JOURNAL OF ADVANCED DIELECTRICS

Vol. 6, No. 4 (2016) 1650032 (8 pages)

© The Author(s)
DOI: 10.1142/S2010135X16500326

Synthesis and electrical properties of BaBiO3 and high resistivity

BaTiO3–BaBiO3 ceramics
§
Nitish Kumar*,†, , Stephen L. Golledge‡ and David P. Cann*
*Materials Science, School of Mechanical Industrial, and
Manufacturing Engineering
Oregon State University, Corvallis, Oregon 97331, USA
†School of Materials Science and Engineering
The University of New South Wales
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New South Wales 2052, Australia

‡
CAMCOR Surface Analytical Facility
University of Oregon, Eugene
Oregon 97403, USA
§
nitishkumar.iitk@gmail.com
J. Adv. Dielect. 2016.06. Downloaded from www.worldscientific.com

Received 25 September 2016; Revised 13 November 2016; Accepted 14 November 2016; Published 16 December 2016
Ceramics of the composition BaBiO3 (BB) were sintered in oxygen to obtain a single phase with monoclinic I2/m symmetry as
suggested by high-resolution X-ray diffraction. X-ray photoelectron spectroscopy confirmed the presence of bismuth in two valence
states — 3þ and 5þ. Optical spectroscopy showed presence of a direct bandgap at
2.2 eV and a possible indirect bandgap at

0.9 eV. This combined with determination of the activation energy for conduction of 0.25 eV, as obtained from ac impedance
spectroscopy, suggested that a polaron-mediated conduction mechanism was prevalent in BB. The BB ceramics were crushed,
mixed with BaTiO3 (BT), and sintered to obtain BT–BB solid solutions. All the ceramics had tetragonal symmetry and exhibited a
normal ferroelectric-like dielectric response. Using ac impedance and optical spectroscopy, it was shown that resistivity values of
BT–BB were orders of magnitude higher than BT or BB alone, indicating a change in the fundamental defect equilibrium
conditions. A shift in the site occupancy of Bi to the A-site is proposed to be the mechanism for the increased electrical resistivity.
Keywords: BaBiO3; BaTiO3; conduction mechanism; transport properties; synchrotron; X-ray photoelectron spectroscopy; im-
pedance spectroscopy; defects.

1. Introduction researchers for use as positive temperature coefficient of re-

sistivity (PTCR) devices.15,16 In one study, it was shown that
The BaBiO3 (BB) has a distorted perovskite crystal structure
addition of BB increased the Curie point so that the PTCR
with an ordered alternating Bi 3þ and Bi 5þ .1,2 At room tem-
effect was initiated above
150  C.17
perature, this charge disproportionation and ordering coupled
This report is focused on BT–BB solid solutions for the
with tilting of BiO6 corner-shared octahedra, result in a cell
with monoclinic symmetry (I2/mÞ.1,3 It was reported that BB purpose of understanding the influence of BB additions on
only has out-of-phase tilting, denoted by a0b  b  and the electrical properties of BT. It has been demonstrated that
a  a  a  in Glazer's notation.4,5 There have been a number of small concentration of BB were enough to increase the re-
reports on the compound BB, especially polycrystalline BB sistivity of BT–BB solid solutions by several orders of
ceramics doped with acceptors such as potassium, lead, and magnitude, suggesting a drastic change in underlying defect
other additives, for potential use in high-temperature super- chemistry. This is an important result because high resistivity
conductor applications.6–13 The transition from semicon- will enable devices made using these ceramics to be used
ducting behavior to superconducting behavior occurs with under high temperature and high electric fields. Application
doping and the critical temperature (Tc Þ typically depends of higher electric fields is also important to increase energy
upon the doping concentration and type.6,7 It has been sug- density values of ceramic capacitors.18 At the same time, it
gested that a phonon-mediated electron pairing mechanism may also help understand the defect chemistry of BT–Bi(Me)
for superconductivity may be significant, rather than Bard- O3 class of ceramics (excellent candidates for high temper-
een–Cooper–Schrieffer (BCS) theory.14 ature and high energy density dielectrics.19,20) as BB has
While doped BB has been studied primarily for super- been found to exist as an intermediate phase during proces-
conductor applications as mentioned above, BaBiO3–doped sing and can potentially influence defect equilibrium condi-
BaTiO3 (BT–BB) solid solutions have been studied by some tions owing to multivalent bismuth.21 In this paper, BT–BB

This is an Open Access article published by World Scientific Publishing Company. It is distributed under the terms of the Creative Commons Attribution 4.0
(CC-BY) License. Further distribution of this work is permitted, provided the original work is properly cited.

