Journal of the European Ceramic Society 23 (2003) 721–728

www.elsevier.com/locate/jeurceramsoc

Electrical properties of Sb and Cr-doped

PbZrO3–PbTiO3–PbMg1/3Nb2/3O3 ceramics
R.W. Whatmore*, O. Molter, C.P. Shaw
School of Industrial and Manufacturing Sciences, Cranfield University, Cranfield MK43 0AL, UK

Received 12 January 2002; accepted 12 May 2002

Abstract
The pyroelectric, dielectric and DC resistive properties of Sb and Cr-doped ceramics with a base composition of Pb(Mg1/3Nb2/3)0.025
(Zr0.825Ti0.175)0.975O3 have been studied. Sb doping has been shown to produce a linear reduction in Curie temperature
(TC=
22z+294  C) with concentration (z) and to give an increase in pyroelectric coefficient from 250 to 310 mCm
2 K
1 for z
increasing from 0 to 3 at.%. It also produces first a reduction and then an increase in both dielectric constant and loss, so that the
33 Hz pyroelectric figures of merit (FOM’s) are as follows: FV peaks at 3.810
2 m2 C
1 and FD peaks at 1.210
5 Pa
1/2. The
resistivity is increased substantially from 1.11011 to ca 61011
m with 1 at.% Sb, thereafter changing little. The behaviour has
been explained in terms of Sb acting as a donor ion, reducing oxygen vacancy concentrations up to 1 at.%, with conductivity
dominated by hole hopping between traps (Ea=0.59  0.05 eV) that are not changed by the Sb doping. It is concluded that addi-
tions of higher levels of Sb do not produce electron-mediated hopping conduction. The Cr additions have no effect upon TC, but
reduce dielectric constant and loss, pyroelectric coefficient and resistivity at doping levels up to 3 at.%. The FOM FV peaks at
3.610
2 m2 C
1 and FD at 1.910
5 Pa
1/2. The behaviour of the electrical resistivity as a function of dopant level is shown to
produce a linear ln(
o) vs z
1/3 dependence (
o=DC conductivity), as would be expected for hole hopping conduction between
Cr3+ sites, with an Ea=0.38 0.03 eV.
# 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Electrical properties; Pb(Mg,Nb,Zr,Ti)O3; Perovskites; PZT

1. Introduction arrays with large numbers (ca 100 K) of very small (ca
40 mm) elements provide excellent thermal imaging per-
The use of the pyroelectric effect for the detection of formance. Typically they use ceramics such as lead
infra-red radiation in the 3–5 and 8–12 mm IR bands has scandium tantalate (PST6) or barium strontium titanate
been known for many years1 and has been extensively (BST7) operated close to their Curie temperatures and
commercialised in applications such as people sensing, under an electrical bias (so-called ‘‘dielectric bolometer
environmental monitoring and gas analysis.2 There has mode’’). The combination of high permittivity (ca 2000)
also been, for about 25 years, an interest in the devel- and very high pyroelectric coefficient (ca 3500 mCm2
opment of pyroelectric devices for thermal imaging.3 K
1) with low dielectric loss (ca 510
3) under these
Solid state arrays are of particular interest.4 These use a conditions makes such materials well matched to the
thin ferroelectric ceramic wafer bonded to a 2D array of very small elements used in thermal imaging.
amplifiers and multiplexer switches integrated on an There is also a need for arrays with a lower resolution
application specific silicon integrated circuit (ASIC). capability to address areas such as: spatially-resolved
Companies such as BAE SYSTEMS Infra-red Ltd. in people sensing (e.g. for monitoring people movements,
the UK have developed arrays with 128256 and environmental control etc); spatially-resolved flame and
384288 elements,3 while Raytheon in the USA have fire sensing; security, automotive sensing, traffic monitor-
developed an array with 320240 elements.5 These ing and low resolution imaging radiometry. A recogni-
sable image is not required for these applications, and a
* Corresponding author. Tel.: +44-1234-750759 x4057; fax: +44- relatively small number (e.g. 1616) of larger (few hun-
1234-751346. dred mm dimension) elements is adequate. There have
E-mail address: r.w.whatmore@cranfield.ac.uk (R.W. Whatmore). been attempts to address these applications with arrays
0955-2219/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S0955-2219(02)00162-0
722 R.W. Whatmore et al. / Journal of the European Ceramic Society 23 (2003) 721–728

