SOLID

STATE
SolidStateIonics66 (1993) 151-158
North-Holland

IOWICS

Electrical characterisation of bismuth orthovanadate

using ac impedance spectroscopy
P. Wood
Johnson Matthey Technology Centre, Blount’s Court, Sonning Common, Reading RG4 9NH. UK

D.C. Sinclair
IRC in Superconductivity, University of Cambridge, Madingley Road, Cambridge CB3 OHE, UK

and

F.P. Glasser
Chemistry
Department, University ofAberdeen. Meston Walk, Aberdeen AB9 2UE, UK

Received 22 April 1993; accepted for publication 24 June 1993

Polycrystalline phase pure BiV , 0250 4+X ceramics were prepared by solid state synthesis. These materials were found to exhibit
mixed oxide ion/electronic conduction from ac impedance measurements recorded between 150-800°C in various atmospheres.
The results indicate predominantly electronic conduction at both low and high temperatures i.e. i 400°C and > 600°C. Oxide
ion conduction was found to dominate the temperature region between 400 and 600°C with an activation energy of 0.80 k 0.01
eV. The bulk conductivity below 400°C was found to be metastable and influenced by the presence of water. The possibility of
protonic conduction at low temperatures is therefore identified.

1. Introduction electrical characterisation [ 1 l-141. BiV04 is found

to be a complex electrical material, exhibiting both
Bismuth orthovanadate, BiV04 exists in three po- oxide ion and electronic conduction. Wide discrep-
lymorphic modifications; one monoclinic and two ancies however arise over the precise nature and
tetragonal forms, of fergusonite, scheelite and zircon temperature range of the mixed conductivity; Lu and
structure types respectively. The zircon polymorph Steele [ 111 report p-type ( > 350°C), whereas Hi-
is only obtained by precipitation routes [ 1,2] whereas rota et al. [ 121 report only oxide ion conductivity
the fergusonite polymorph can be prepared by both ( 150-550°C). Detailed electrochemical studies, in-
precipitation and solid state techniques [ l-41. A re- cluding Seebeck and ac impedance measurements
versible ferroelastic phase transition occurs, to the have been carried out above 600°C by Vinke et al.
scheelite polymorph, on heating the fergusonite po- [ 131 in which n-type mixed conduction was
lymorph at ca. 255°C [5,6]. The scheelite poly- identified.
morph is often referred to as the high temperature In the present paper we report ac impedance data
polymorph as it is unstable at room temperature in for the temperature range 150-800°C in atmo-
the stoichiometric form. spheres of air, argon and oxygen, with attention paid
Research into BiV04 has concentrated mainly on to equilibration times at low temperatures. Further-
the fergusonite polymorph and, in particular, its fer- more, interference in the intrinsic conductivity due
roelastic phase transition. Although it has been widely to water adsorption below 400°C is reported for the
studied for pigment [ 781 and catalytic applications first time.
[ 9,101, there are relatively few reports regarding

0167-2738/93/$06.00 0 1993 Elsevier Science Publishers B.V. All rights reserved.

152 P. Wood et al. /Electrical characterization ofBiVO.,

2. Experimental TEMPiOC

600 100 200

Bi,O, and V,O, reactants (both Johnson Matthey
0t
99.5%) were dried at 240°C and stored in a vacuum
desiccator prior to use. Appropriate weights totalling
l-2 g were mixed to a slurry with acetone in an agate
mortar and pestle. The resultant powders were cal-
cined in gold boats, initially at 500’ C for three hours
and then at 880°C for 24-48 h. Two subsequent
grinding and recalcination steps followed to ensure
homogenisation of the samples. No significant weight
loss was recorded at any stage of the reaction pro-
cess. 9 mm pellets were cold pressed, sintered at
880” C for 24 h and gold paste electrodes fired on at
200-600°C. All heat treatments were conducted in