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 N. Kumar, S. L. Golledge & D. P. Cann J. Adv. Dielect. 6, 1650032 (2016)

solid solutions were prepared with small mole fractions of BB parameters, scale, lattice parameters, atomic positions, isotro-
to study the resultant dielectric and transport properties. This pic displacement parameters, thermal parameters, and others.
work also includes a full structural characterization of the BB Prior to any electrical measurements, Ag electrodes were
and BB–BT ceramics prepared in this study. applied on both sides of the pellets and then fired at 700  C
for 30 min. For undoped BB ceramics, instead of Ag, Pt
electrodes were used and with a firing temperature of 700  C
for 2 h in oxygen. The pellets were placed in a high tem-
2. Experimental Procedure
perature measurement cell (NorECs AS ProbostatTM, Oslo,
Solid-state methods was used to prepare BB ceramics using Norway) or low temperature environmental chamber (Delta
the precursors BaCO3 (Alfa Aesar, >99.8%) and Bi2O3 Design 9023, California, USA) and the dielectric properties
(Aldrich, >99.9%). The powders were mixed together in the were measured using an LCR meter (Agilent 4284A, Santa
proper stoichiometric ratio, ground using a vibratory mill for Clara, CA, USA). An impedance analyzer (Solartron
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6 h and dried overnight in an oven (
80  C). The powders SI1260A equipped with Solartron 1296A dielectric interface,
were then calcined in alumina crucibles at 725  C for 24 h and Farnborough, UK) was used to measure the impedance in the
then milled with
3 wt.% Rhoplex binder and dried again. frequency range 0.1 Hz to 1 MHz. The SMaRT impedance
Green pellets in the shape of thin discs were prepared by measurement software program was used to collect the data.
cold-pressing uniaxially at a pressure of
200 MPa and then The optical measurements were carried out on crushed sin-
sintered in oxygen at 825  C for 12 h. It was difficult to
J. Adv. Dielect. 2016.06. Downloaded from www.worldscientific.com

tered pellets over the wavelength range of 200–1100 nm at

achieve single phase on sintering in air, as will be seen later. room temperature using an Ocean Optics HR4000 UV-Vis
To make solid solutions of BT and BB, the sintered BB Spectrometer (Ocean Optics, Dunedin, FL) with a balanced
pellets were ground into powder form and then mixed with deuterium/tungsten halogen source. X-ray Photoelectron
appropriate amounts of BT (Sakai Chemical Industry). The Spectroscopy (XPS) spectra from the BB ceramics were ac-
mixture was then milled with
3 wt.% Rhoplex binder and quired on a ThermoScientific ESCALAB 250 spectrometer
dried. The green pellets were prepared using similar condi- located at the Center for Advanced Materials Characterization
tions as described above, and then sintered in air on a bed of in Oregon (CAMCOR). Photoemission was stimulated by a
calcined powder in closed alumina crucibles. The composi- beam of monochromatized Al K
X-rays with a nominal spot
tions investigated were (1xÞBT–xBB, where x ¼ 0.001, size at the sample surface of 500 m. A low energy electron
0.003, 0.005, 0.01, and 0.02, and will be henceforth abbre- source was used for charge neutralization. The spectra were
viated as 0.1BB, 0.3BB, 0.5BB, 1BB, and 2BB, respectively. acquired at a pass energy of 20 eV (high-resolution spectra)
These compositions were sintered at 1050  C for 4 h, 1000  C or 150 eV (survey spectra). Data analysis, including peak
for 4 h, 950  C for 4 h, 990  C for 8 h, and 990  C for 8 h, fitting, was performed with Avantage software, provided by
respectively. For purposes of comparison, some bismuth- the manufacturer.
doped ceramics were also prepared with 0.3 mol% Bi (or
0.15 mol% Bi2O3 Þ and 0.5 mol% Bi (or 0.25 mol% Bi2O3 Þ
added to BT. For this, excess Bi2O3 was added to BT pow- 3. Results and Discussion
ders, so as to achieve the above-mentioned doping levels. The
3.1. BB ceramics
powders were milled with 3 wt.% binder, dried, and then
green pellets were sintered at 1000  C for 4 h and 950  C for Figure 1(a) shows the comparison between XRD patterns for
4 h, respectively, on a bed of calcined powders. All the sin- the samples sintered in oxygen and air for the same temper-
tered pellets were polished to sub-millimeter thicknesses. ature and time. The pellet which was sintered in air had much
X-ray diffraction (XRD) (Bruker AXS D8 Discover, higher concentration of secondary phases and underscored
Madison, WI, USA) was performed on ground pellets for the importance of oxygen partial pressure during processing
phase and crystal structure determination. High-resolution of BB. The pellets were suitably dense after sintering and had
synchrotron powder diffraction data were collected on BB density values greater than 94% of theoretical value, as
powders using beamline 11-BM at the Advanced Photon measured via Archimedes' method. Figure 1(b) shows the
Source (APS), Argonne National Laboratory. An appropriate room temperature high-resolution XRD pattern of BB sin-
amount of the sample was loaded into a Kapton tube, sealed tered in oxygen, which was performed to confirm the phase
and mounted on the base provided by the 11-BM beamline of purity and formation of BB. Even within the detection limits
the APS. The diffraction experiments were carried out at of synchrotron radiation, no evidence of secondary phases
room temperature using monochromatic synchrotron radia- was observed. Consistent with literature reports, a distorted
tion of wavelength 0.413639Å and a step size of 0.001  . perovskite structure with a monoclinic unit cell (I2/mÞ was
The crystal structure was refined using the Rietveld refine- used to fit the pattern.3,23,24 The refinement resulted in a rea-
ment program GSAS-II.22 The Chebyschev profile was used sonably good fit can be seen in the difference curve in Fig. 1(b)
to fit the background and the number of background para- (wR ¼ 8.7%). The lattice parameters obtained were a ¼ 6.1865
meters used was 10. Parameters refined included peak-shaped (7) Å, b ¼ 6.1399(4) Å, c ¼ 8.6705(0) Å, and  = 90.178  ,