based upon ferroelectric polymers such as PVDF/ paper reports that Cr behaves in a rather similar way to
TrFE,8,9 with linear arrays using ferroelectric thin films uranium, first increasing and then decreasing the resis-
on MgO10 and with 2D arrays using ferroelectric thin tivity as the dopant level is increased. This has also been
films directly integrated onto silicon.11 The performance confirmed by other workers.18 There is thus a good case
of the first is inadequate because of the low pyroelectric for a more detailed assessment of single and multi-
figures of merit (FOM)2 of the ferroelectric polymers, valent dopants on the electrical properties of pyro-
the linear arrays require a relatively expensive and bulky electric ceramics. The study reported here is an assess-
optical scanning system to provide the 2D spatial infor- ment of the effects of Sb and Cr in the PMNZT system.
mation. The technology for making 2D arrays based The base composition chosen for the study was for-
upon ferroelectric thin films on silicon is difficult and mulated as Pb(Mg1/3Nb2/3)0.025(Zr0.825Ti0.175)0.975O3. This
not yet ready for the market. was chosen on the basis of earlier studies14 as having
Ferroelectric ceramics based on the PbZrxTi1
xO3 particularly interesting pyroelectric properties.
(PZT) system with x1 or 0, offer a combination of
pyroelectric figures-of merit that make them ideal for
such low resolution arrays,2,3 possessing moderate per- 2. Experimental
mittivities (ca 200–300), low dielectric losses and good
pyroelectric properties (ca 300 mCm2 K
1). A particu- Ceramic pellets with the composition Pb{(Mg1/3
larly important aspect of the performance of such Nb2/3)0.025(Zr0.825Ti0.175)0.975}1
zXzO3 (where X=Sb or
materials is the control of DC resistivity. (This is in Cr) were fabricated from 99.9% pure raw materials
contrast with the fine-pitch arrays using bolometer- using a standard mixed-oxide process as described pre-
mode ceramics, for which high resistivity is essential.) It viously.19 Excess PbO (1 at.%) was added to the for-
permits the electrical time constant of the element to be mulation to help compensate for PbO losses during
fixed without recourse to an external resistor and it processing. Sample densities were all between 94 and
allows the bias point of the input amplifier on the ASIC 96% theoretical. The samples were polished, immersed
to be determined. Previous work has shown12 that ura- for approximately 2 s in a grain boundary etch [HCL
nium is a very effective dopant both to reduce permit- 4.5 vol.%/HF 0.5 vol.%/distilled water] and studied
tivity and loss, and for the control of electrical resistivity using optical microscopy and a Cambridge Instruments
in pyroelectric ceramics. This was originally demonstrated scanning electron microscope (SEM) with backscatter
for the PbZrO3–PbTiO3–PbFe1/2Nb1/2O3 (PZFNT) sys- detector. The mean grain size was determined using the
tem.13 Compositions close to PbZrO3 in the PbZrO3– linear intercept technique proposed by Wurst and Nel-
PbTiO3–PbMg1/3Nb2/3O3 (PMNZT) system have been son.20 Evaporated Cr/Au electrodes were applied for the
shown to possess excellent pyroelectric properties14,15 electrical measurements. Resistivity measurements were
and uranium has also been demonstrated to be an made on unpoled samples (to avoid confusion between
effective dopant for the control of electrical resistivity in resistive and pyroelectric currents) and under vacuum
this system.16 However, there are potential problems (to remove surface moisture). A thermoelectric heater/
with the acceptability of uranium as a dopant and there cooler was employed to maintain a constant tempera-
is therefore a need to find an effective alternative for ture during the measurement. A constant applied vol-
resistivity control. The role of uranium as a dopant has tage of 2 V was used, with a Keithley 6217 electrometer
been previously reported as being due to its multi-valent to measure the resistive current. The temperature was
donor character,13 as it possesses a valency of between raised from 15 to 65  C in steps of 10  C. The current
4+ and 6+ and substitutes on the perovskite ‘‘B’’ site was monitored for 10 min at each temperature and was
for ions with an average valency of 4+. The observed observed to follow an exponential decay: i(t)=i0 e1/t
behaviour of the electrical resistivity with dopant level where i(t) is the current at time t and i0 is the current at
(which first increases and then decreases above a doping infinite time. The values of i0 were obtained by extra-
level of ca 0.2 mol%) has been interpreted as initial polation of ln(i(t)) vs 1/t and used to compute the DC
compensation for intrinsic acceptor sites caused by loss resistivities discussed below. Unpoled dielectric proper-
of PbO, followed by the donated electrons acting as ties (1 kHz) were measured from 20 up to 300  C using
charge carriers, which hop between localised trap-sites. an HP4192A impedance analyser to obtain the Curie
Based on this observation, there is a good case for the temperatures from the maximum in the permittivity.
examination of other donor dopants for this role. Pre- Samples were poled under an electric field of 3 kV/
vious work by Takahashi17 has shown that donor mm in hot mineral oil at 120  C for 10 min, the field
dopants such as Nb (B-site) and Sb (A-site) generally being maintained until the oil temperature had cooled
act to increase the resistivity of morphotropic phase to 40  C. Prior to any measurements, they were placed
boundary lead zirconate titanate (PZT) compositions, in an oven at 50  C overnight with their electrodes
with no evidence for a significant decrease in resistivity shorted to remove any space charges that may have
at high doping levels. On the other hand, the same been introduced by the poling process. The dielectric
 R.W. Whatmore et al. / Journal of the European Ceramic Society 23 (2003) 721–728 723