!
air unless stated otherwise. Phase purity was estab-
lished by X-ray diffraction using a HHgg-Guinier
z
camera. The presence of water was confirmed by I --'At
I
thermogravimetric analysis, Stanton Redcroft, I I I II I I
STA78 1, and reflectance infra-red spectroscopy, Per- 10 12 14 16 18 20 22 2L 26

kin Elmer, PE 1720X FTIR. 103K/T

ac impedance measurements were carried out us-
ing combined Solartron 1250/1286 and Hewlett
Packard 4 192A instrumentation, covering the fre-
quency range 1Op2 to 10’ Hz with an applied voltage
of 100 mV. Experiments were conducted in an at-
mosphere/temperature controlled jig using flowing
gases of oxygen, argon and air. Wet and dry atmo-
spheres were obtained by passing the gases initially
through Dreschel bottles of water or concentrated
H2S04 respectively. All recorded data were corrected
for a measured jig capacitance of 4pF.
3. Results and discussion
Solid state samples were prepared in the compo-
sitional range 40 to 60 mole% V20s in order to clar-
ify the region around the 1: 1 Bi203: V20s compo-
sition. Contrary to the reported literature [ 15, 161
only the composition BiV,.02504+x was found to be
single phase, whereas the stoichiometric composi-
tion yielded a two phase mixture of “1: 1” and trace
amounts of “2: 1”. In an attempt to synthesize the
stoichiometric composition as a single phase, sam-
ples were prepared under various conditions i.e. us-
ing higher purity oxides (Johnson Matthey 99.9%)
and oxygen and argon anneals close to the melting
Fig. 1. Arrhenius plots for BiV 1.025O4+Xobtained in dry atmo-
spheres of air, oxygen and argon. Closed and open circles repre-
sent heating and cooling data respectively.
point ca. 930°C followed by rapid quenching into
mercury. In each case two phase mixtures were ob-
tained, thus identifying the nonstoichiometric na-
ture of fergusonite-type bismuth orthovanadate. The
single phase sample composition BiV1.02504+x was
therefore used for subsequent electrical characteris-
ation. Arrhenius plots for the ac impedance data ob-
tained in dry atmospheres of air, oxygen and argon
are illustrated in fig. 1. The data are discussed with
respect to two temperature ranges; above and below
400°C.
3.1. Above 400” C
Complex impedance plane plots obtained in ox-
ygen and argon atmospheres at 549°C are shown in
fig. 2 and are representative of the temperature re-
gion 400-600°C. The high frequency arc has an as-
sociated capacitance of ca. 5 pF cm- ’ (from the re-
lationship wRC= 1 at Z&,, where w= 2nf and f is
 P. Wood et al. /Electrical characterization ofBiV0, 153

TEMPIOC

600 LOO 200

1 I I

-Z"/
kohmrm

0
L 1 2 3
Z'lkohmcm

Fig. 2. Complex impedance plane plots recorded at 549°C in dry

atmospheres of (a) oxygen, and (b) argon. Selected frequencies, I I I I
I
I I I I

in Hz on a logarithmic scale, are identified by solid circles. 10 12 14 16 18 20 22 24 ; 6

103K/T

the applied frequency) and is therefore indicative of
a bulk component. In the oxygen atmosphere, fig. 2a,
the low frequency response shows both a charge
transfer component, with an associated capacitance
of 0.2 mF cm-’ and an inclined spike. In compar-
ison, the low frequency data in the argon atmo-
sphere, fig. 2b, yields only an inclined spike of ca.
45 O, indicative of a Warburg-like response. Such low
frequency behaviour is associated with diffusion of
oxygen through the electrode [ 171 and confirms ox-
ide ion conductivity in this system [ 1 l- 13 1.
As highlighted in figs. 1 and 2, the bulk response
with an activation energy of 0.80 t 0.01 eV, is at-
mosphere independent with one hour equilibration
periods and is fully reversible on thermal cycling. This
behaviour, over the temperature range 400 to 6OO”C,
is consistent with the previously reported data as
shown in fig. 3.
Longer equilibration times and higher tempera-
tures, however, suggest more complicated behav-
iour. In argon a small increase in bulk conductivity
of 0.12 + 0.02 pQ cm-‘, at 598’ C was observed over
a 68 h equilibration period, whereas no significant
change was recorded in oxygen. At elevated temper-
atures, up to 8OO”C, deviation from the Arrhenius
Fig. 3. Combined Arrhenius plots from the present data and the
reported literature, conducted in air.
behaviour was observed with higher than expected
bulk conductivities recorded. Although this region
was not studied in detail, significant depression of
the electrode spike in the complex impedance plane
was observed. These features indicate the added
presence of electronic conduction in the temperature
range 600 to 800” C. A possible equivalent circuit,
modelling the observed mixed type behaviour, in-
cluding both bulk ionic and electronic components,
is shown in fig. 4.
Normally in such mixed ionic/electronic oxide
conductors, an increase in bulk conductivity with
lowering oxygen partial pressures, PO,, infers that the
electronic conduction is n-type in nature. We need to
confirm this however using other. techniques e.g.
thermoelectric power measurements.
A recent report by Vinke et al. [ 13 1, published
shortly after the completion of our work, identifies
mixed n-type conductivity in the system between 400
and 750°C. In particular, ionic conductivity pre-
dominates the ac response between 400 and 6OO”C,
and is atmosphere independent with an activation
154 P. Wood et al. /Electrical characterization ofBiV0,