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 N. Kumar, S. L. Golledge & D. P. Cann J. Adv. Dielect. 6, 1650032 (2016)

(a) (b)
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Fig. 1. (Color online) (a) XRD pattern of BB sintered in air (bottom) and oxygen (top). The square boxes show the color of the pellets after
being sintered in air and oxygen. (b) Rietveld refinement of a high-resolution XRD pattern of BB sintered in oxygen. The data presented with
(þÞ symbol is the observed data and the black curves are calculated intensities. The bottom-most curve (blue) is the difference between
observed and calculated intensities.

the Bi(4f5∕2 , 4f7∕2 Þ peaks have been presented. The XPS

J. Adv. Dielect. 2016.06. Downloaded from www.worldscientific.com

and Table 1 shows the parameters obtained from the refine-

ment — atomic coordinates, site occupancy, and isotropic measurements were performed on powdered ground pellets.
thermal parameters. All these parameters were within rea- In considering past reports on BB in the literature, the pho-
sonable limits and corroborated the choice of unit cell and toemission studies performed by various groups are not in
confirmed the phase purity of BB to be used later for fabri- agreement. Jeon et al. and Kulkarni et al. reported the pres-
cating the BT–BB solid solutions. ence of multiple Bi 4f lines which they attributed to multiple
Even though bismuth with two different valence states valence states of bismuth.25,26 Several other groups have
(þ3 and þ5 in Table 1) were used for the structural refine- reported narrow bismuth core level spectra.27–30 Some at-
ment above, XRD may not be sensitive enough to properly tributed it to the presence of just one bismuth state in the
differentiate between trivalent Bi 3þ and pentavalent Bi 5þ , compound and some suggested that the level of dispropor-
which are the expected valence states of bismuth in BB.23 To tionation was too small to be detected by photoemission. As
investigate the valence state of bismuth in BB, XPS was is evident in the Bi4f spectra presented in Fig. 2, a shoulder is
performed and the results have been shown in Fig. 2, where clearly present on the high binding energy side of the Bi4f
peaks. As determined by peak fitting, the most intense
Table 1. Parameters for I2/m space group from the Rietveld refinement.
component of the Bi4f7∕2 peak was at 157.7 eV; the higher
binding shoulder was at 158.9 eV. These binding energies,
x y z Occupancy Uiso (Å 2 Þ and their separation, are close to those described in litera-
ture.25 The peaks used in the fit were symmetric, and the
Ba 0.4969(34) 0 0.2512(84) 0.999(3) 0.0039(6) relative intensities of each pair of Bi4f7∕2 and Bi4f5∕2 peaks
Bi(1) 0 0 0 1.021(6) 0.0001(1)
Bi(2) 0 0 0.5 1.023(4) 0.0001(8)
were constrained to be 4:3. The widths of the peaks corre-
O(1) 0.637(33) 0 0.2420(46) 1 0.0119(5) sponding to the þ5 state were slightly larger than those for
O(2) 0.2372(31) 0.2381(66) 0.0316(85) 1 0.0131(0) the þ3 state. In summary, the valence state of the target ion is
directly proportional to the binding energy, and therefore,
these shoulders can be attributed to the presence of Bi 5þ in
the sample, and therefore the data here clearly show evidence
of the presence of multiple valence states for bismuth in the
spectra for BB ceramics.
Figure 3 shows the dielectric permittivity and loss data for
BB over the temperature range of approximately 150  C to
200  C. Past reports on BB suggest a phase transition from
monoclinic I2/m to rhombohedral R 3 at around 132  C,31,32
however, this could not be observed in Fig. 3 due to the
effects of conduction losses. The dielectric permittivity values
