tetragonality is coupled to the cation displacements, and shown in Sec. III C.
therefore coupled to the polarization of the unit cell.55–57
C. Average structures at elevated temperatures
This spontaneous polarization creates dipoles, and dipole
moments under an external stimulus, e.g., electric field, The PDF patterns of BT-0.06BZT at selected tempera-
result in the high permittivity of dielectrics. It is likely that tures obtained by the in situ high temperature scattering tech-
the observed tetragonal distortions are the origin of the nique are shown in Fig. 5. The in situ PDF patterns for other
anomalous dielectric permittivity in BT-xBZT, similar to compositions are included in Fig. S6 in the supplementary
the dielectric observations in the canonical relaxor Pb(Mg1/3 material. Two features are prominent in Fig. 5: the peaks
Nb2/3)O3 which is attributed to different types of PNR shift to higher r with increasing temperature, especially for
responses.9,10 the peaks above 10 Å, and peak broadening occurs. The peak
In addition, the structures from box-car fitting begin to shifts are due to the positive thermal expansion coefficient of
follow the average structure in around the 20–30 Å range, BT-xBZT, while the peak broadening is mainly attributed to
suggesting that the possible polar clusters have a limited enhanced thermal motion at higher temperatures, giving rise
diameter of 2–3 nm. Since PDF is a bulk average probe that to a wider distribution of atom-atom distances (r). Whole
is sensitive to local structures, the determined polar cluster profile refinement was conducted at selected temperatures

FIG. 5. The PDF patterns of BT-

0.06BZT at selected temperatures
obtained by the in situ high tempera-
ture total scattering technique.
064103-7 Hou et al. J. Appl. Phys. 122, 064103 (2017)

using the four plausible single phase models, and Fig. S7 unit cell volume and isotropic ADP of A-sites atoms have a
(supplementary material) shows the refined results for BT- linear correlation with temperature as shown in Figs. 6(c)
0.06BZT at 475  C as an example. At 475  C, which is much and 6(d), with no sharp changes near 125  C observed. The
higher than T C or T m of this composition, the material should unit cell behavior of BT-0.06BZT at elevated temperatures
be in its paraelectric phase with a Pm3m cubic average struc- suggests that a second-order phase transformation occurs in
ture. However, the phase determination using the least- the vicinity of 125  C, which can be described as the tetrago-
squares fitting method suggests that tetragonal P4mm nal to cubic average structure phase transition. In the sequen-
remains the most likely representation of the local and inter- tial fitting, a temperature increment of 50  C was used to
mediate scale PDF data. The reason might be that P4mm detect the general trend. Thereafter, sequential fitting with an
allows atomic displacements along the c-axis while in the increment of 10  C was performed on patterns measured
Pm3m prototype perovskite structure the atom coordinates are from 50  C to 150  C to show more details about the struc-
fixed. Such atomic displacements appear to occur in BT- tural changes in the vicinity of transformation temperature.
xBZT even at high temperatures. Using different plausible The refinement results in the magnified temperature range are
single phase models to fit PDF patterns at selected elevated shown in Figs. 6(e) and 6(f). It follows the same general trend,
temperatures has also been trialed for other BT-xBZT compo- and the transition temperature is narrowed to between 125
sitions, and the results show that P4mm gives better fits than and 135  C. The transition temperature identified using whole
other structures. Therefore, P4mm is sufficient to describe the PDF profile refinement is much higher than T m of the same
most likely phases occurring in the studied temperature range, composition (71  C), but has a better agreement with the devi-
and was adopted in the following sequential fitting of the tem- ation temperature from the CW law (136  C). Therefore, our
perature series for all the BT-xBZT compositions. results suggest that the tetragonal distortion persists to above
Crystallographic structure information was determined T m for BT-0.06BZT in the scale range up to 50 Å, resulting in
by sequential fitting of the temperature series (from 25  C to the deviation from the CW law in the temperature range from
475  C) of BT-0.06BZT, and is presented in Fig. 6. The fit- T m to T dev for BZT modified BT samples.
ting range is from 1 to 50 Å, and the refined results can be The long-range lattice parameters as a function of tem-
used to approximate the average structure as described in the perature for all compositions are summarized in Fig. 7. The
above section. Figure 6(a) represents the changes in the lat- unit cell changes of BT-0.08BZT and BT-0.10BZT (in the
tice parameters a and c as a function of temperature: from vicinity of the critical transition point), which show traditional
25  C to 125  C, c decreases while a increases, correspond- relaxor-like behaviors, are presented. These changes follow
ing to the tetragonality decrease in Fig. 6(b). At around the same trend as in BT-0.06BZT, indicating that a tetragonal
125  C, the difference between a and c is subtle (<0.15%), to cubic transition occurs above the T m of these compositions.
and the tetragonality approaches unity. Above 125  C, In addition, the transition temperature decreases with increas-
increasing temperature only results in a linear increase of c ing BZT concentration, as shown in Fig. 7, suggesting that the
and a, and the tetragonality remains nearly unity. The slopes addition of BZT disrupts the typical tetragonal distortion in a
of a and c curves at high temperature have similar values, ferroelectric material, lowering the polar to non-polar transi-
suggestive of isotropic thermal expansion above 125  C. The tion temperature. For BT-0.20BZT, the average structure is