from the low frequency intercept of this arc, as in-

dicated in fig. 5. At lower frequencies, no charge
transfer or significant spike was observed; instead an
extended tail was recorded. We saw no evidence in
Cct our data of the grain boundary arc reported by Hir-
‘b
otaetal. [12] andLuandSteele [ll].
i..._.........__..._.
._.....f$& _...___________
i On comparison of the Arrhenius plots, fig. 1, at-
mosphere-dependent bulk conductivity was ob-
Fig. 4. A possible equivalent circuit used to model the ac imped-
ance data of BiV,.02504+Xin the temperature region 400 to 8OO”C, served below 400°C. In each atmosphere studied, re-
Ri, R, and R,, correspond to bulk ionic, electronic and charge versible behaviour on thermal cycling was detected
transfer resistances respectively and Ct, and C,, refer to the bulk from 25 to 255°C; however slight variations were
and charge transfer capacitances. detected between 255 and 400°C particularly in ar-
gon and air. From the atmosphere dependent bulk
conductivities recorded, the presence of a low fre-
100 396OC quency tail in the complex impedance plane plots and
t 1
the associated change in slope of the Arrhenius plots
at ca. 4OO”C, it can be inferred that this material ex-
hibits electronic conductivity in this low tempera-
ture region. Additional measurements are required
however in order to confirm the precise nature of the
0 100 200 electronic charge carriers.
Zlkohmrm
Further changes in Arrhenius slopes are detected
Fig. 5. Complex impedance plane plot recorded at 396°C in dry at ca. 255°C corresponding to the ferroelastic phase
oxygen. Selected frequencies, in Hz on a logarithmic scale, are
transition temperature of BiV,.02504+x, with acti-
identified by solid circles.
vation energies of 0.38, 0.35 and 0.10 eV in argon,
energy of ca. 0.8 eV. Above 600°C deviation from air and oxygen respectively. This change in slope at
the single Arrhenius line and depression of the elec- 255°C is consistent with electrical data obtained in
trode spike in the complex impedance plane plots air using single crystals [ 141; however, the transition
were also detected, in conjunction with decreasing is previously unrecorded for ceramic samples
oxide ion transference numbers. This deviation from [ 11,12 1. The temperature of the phase transition was
linearity in the total conductivity was attributed to confirmed by high temperature XRD [ 18 1. No at-
the increasing dominance of n-type electronic con- tempt was made to extract activation energy values
ductivity above 600°C. This is consistent with our for the data between 255 and 400°C due to the oc-
own data whereby the electronic conductivity above currence of non-ideal Arrhenius behaviour, arising
600°C starts to “short-circuit” the ionic response from the transition between predominantly ionic
observed between 400 to 600’ C, thus giving rise to ( > 400°C) to electronic conduction ( < 400°C).
non-Arrhenius type behaviour in conductivity above Arrhenius data in fig. 1 corresponds to one hour
600°C. equilibration periods, however, complications were
found to arise with longer equilibration times, par-
3.2. Below 400°C ticularly in the intermediate temperature range. For
example, at 318°C the bulk conductivity in oxygen
3.2.1. Dry atmospheres decreased by a factor of two over a period of 32 h.
A typical complex impedance plane plot for this It was also found that the absolute magnitude of the
low temperature region, showing a single semi-cir- bulk conductivity values obtained below 400’ C are
cular arc, with an associated capacitance value of 5 dependent on the thermal history of the sample. Data
pF cm-‘, is shown in fig. 5. Bulk conductivity data recorded below 400°C therefore represents a quasi-
used in the Arrhenius plots, fig. 1, were extracted equilibrium state. Constant equilibration times of one
 P. Wood et al. / Electrical characterization of Bi VO, 155