properties of the poled samples were measured at 1 kHz

and 33 Hz using a GenRad 1689 RLC Digibridge. It
should be noted that measurement at a low frequency (a
few 10s Hz) is very important for any material being
considered for use in pyroelectric applications, as this is
the frequency range in which most pyroelectric devices
are operated. The pyroelectric coefficients were mea-
sured under vacuum using the same rig as that used for
the DC resistivities. Two techniques were used. The first
was the linear temperature ramp (Byer and Roundy21)
method, whereby the temperature (T) of the sample was
raised (or lowered) from 20 to 90  C at constant rate
and the pyroelectric current ip measured. The pyro-
electric coefficient p(T) was computed from p(T)=ip/
(A.dT/dt) (where A is the area of the sample). The sec-
Fig. 1. SEM image of a 1 mol% Cr-doped sample surface after pol-
ond technique was method whereby the temperature
ishing and etching. The scale bar is 4 mm.
was oscillated sinusoidally by  2  C about a mean
temperature, the pyroelectric current being monitored
continuously over this period. It is easy to show that the
pyroelectric coefficient can be computed as follows:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 2
i0m Re
pðTÞ ¼ : þ 1 þ!2 Re2 C 2 ð1Þ
T:A:! Rs

where i0m is the average of the maximum and minimum

currents, o is the angular frequency of temperature
oscillation of amplitude T, A is the electrode area, Re
is the resistance of the electrometer (this depends on the
instrument range and was taken from the electrometer Fig. 2. Grain sizes of Cr and Sb doped ceramics as functions of the
specification), and RS is the resistance of the sample, mea- doping level.
sured as described above and C its capacitance. The
advantages of this method in comparison with the Byer–
Roundy technique are that it is less susceptible to effects
due the thermally stimulated release of trapped charge.
Furthermore, it permits consideration of the leakage of
charge through the resistance represented by the sample,
which can be significant at the high levels of doping. The
agreement between the results obtained from the two
methods was excellent.

3. Results

Fig. 1 shows a typical SEM image from a ceramic

sample, as observed after polishing and etching. The Fig. 3. Curie temperatures (measured on heating) of Cr and Sb doped
grains are clearly delineated by the etch, which has also ceramics as functions of the doping level.
revealed the domain structure within the grains. The
grain sizes of the Sb and Cr-doped samples as functions Curie temperature with doping level. The hysteresis in
of the doping level are shown in Fig. 2. Average errors the transition temperature was virtually the same in all
on the grain size measurement are 10%. It can be seen samples, averaging at 4  C. It indicates a weak first-
that both dopants tend act as grain refiners, producing order nature to the transition. The Sb-doped samples,
an average grain size of around 4 mm, compared with ca on the other hand, exhibit a linear decrease in Curie
12 mm in the undoped material. The Curie temperatures temperature with doping level (z) such that
measured on heating are shown in Fig. 3. The Cr doped TC=
22z+294  C. In these specimens, the hysteresis
samples show a slight, but non-systematic reduction of was also 4  C up to 1 at.% Sb, rising to 7  C for 2 and 3
724 R.W. Whatmore et al. / Journal of the European Ceramic Society 23 (2003) 721–728

Fig. 4. Dielectric constant (a) and loss (b) of Sb-doped ceramics at 1 kHz and 33 Hz.