FIG. 6. Structure information of BT-0.06BZT as a function of temperature extracted from sequential whole profile fitting of temperature series PDF patterns:
(a) lattice parameters a and c; (b) tetragonality (c/a); (c) unit cell volume; (d) anisotropic ADP of A-sites atoms where U11¼U226¼U33 for P4mm. (e) and (f)
show lattice parameters and tetragonality in a magnified temperature range from 50  C to 150  C.
064103-8 Hou et al. J. Appl. Phys. 122, 064103 (2017)

and the refinement results are summarized in Fig. 8. The maxi-

mum temperature for the local PDF refinements is limited to
225  C rather than 475  C because significant total scattering
signal decay occurs at elevated temperatures due to the
increased Debye-Waller factor. Figure S9 (supplementary
material) shows the reduced total scattering function
QðSðQÞ  1Þ at 225  C, and the inset clearly shows that the
signal terminates at Qmax20 Å1, beyond which is mainly
amplified noise. In general, with lower Qmax, the real-space
resolution decreases. Therefore, less detailed structural infor-
mation can be obtained from the higher-temperature data due
to the reduced effective Qmax (<20 Å1).38,44 Consequently,
refinements using an r-range of 1–10 Å for PDF patterns above
225  C give structural information with large standard devia-
tions, and are unsuitable for drawing conclusions concerning
the local structure. Therefore, the maximum temperature for
local PDF refinements was limited to 225  C in this study. This
FIG. 7. The lattice parameters of BT-xBZT average structures as a function
of temperature, where x ¼ 0.06, 0.08, 0.10, and 0.20. limit of 225  C is higher than the Tm or Tdev of these BT-xBZT
compositions and the local scale structure in this temperature
nearly cubic at room temperature, and during heating only a range can be used to investigate the temperature-stable permit-
near-linear increase is observed, with the lattice parameters a tivity in BT-xBZT relaxor dielectrics.
and c overlaying each other. This behavior indicates that the Compared to Fig. 7, the local structures as a function of
average structure of the BT-0.20BZT relaxor remains pseudo- temperature in Fig. 8 exhibit totally different behaviors from
the average structure: for all the compositions, the lattice
cubic with negligible changes at elevated temperatures.
parameter c remains nearly constant with increasing temper-
Clearly, the negligible changes with increasing temperature in
ature, while the lattice parameter a gradually and slightly
the pseudocubic average structure are not directly responsible
increases. The error bars increase at higher temperature due
for the high dielectric permittivity. Considering the possible
to the enhanced atomic thermal vibration. One important
existence of nano clusters (or local tetragonal distortions) in
thing to note is that at temperatures as high as 225  C, the
these materials and the fact that these local structures may be
local tetragonal distortion persists, even though the average
closely related to the dielectric permittivity, it is crucial to have
structure approaches cubic. It is interesting that the local dis-
a systematic study of the local structural changes as a function
tortion within the 10 Å range is composition independent as
of temperature. These results are reported in Sec. III D.
well as temperature insensitive. These in situ high tempera-
ture PDF measurements suggest the persistence of the
D. Local structures at elevated temperatures
BT-xBZT local structures at elevated temperatures, which
Referring to the in situ PDF patterns in Fig. 5, it is corresponds to the existence of polar nanoscale clusters
important to reiterate that the low-r PDF peaks have different according to the PNR explanation. In addition, the box-car
behaviors compared to the high-r PDF peaks: peak broaden- method was performed for the PDF of BT-0.20BZT at 125
ing occurs with increasing temperature for low-r peaks, but and 225  C, respectively, and the lattice parameters a and c
the peak position appears unchanged, especially for the first
three peaks. Fitting the first three PDF peaks of all the PDF
patterns using a Gaussian function confirmed this observa-
tion: as shown in Fig. S8(a) (supplementary material) using
BT-0.06BZT as an example, the positions of local PDF
peaks remain at almost the same value with increasing tem-
perature. In addition, a linear decrease in the peak height and
increase in peak width for low-r peaks were also confirmed
by this peak fitting method, as shown in Figs. S8(b) and
S8(c) (supplementary material). The same trend of low-r
peak behaviors with increasing temperature was obtained for
all the other compositions. If a phase transition happens at
the local scale, we would expect to see shifts of local PDF
peak positions, and abrupt changes in the peak shape instead
of the linear gradual peak broadening effect. These observa-
tions indicate that the local scale structure in BT-xBZT may
persist at high temperatures.
Sequential temperature series fitting of BT-xBZT local FIG. 8. The lattice parameters of BT-xBZT local structures as a function of
PDF data was conducted with a scale range from 1 to 10 Å, temperature, where x ¼ 0.06, 0.08, 0.10, and 0.20.
064103-9 Hou et al. J. Appl. Phys. 122, 064103 (2017)