hour, at each temperature, were adhered to in our esis loops in the stress-strain relation around 255’ C
study. [ 221. We propose that the existence of residual strain,
At this point it is instructive to consider the com- associated with the ferroelastic phase transition, is
bined spectroscopic plots of the imaginary compo- responsible for the M” peak broadening and for the
nents of impedance, Z”, and electric modulus, M”. non-ideality observed in both the combined Z” and
Such plots have been found to give additional in- M” spectroscopic and Arrhenius plots obtained in
formation, not readily available from the complex the temperature region close to the aGP phase
impedance plane alone, regarding the electrical transition.
“constitution” of complicated electrical materials e.g. Combining the results obtained below 400°C it is
donor-doped BaTiO, [ 19,201. Fig. 6 illustrates the apparent that bismuth orthovanadate is much more
data obtained at 396°C in oxygen, in which coin- complicated in this temperature region than previ-
cident Z” and M” Debye peaks, corresponding to the ously suggested, with a number of contributing fac-
bulk component, are observed with near ideal half- tors. The ac response in different atmospheres may
height peak widths of 1.33 decades of frequency, point towards p-type electronic conduction, how-
compared with an ideal theoretical value of 1.14 ever, further characterisation using alternative tech-
[ 2 11. In terms of equivalent circuit analysis, such a niques, e.g. thermoelectric power measurements, are
response can be modelled on a single parallel RC required in order to confirm this hypothesis.
element. Fig. 3 provides a comparison between the present
Spectroscopic plots obtained below ca. 396°C study and that reported in the literature. Above
however, show a divergence of Z” and M” peaks. At 400°C comparable bulk conductivity data are ob-
lower temperatures a reduction in M” peak height is tained in all cases, however, discrepancies arise be-
observed with an associated asymmetric peak broad- low 400 ‘C. Hirota et al. [ 12 ] report linear Arrhen-
ening, e.g. 1.96 decades at 201 “C as illustrated in ius behaviour throughout the temperature range
fig. 7. Arising from this non-ideal response below studied whereas Lu and Steele [ 111 illustrate four
400°C we can no longer use a single ideal parallel separate regions. Furthermore, in both these studies
RC element to model this bulk component. Bismuth no atiP phase transition was observed. In compar-
orthovanadate is reported to exhibit marked hyster- ison with the present data, these discrepancies may

-Z”/ k ohm

Fig. 6. Combined Z” (0 ) and M” (0 ) spectroscopic plot recorded at 396°C in dry oxygen.

156 P. Wood et al. /Electrical characterization of BiVO,

lustrated in fig. 8. The following features are

3 6
log,,
Fig. 7. M” spectroscopic plots recorded at selected temperatures
in dry oxygen. Temperatures
possibly be attributed
chiometry, preparative
cipitation/hydrolysis)
tion time.
If/Hz)
are given in degrees Celcius.
to variations in cation stoi-
routes (via solid state or pre-
and/or length of equilibra-
observed:
(a) an irreversible plateau region is exhibited on
the initial heating cycle,
(b) the bulk conductivity values are irreversible
on cycling below 400°C
(c) a change in slope of the Arrhenius plot at the
a=P phase transition is absent on the initial heating
cycle but is present on cooling (and subsequent heat-
ing cycles),
(d) a marked increase in activation energy is ob-
served in the initial heating cycle at low temperatures.
The irreversible nature of the initial heating/cool-
ing cycle can be attributed to the release of water from
the sample. We propose that the high activation en-
ergy observed at low temperatures may be associated
with the presence of protonic conduction. The data
obtained for the initial heating cycle is reminiscent
of studies conducted on SnO, gas sensors by Wil-
liams et al. [ 231 and also by one of the authors [ 241,
in which close control of humidity is required. The
irreversible plateau region, involving temperature