Fig. 5. Dielectric constant (a) and loss (b) of Cr-doped ceramics at 1 kHz and 33 Hz.

at.% Sb. This is also indicative of a first order transi-

tion, for which hysteresis would be expected to increase
as the transition temperature reduces.
Fig. 4 shows (a) the dielectric constant and (b) the loss
tangent at 1 kHz and 33 Hz of poled Sb-doped ceramics
as functions of the doping level. Fig. 5 shows the same
parameters for poled Cr-doped samples. It can be seen
from Fig. 4a that the dielectric constant minimises for
both frequencies at around 1 at.% Sb. The loss at 33Hz
also minimises at the same level of doping. The loss
tangent at 1 kHz shows a slight tendency to rise with
increasing frequency. By contrast, there is a dramatic
reduction in dielectric constant with increasing doping Fig. 6. Pyroelectric coefficients of Cr and Sb-doped ceramics.
level for the Cr-doped specimens, at both frequencies.
At 1 kHz, there is a tendency for the loss to minimise at these measurements is estimated as being between 2 and
between 0.5 and 1 at.% Cr, where it falls to < 1% at 3%. There is an interesting contrast between the Sb and
33Hz, the loss also minimises at around 0.5 at.% Cr, the Cr-doped specimens. The former shows an almost
and then rises very rapidly above this level of doping. linear increase in the pyroelectric coefficient with
There is a very strong low frequency dependence of the increasing Sb content. This is almost certainly related to
dielectric loss in the range 0.5–3 at.% Cr, probably the monotonic reduction in the Curie temperature over
caused at least to some degree by the contribution of the the same range of doping levels reported above and is
DC conductivity, which increases markedly in this range discussed further below. The Cr-doped specimens,
of doping level (see below). however, show a slight increase in pyroelectric coeffi-
Fig. 6 shows the pyroelectric coefficients at 25  C for cient up to a doping level of 0.5 at.%, followed by a
the Cr and Sb-doped ceramics. The results reported here linear reduction.
are the means of the values obtained from the two The dependence of the DC resistivities at 25  C of the
measurement methods described above. The average specimens upon doping levels are shown in Fig. 7. The
error estimated from distribution of the results from effect of the Sb doping is to increase the resistivity and
 R.W. Whatmore et al. / Journal of the European Ceramic Society 23 (2003) 721–728 725