were high over the entire temperature range of measurement,
Fig. 2. (Color online) XPS on powdered BB ceramics. The data again an artifact of high losses. A frequency-dependent re-
shown with \x" symbols are actual data obtained from the experi- laxation was observed in the dielectric loss at sub-zero tem-
ment. The background and fitted peaks have also been indicated. peratures and the temperature of the relaxation peak maxima
The low intensity fitted peaks (red) are from Bi 5þ . increased with increasing frequency. Lee et al. observed a

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 N. Kumar, S. L. Golledge & D. P. Cann J. Adv. Dielect. 6, 1650032 (2016)
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(a) (b)
Fig. 3. (a) Permittivity and dielectric loss as a function of temperature at 1, 10 and 100 kHz for BB ceramics, and (b) Arrhenius plot of applied
frequency and 1/Tm , where Tm are the temperatures at dielectric tangent maximum.

similar thermally activated phenomenon in their study and The value of 0.92 eV reported here is based on the as-
J. Adv. Dielect. 2016.06. Downloaded from www.worldscientific.com

attributed it to polaron hopping.33 Debye theory can be used sumption that the rise in the intensity of the signal close to
to analyze the dielectric relaxation involving polaron hop- 1 eV in Fig. 4(b) was due to the indirect bandgap in BB. The
ping. An Arrhenius plot of the frequency and the temperature presence of these bandgaps makes BB an indirect bandgap
of relaxation peak yielded the activation energy for relaxation semiconductor. Band-structure calculations have predicted
as shown in Fig. 3(b).33,34 The activation energy calculated in that BB should be metallic if bismuth were present in the 4þ
Fig. 3(b) was approximately 0.24 eV, which was consistent state as it would have a half-filled Bi 6s conduction
with literature reports.26 It was also close to the activation band.40,41 The origin of semiconduction in BB is believed to
energy for conduction calculated through ac impedance be due to result of the disproportionation of bismuth into 3þ
spectroscopy (
0.25 eV, Fig. 4(c)), which may suggest that and 5þ valence states, followed by ordering and accompa-
similar mechanisms control both the dielectric relaxation and nied by alternate expansion and contraction of oxygen oc-
conduction mechanism. tahedra. In other words, the strong soft-phonon related
The Kubelka–Munk function and Tauc plot were used to electron–phonon interaction, which is considered to be re-
calculate the indirect and direct bandgaps, which were esti- sponsible for superconductivity in BB-based ceramics, is
mated to be
0.92 eV and
2.2 eV, respectively (Figs. 4(a) completely softened leading to static displacement of the
and 4(b)).35–37 These values were consistent with literature oxygen atoms in undoped BB. This, in turn, leads to a
values.38,39 It is worth mentioning that previous literature configuration called charge density wave (CDW) or
reports have largely failed to directly assess the indirect band- breathing mode distortion, and is believed to be responsible
gap through techniques like optical reflectance, photocon- for the observed indirect bandgap at the Fermi level, which
ductivity, photoacoustic spectroscopy, and other techniques. then gives rise to semiconducting properties.31,33

(a) (b) (c)

Fig. 4. Kubelka–Munk and Tauc plots for BB ceramics. The appropriate functions for direct and indirect bandgaps were chosen for (a) and (b)
respectively. (a) and (b) also show representative fit lines used to estimate bandgaps. (c) shows Arrhenius plot with linear fit for bulk resistivity
obtained from ac impedance spectroscopy.