TEMP I°C
3.2.2. Initial heating cycle and wet atmospheres
800 600 400 200
The presence of structural and/or adsorbed water I I I I

in BiV 1.0250 4+x, was identified using TGA and IR

spectroscopy [ 18 1. A small OH stretch was observed
at ca. 3350 cm-’ by IR spectroscopy, however, the
existence of an OH bend at 1600-1750 cm-‘, iden-
tifying absorbed water, was not conclusive due to the
presence of broad vanadate IR bands occurring at
1200-1750 cm-‘. A weight loss of ca. 0.11 wt.% was
recorded from room temperature to ca. 300°C by
TGA. The weight loss of 1.6% at 130” C, recorded by
Hirota et al. [ 121, is attributed to the release of ab-
sorbed water, resulting from the hydrolysis prepa-
rative route. In our case, however, it is harder to dis-
criminate between structural and/or adsorbed water
due to the higher retention temperature of ca. 350°C
and the unconfirmed OH bend. The influence of this
water can account for additional complications ob- z
served in the initial bulk conductivity data recorded t
I I I I I I I I I I
below 400°C and in subsequent studies conducted 08 10 12 1L 16 18 20 22 2L 26

in wet gas atmospheres. 103K/T

The bulk conductivity data for the initial heating/ Fig. 8. Arrhenius plots obtained for the initial heating/cooling/
cooling cycle of BiV,.02504+x, aged in air at room heating cycle in air for a BiV,.,2,0,+, sample aged at room tem-
temperature for a period of ca. one month, are il- perature in air for ca. one month.
 P. Wood et al. /Electrical characterization ofBiV0, 1.57

In order to investigate the influence of humidity,

variations in bulk conductivity were recorded in wet
oxygen atmospheres as a function of time, at 200,
303 and 401 “C, fig. 9. A marked increase in bulk
conductivity was observed at 200 and 303°C with
short equilibration times of one to two hours. Full
equilibration was achieved after ca. 80 h with the
conductivities increasing by a factor of three and two
at 200 and 303°C respectively. At 400°C however,
only a small increase was observed with full equili-
bration achieved after a shorter time, of ca. 10 h.
Complex impedance plane plots obtained at 303 ‘C
for various equilibration periods are shown in fig.
10. Although a change in resistivity is clearly appar-
ent, no change in the associated bulk capacitance was
i a- calculated, thus suggesting the existence of structural
water (as opposed to adsorbed water).
2OO'C
In summary, the presence of water clearly influ-
ences the electrical properties of bismuth ortho-
06-
vanadate. The ability of this material to retain water
I I / 1
0 20 40 60 80
to temperatures as high as 400°C makes it an inter-
TIME /HOURS
esting system for possible protonic conduction and/
or gas sensing applications.
Fig. 9. Variation of the bulk conductivity with time in wet oxygen
atmospheres at 200,303 and 40 1 “C.

4. Conclusions

Phase pure bismuth orthovanadate was prepared

50
by solid state reaction with an overall composition
- Z"/k of BiV 1.o25O4+X.Electrical characterisation was con-
ohm cm
ducted using ac impedance spectroscopy over the
temperature range 150 to 800°C in dry atmospheres
of air, oxygen and argon. This material was identi-
0 50 100 150 fied as a mixed ionic/electronic conductor, whereby
Z'lk ohm cm
electronic conduction predominates below 400°C
Fig. 10. Complex impedance plane plots recorded in dry and wet
oxygen atmospheres at 303°C for various equilibration periods,
and above 600” C. In the intermediate 400-600°C
time given in hours. Selected frequencies, in Hz on a logarithmic temperature range, atmosphere-independent oxide
scale, are identified by solid circles. ion conductivity was recorded. Atmosphere-depen-
dent Arrhenius behaviour, of the bulk conductivity
independent conductivity data, is associated with the below 400°C is reported for the first time.
removal of water from the sample. The ferroelastic a+3 phase transition of
Extrinsic conductivity recorded below 400°C in BiV 1.0250 4+x was identified by a change in slope of
the initial heating cycle is therefore due to the pres- the Arrhenius plots at ca. 255’ C. It is proposed that
ence of water, whereas at higher temperatures re- the non-ideal M” spectroscopic plots obtained around
versible intrinsic behaviour is observed. Thus, in or- the phase transition temperature are associated with
der to ensure the measurement of the intrinsic residual strain arising from this phase transition.
response below 400°C conductivity experiments Results obtained from TGA, reflectance IR and ac
must be conducted in dry atmospheres. impedance spectroscopy indicate that fergusonite-
158 P. Wood et al. /Electrical characterization of Bi VO.,