(TC
T) so that, at constant tan, the value of FD should

be independent of temperature. At levels of Sb doping
of 1 at.% and above, the ratio p/(")1/2 varies by less than
3%, indicating that the observed increase in pyroelectric
coefficient and dielectric constant in this range are
probably determined by the reduction in TC caused by
the doping. Similarly, the increase in the 1 kHz and 33
Hz dielectric losses in this doping range are probably
caused by an increased domain wall mobility. Donor
ions such as Sb act to reduce the concentration of oxy-
gen vacancies, which will pin the domain walls, and a
Fig. 7. DC resistivities at 25  C of Cr and Sb-doped ceramics. reduction in TC will also make the domain walls more
mobile. However, the initial reduction in dielectric con-
then to hold it at that increased level, with a small stant and 33 Hz loss at doping levels up to 1 at.% Sb
reduction in resistivity as the doping level is increased cannot be explained through the reduction in TC. A
up to 3 at.% Sb. By contrast, the Cr doping first slightly reduction in the number of oxygen vacancies will reduce
increases the resistivity and then markedly reduces it. the number of acceptor centres.22 It is likely that this
initial reduction in permittivity and loss is associated
with the consequential reduction in the number of
4. Discussion mobile charge carriers in the lattice, a conclusion that is
supported by the observed increase in DC resistivity (see
There are many interesting aspects to the results Fig. 7). It would also appear from the concentration
reported here. The first aspect is the effects of the dependence of the DC resisitivity that the intrinsic level
dopants upon pyroelectric performance. This can be of oxygen vacancies is fully compensated at ca 1 at.%
measured in terms of the usual ‘‘figures-of-merit’’ Sb, and above this level the effects of TC reduction can
(FOM), defined2 as FV=p/(c’""o) and FD=p/ then be observed in that the permittivity and loss both
{c’(""otan)1/2} (where p is the pyroelectric coefficient, c’ increase. The changes in FV and FD (33 Hz) with com-
the volume specific heat, " the dielectric constant, "o the position for the Sb (and Cr) doped specimens are shown
permittivity of free space and tan the loss tangent). FV in Fig. 8(a) and (b), respectively. It can be seen that
is the relevant FOM for devices in which the device there is an increase in FV of ca 40% in going from the
noise is dominated by the readout amplifier. FD is the undoped composition to 1 at.% Sb, as the permittivity
relevant FOM when the device noise is dominated by decreases, followed by a reduction in FV above 1 at.%
the AC Johnson noise in the element. The computed Sb as the permittivity increases faster than the pyro-
values of FV and FD at 33 Hz are given in Fig. 8 (a) and electric coefficient as TC is reduced. As would be
(b), respectively. First consider the composition depen- expected from the argument presented above, there is a
dence of FV for the Sb doped specimens. A reduction in much smaller change in the value of FD with composi-
TC would be expected to produce an increase in both p tion, the reduction above 1 at.% Sb being associated
and ". As the temperature of measurement (T) approa- with the observed increase in loss. The change in resis-
ches TC (or vice versa, in this case), then Devonshire tivity as the Sb level is increased is interesting. As the
theory predicts that "=/(TC
T) and p=/(TC
T)1/2 oxygen vacancies are compensated, the resistivity
and hence FV=g(TC
T)1/2 (where ,  and g are con- increases by almost an order-of-magnitude and then
stants). By this theory, p/(")1/2 should be independent of stays at this increased level.

Fig. 8. Pyroelectric figures of merit FV and FD for Cr and Sb-doped ceramics. (Assuming that c’=2.5106 J m
3 K
1).
726 R.W. Whatmore et al. / Journal of the European Ceramic Society 23 (2003) 721–728

Electronic conduction in the perovskites in this tem- Table 1

perature range is entirely determined by carrier hopping Variation of activation energy for hopping conduction with doping
level for Sb-doped ceramics
between trapping sites.13,22 Donors or acceptors are not
fully ionised, but holes or electrons hop between loca- At.% Sb Activation energy Ea (eV)
lised traps. The fact that the resistivity is reasonably
0 0.62
independent of the Sb concentration above 1 at.% con- 0.5 0.55
firms the hypothesis that the ‘‘donor’’ Sb ions are not 1 0.63
ionised, the electrons associated with these dopant sites 2 0.64
are trapped, and that therefore we do not see a change 3 0.52
to electron-mediated hopping conduction as the Sb ion
concentration is increased. Conductivity remains hole-
mediated. The conductivity (
o) of a ceramic dominated conductivity is only weakly dependent upon the Sb
by this form of hopping conduction is given13 by: doping level above 1 at.% is presumably because the
  concentration of acceptor centres does not change much