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 N. Kumar, S. L. Golledge & D. P. Cann J. Adv. Dielect. 6, 1650032 (2016)

pellets had measured density values greater than 95% of the

theoretical value, as measured via Archemedes' method. It
can also be noted in Fig. 5 that phase-pure perovskite could
be achieved for BB–BT solid solutions with less than 2 mol%
BB. The secondary phase shown for 98BT–2BB is believed
to be BB itself as the peak position matched well with the
most intense peak of BB (Fig. 1).
Figure 6 shows the dielectric constant as a function of
temperature. All the compositions exhibited a sharp phase
transition as expected for a normal ferroelectric material. The
Curie point was recorded to be between 122  C and 125  C for
Fig. 5. XRD pattern of (1xÞBT–xBB ceramics, where x lies be- all compositions, and was in contrast with a previous report
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tween 0.1 mol% and 2 mol%. The \  " indicates secondary phase, if which claimed an increase in Curie point by
30  C on
present.
adding
0.5% BB to BT.17 The room temperature dielectric
constant varied between
2000 and
3000. Notably, the
Figure 4(b) shows the activation energy for bulk con- dielectric loss values remained low (<5%) up to
300  C at
duction for BB, calculated using ac impedance spectroscopy. 1 kHz for all compositions, which was better than BB (Fig. 3)
or BT44 alone.
J. Adv. Dielect. 2016.06. Downloaded from www.worldscientific.com

Impedance spectroscopy is a powerful tool and can effec-

tively separate the bulk transport properties from other con- In order to further investigate long-range conduction in
tributions such as interfaces, inhomogeneity, and other these ceramics, ac impedance spectroscopy was performed
mechanisms.42 On plotting the bulk resistivity as a function and Fig. 7(a) shows the Arrhenius plots of the bulk resistivity
of temperature using the Arrhenius equation, the conduction values obtained from the same. The data for undoped BT and
was shown to be a thermally activated process with an acti- BB have also been shown for reference. In the plots, the BT–
vation energy estimated to be
0.25 eV. This is consistent BB ceramics appear to have multiple orders of magnitude
with the activation energy values reported using Seebeck and higher resistivity than either BT or BB alone. The activation
Hall measurements.38 This activation energy value is signif- energy for conduction, estimated from the slopes of the plots,
icantly lower than the measured bandgap values reported also increased significantly for the solid solution as compared
above. However, it has been suggested that this is closely to the end-member compounds. This suggests a dramatic
related to the indirect bandgap and not related to impurities.41 change in the underlying defect chemistry in these solid
It was also supported by the fact that the number of states solutions, which warrants further examination. The undoped
contributing to electrical conduction calculated by using Hall BT used in this study is characterized by a defect-dominated
measurements by Takagi et al. was comparable to the number p-type conduction mechanism, as reported in a previous
of bismuth atoms in the crystal structure.43 However, to ex- paper.45 In BT, the p-type behavior is commonly attributed to
plain the low activation energy (as compared to bandgap frozen-in cation vacancies formed during high temperature
measurements), it has been suggested that polaronic bands processing and low valence acceptor impurities associated
accommodating holes are formed above the top of occupied with starting reagent oxides.46–48 These vacancies and
Bi 6s band (
0.25 eV below Fermi level) and a polaron band acceptors can be compensated by oxygen vacancies, which
accommodating electrons are formed below the empty Bi 6s can in turn give rise to p-type behavior at high oxygen partial
band (
0.25 eV above Fermi level).41 Due to these polaron pressures as per following defect reaction:
bands, the conductivity gap is reduced to
0.5 eV, which can
explain the measured activation energy of 0.25 eV obtained
1
from impedance spectroscopy. V O þ O2 ! O X 
O þ 2h ; ð1Þ
2
where V O is a doubly ionized oxygen vacancy, O X
O represents
3.2. BB–BT ceramics an oxygen ion located on the anion sublattice, and h repre-
Following the results of the synthesis and characterization of sents a hole. In considering the significant change in con-
pure BB, this section aims to examine the change in transport ductivity with the addition of BB, a number of factors could
properties on adding small amounts of BB to BT. Figure 5 be responsible. First, the concentration of cation vacancies
shows the XRD patterns of pulverized BT–BB solid solution in BT–BB ceramics may be lower than BT alone owing to
ceramics. All the samples had split {200} peaks (
45  ), the significantly lower sintering temperatures (i.e., 1350  C
indicating tetragonal symmetry. Within the resolution of for BT and 950–1050  C for BT–BB). Secondly, there may
laboratory XRD, it was difficult to note any change in lattice be an unintended donor dopant species present which is
parameters with the addition of such small amounts of BB. compensating for the holes and thus effectively increasing
Notably, the sintering temperatures get reduced significantly the resistivity values. One of the many possible candidates
(by 300  C–400  C) on adding BB to BT. Still, all sintered for unintentional donor doping could be the occupation of