type BiV,.02504+x, prepared by solid state synthesis, [2] I.M. Gottlieb and D.P. Kelley, J. Therm. Anal. 1 (1974)
can retain structural and/or adsorbed water to 350- 675.
[ 31 R.S. Roth and J.L. Waring, Am. Mineral. 48 ( 1963) 1348.
400°C. The presence of this water was shown to have
[4] I.M. Gottlieb and Ch.R. Rowe, J. Therm. Anal. 2 ( 1971)
a marked influence on the bulk conductivity ob- 303.
tained below 400°C in wet atmospheres; however, [ 51 W.I.F. David and A.M. Glazer, Phase Transit. 1 ( 1979) 155.
no change in associated bulk capacitance was cal- [6] A.W. Sleight, H.-y. Chen, A. Ferretti and D.E. Cox, Mat.
ResBull. 14 (1979) 1571.
culated, thus indicating structural water. Arising from
[7] P. Koehler, P. Ringe and H. Heine, Patent DE 3315850
this presence of water, the possibility of protonic
(1984).
conduction in the system below 400°C is identified. [8] D.H. Piltingsrud, Patent GB 1585525 (1981).
In summary, general agreement is obtained be- [9] J.W. Ward and R.H. Hass, Patent EP 085213 (1982).
tween this data and that of the reported literature [ lo] P.K. Sinhamahapatra, V.K. Sharma, S. Sinhamapahaptra
and S.K. Bhatta, React. Kinet. Catal. Lett. 7 ( 1977) 17 I.
above 400°C but with discrepancies arising at lower
[ 1 I] T. Lu and B.C.H. Steele, Solid State tonics 21 (1986) 339.
temperatures. The electrical response of BiVL.02504+x [ 121 K. Hirota, G. Komatsu and M. Yamashita, Mat. Res. Bull.
was found to be highly complex below 400°C with 27 (1992) 823.
a number of contributing factors; equilibration de- [ 131 I.C. Vinke, J. Diepgrond, B.A. Boukamp, K.J. de Vries and
pendence, the occurrence of an aep phase transi- .4.J. Burggraaf, Solid State Ionics 57 ( 1992) 83.
141 A. Sawada and T. Fuju, Toyoda Kenkyu Hokoku 35 ( 1982)
tion, non-ideal combined Z” and M” spectroscopic
6.
and Arrhenius plots, and the influence of structural
151 Ya.N. Blinovskov and A.A. Fotier, Russ. J. Inorg. Chem. 32
and/or adsorbed water. In conclusion BiVL.02504+x (1987) 145.
is electrically metastable below 400’ C. 161 M. Touboul and C. Vachon, Thermochim. Acta 133 ( 1988)
61.
171 J.T.S. Irvine, D.C. Sinclair and A.R. West, Adv. Mater. 2
(1990) 132.
Acknowledgement [ 181 P. Wood, Synthesis and characterisation of bismuth
orthovanadate, PhD Thesis (Aberdeen University), to be
We would like to thank A.R. West (Aberdeen Uni- submitted.
[ 191 D.C. Sinclair and A.R. West, J. Mat. Sci. Lett. 7 (1988)
versity) for the use of ac impedance apparatus and
823.
also the SERC and Johnson Matthey (Case stu- [20] D.C. Sinclair and A.R. West, J. Appl. Phys. 66 (1989) 3850.
dentship P. Wood) for financial support. [ 2 I ] 1.M. Hodge, M.D. Ingram and A.R. West, J. Electroanal.
Chem. 74 (1976) 125.
[22] A.R. Lim, S.H. Choh and M.S. Jang, Ferroelectrics 106
(1990) 81.
References [23] P.T. Moseley and B.C. Totield, Solid State Gas Sensors
(Adam Hilger, London, 1987) Ch. 5, p. 221.
[I ] H.E. Swanson, Nat. Bur. Stds. (US) mono. 25 (1964) p. [24] D.C. Sinclair, A.R. West and P.T. Moseley, private
14, sec. 3. communication.