at different length scales are shown in Fig. S10 (supplemen- estimated to be 2–3 nm. During heating, a polar to non-polar
tary material). Even though the local tetragonal distortion phase transformation was captured for the ferroelectric-like
persists at elevated temperatures for BT-0.20BZT, e.g., 125 compositions by whole profile fitting of the in situ PDF data,
and 225  C, the tetragonality converges to near unity at a while the relaxor-like compositions show negligible average
shorter atom-atom distance (r). This infers a decrease in the structure changes. Examination of the local scale PDF data
size of nanoscale polar clusters among the non-polar matrix presents the persistence of tetragonal distortion at elevated
upon heating. temperatures to at least 225  C, indicating that stable polar
To summarize, the presence of a local tetragonal distor- clusters exist in BT-xBZT. The persistence of these polar
tion in relaxors decreases smoothly with increasing tempera- clusters may be the key to the mechanism of temperature-
ture, but can maintain its existence at temperatures above stable dielectric relaxors. Based on the results, the effect of
T m. Box-car fitting of high temperature PDF suggests that chemical doping Bi3þ and Zn2þ on A- and B- sites was dis-
the persistence of local polar clusters at elevated tempera- cussed, relating to the increased disorder, off-center dis-
tures is accompanied by a shrinkage of the cluster size. placements of Ti4þ, and local ferroelectric distortion. This
These nanoscale clusters with tetragonal distortions may be study demonstrates that the in situ PDF technique can be
responsible for the large relative permittivity in BT-BZT due used to investigate the fundamental mechanism of anoma-
to being highly responsive to an external stimulus, e.g., lous properties found in dielectric and ferroelectric materials,
electric-field. Therefore, our systematic PDF study assists in and can be extended to research of other functional
the interpretation of the high temperature dielectric permit- ceramics.
tivity of the relaxor compositions. In addition, for the
ferroelectric-like compositions (e.g., x ¼ 0.06), a combina- SUPPLEMENTARY MATERIAL
tion of average and local structure changes with temperature
See supplementary material for additional analysis of
shows evidence that the polar to non-polar phase transforma-
the dielectric permittivity, surface microstructure characteri-
tion is order-disorder type, demonstrates how global symme-
zation, and refinements of PDF patterns.
try may emerge from local symmetry-breaking distortions,
and agrees with other theoretical and experimental studies of ACKNOWLEDGMENTS
similar BT-based systems.59–62 The detected local ferroelec-
tric distortions in the current study might be partially induced This research used resources of the Advanced Photon
by the pseudo Jahn-Teller effect,62,63 in which the off-center Source, a U.S. Department of Energy (DOE) Office of
displacements of the Ti4þ are thought to be maintained in all Science User Facility operated for the DOE Office of
the phases and phase transitions in BT-xBZT. In addition, Science by Argonne National Laboratory under Contract No.
the strong covalent driving forces in the Zn-O bond, as well DE-AC02-06CH11357. This work was performed in part at
as the tendency of Bi3þ to occupy an offset position, might the Analytical Instrumentation Facility (AIF) at North
also be responsible for the local tetragonal distortions. The Carolina State University, which is supported by the State of
effects of Zn2þ and Bi3þ on the enhanced tetragonality have North Carolina and the National Science Foundation (Award
been studied and reported in other perovskite systems.53,64–66 No. ECCS-1542015). The AIF is a member of the North
On the other side, the addition of Bi3þ on A-sites and Zn2þ Carolina Research Triangle Nanotechnology Network
on B-sites also starts to break the long-range dipole order (RTNN), a site in the National Nanotechnology Coordinated
and inhibits the formation of a long-range ferroelectric Infrastructure (NNCI). D.H. thanks financial support from
phase, attributed to the higher degree of diffuseness and China Scholarship Council. T.-M.U. acknowledges support
stronger relaxor character. In general, this study suggests from the U.S. Department of Commerce under Award No.
that the local scale ferroelectric distortions (especially in 70NANB13H197. This material is based on work supported
1–10 Å range) are not affected by the increased disorder at by the U.S. Department of Energy, Office of Science, Office
elevated temperatures, resulting in the temperature-stable of Basic Energy Sciences under Contract No. DE-AC05-
feature of the dielectric permittivity in BT-xBZT relaxors. 00OR22725.
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