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 N. Kumar, S. L. Golledge & D. P. Cann J. Adv. Dielect. 6, 1650032 (2016)

(a) (b) (c)

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(d) (e)
Fig. 6. Permittivity and dielectric loss as a function of temperature at 1, 10 and 100 kHz for (a) BT–0.1BB, (b) BT–0.3BB, (c) BT–0.5BB, (d)
BT–1BB, and (e) BT–2BB ceramics.

bismuth cations on the A-sublattice, where by replacing apparent with increasing BB concentrations. Generally, it is
barium it will act as a donor. This possibility will be dis- considered to originate from disorder in a crystal such as
cussed later in this paper. localized defects, lattice vibrations, and other factors.36 These
Figure 7(b) shows the Tauc plots using the Kubelka– features lead to electronic states just above the valence band
Munk function, as was shown for undoped BB ceramics or immediately below the conduction band, and the transition
earlier. The indirect bandgaps for all compositions were between these bandtail states may give rise to Urbach tails.

3.1 eV, which is close to the value expected for titanate- More details about these Urbach tails can be found else-
based perovskites and is consistent with previous literature where.49,50 Another observation which can be made is that
reports.44 The peculiar characteristic present in all these plots the extrapolations of these tails intercept at the x-axis at
were the Urbach tail-like features, which became more
1.8–2.2 eV, which is close to the value of direct bandgap

(a) (b)
Fig. 7. (a) Arrhenius plots for bulk resistivity obtained from ac impedance spectroscopy for BT–BB ceramics. Plots for undoped BB and BT
have been shown for reference. (b) Kubelka–Munk and Tauc plots for BT–BB ceramics. The appropriate function for indirect bandgap was
chosen. Representative fit lines have also been shown.

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 N. Kumar, S. L. Golledge & D. P. Cann J. Adv. Dielect. 6, 1650032 (2016)

fabricated to investigate the effect of adding small amounts of

BB on the conduction mechanism of BT. It was observed that
the BT–BB ceramics had significantly higher resistivity
values as compared to undoped BT or BB, suggesting a de-
crease in the concentration of mobile defect species. The
resistivity values remained high even with a coexisting sec-
ondary BB phase. This is important for high temperature and
high energy density capacitor applications. Data from ac
impedance spectroscopy on Bi-doped BT suggested that a
shift in the site occupancy of Bi onto the A-sublattice is the
dominant mechanism resulting in donor doping which results
in the observed high resistivities.
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Fig. 8. Arrhenius plots for bulk resistivity obtained from ac im-

pedance spectroscopy for Bi-doped BT ceramics. Data for BT–BB
ceramics have been shown for reference. Acknowledgments
This material is based upon work supported by the National
for BB. Therefore, these features may also be a direct result Science Foundation under Grant No. DMR-1308032. Use of
of a secondary BB phase which may be undetectable by
J. Adv. Dielect. 2016.06. Downloaded from www.worldscientific.com

the Advanced Photon Source at Argonne National Laboratory

laboratory scale XRD techniques. was supported by the U. S. Department of Energy, Office of
In considering the mechanism for the increase in resis- Science, Office of Basic Energy Sciences, under Contract
tivity for BT–BB ceramics as compared to BT, unintentional No. DE-AC02-06CH11357. Thanks to Fallon Fumasi for her
donor doping due to changes in bismuth site occupancy was help with XPS measurements.
proposed to be a possibility. Direct confirmation of bismuth
on the A-site is extremely challenging due to the relatively
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