o ¼ Aexp
az
1=3
Ea =kT ð2Þ above this doping level, under the synthetic conditions
used for the ceramics and so the average distance for
where A and  are constants, a is the lattice parameter, z hole hopping between the acceptor traps is also
is the atomic fraction of trap sites, Ea the activation unchanged.
energy for the hopping process, T the absolute tempera- By contrast with Sb, Cr would be expected to take a
ture and k is Boltzmann’s constant. The ‘‘exp(
az
1/3)’’ valency of 3+ (it is added as Cr2O3) and thus might be
part of this expression is determined by the average expected to sit on the B-site as an acceptor. There is the
hopping distance that a carrier has to traverse between possibility of Cr existing as Cr5+23 or even Cr6+, but
traps and the way it affects the probability of hopping. these would require very strongly oxidising conditions.
Fig. 9 shows a plot of ln(
) vs 1/T for the Sb doped If we assume that it is present as Cr3+24 and is acting
specimens. The activation energies determined from the as an acceptor, we can understand the effects on the
linear portions of these curves (i.e. above 35  C) are dielectric properties (Fig. 5) as being due firstly to an
given in Table 1. The Ea does not vary much across the increase in oxygen vacancies, which will tend to increase
series, confirming that the conduction mechanism does the pinning of the domain walls and thus to reduce the
not change across the composition series, and giving an dielectric constant and loss up to a doping level of 1
average value of Ea=0.59  0.05 eV for hole-hopping at.%. The loss is then increased (particularly dramati-
conduction. This value is not too dissimilar from the cally at 33 Hz) as the DC conductivity is increased. The
value of 0.78 eV for U-doped PZFNTU ceramics at low pyroelectric coefficient (Fig. 6) is also decreased above a
levels of U-doping, where conductivity is still deter- level of doping of 1 at.% Cr. This is harder to under-
mined by the intrinsic acceptor level. The fact that the stand and may not be understood (as for Sb doping) as
an intrinsic ferroelectric effect (as the TC is unchanged).
It may be due to the increase in DC conductivity
affecting the efficiency of poling, but this needs further
work to understand more fully. The consequent effects
upon FV and FD of the changes in the pyroelectric and
dielectric properties are shown in Fig. 8 (a) and (b)
respectively. FV is increased at low doping levels as " is
reduced, but then reduces at higher doping levels as p is
reduced. FD is increased dramatically at low doping
levels as " and tan are reduced, but is then compro-
mised at the higher doping levels as p reduces and tand
increases.
The decrease in the DC resistivity (see Fig. 7) with
increasing Cr level above 0.2 at.% can be understood in
terms of Eq. (2). Fig. 10 shows a plot of ln(
o) vs z
1/3
(
o=DC conductivity) for the Cr-doped ceramics at
25  C. Here, z is taken as the doping level for the Cr,
which assumes that the Cr acceptor sites act as the hole
traps. The line is a best fit to the data and gives =0.38
Å
1 (using a lattice parameter determined by powder
Fig. 9. Loge(DC resistivity) vs 1/T for the Sb-doped ceramics. The X-ray diffraction of 4.125 Å). Similar results are
legend indicates the doping level for each specimen in at.%. obtained at 65  C. This value of  for hole-hopping
 R.W. Whatmore et al. / Journal of the European Ceramic Society 23 (2003) 721–728 727

Table 2
Variation of activation energy for hopping conduction with doping
level for Cr-doped ceramics

At.% Cr Activation energy Ea (eV)

0 0.62
0.2 0.59
0.5 0.31
1 0.40
2 0.42
3 0.38

Fig. 10. Variation of loge(DC conductivity) with z
1/3 for Cr-doped

ceramics.
energy for hopping (average 0.38  0.03 eV) coupled
with the linear ln(
o) vs z
1/3 dependence implies that
conduction between Cr-sites compares with values of the hole traps are now the Cr3+ sites. The Ea measured
=0.66 Å
1 determined for electron hopping conduc- here is very similar to the values of Ea=0.37  0.01 eV
tion between U-sites in U-doped PZFNT13 and =0.63 determined for U-doped PZFNT13 and 0.28  0.02 eV
Å
1 in U-doped PMNZT.14 The variation of resistivity for U-doped PMNZT14 ceramics. In these cases, the
with temperature for the Cr-doped ceramics is shown in trapping sites are thought to be for electrons.
Fig. 11 and the activation energies for conduction in
Table 2. It is clear that there is a significant change in
activation energy in going from the 0 and 0.2 at.% Cr 5. Conclusions
samples to the 0 samples with 5 at.% Cr and higher. For
the first two, the Ea values are very similar to the values The electrical properties of Sb and Cr-doped
obtained with all the Sb doped samples. It can also be Pb(Mg1/3Nb2/3)0.025(Zr0.825Ti0.175)0.975O3 ceramics have
seen from the temperature plots that these two samples been studied in detail. Both dopants act as grain refi-
have very similar resistivities across the range of tem- ners. It has been shown that Sb acts as a donor dopant,
peratures explored. These results imply that the sites for linearly reducing the Curie temperature and increasing
the hole traps are the same in both these samples and in the pyroelectric coefficient and the dielectric constant.
the Sb-doped ceramics. Presumably at the 0.2 at.% At low levels of Sb doping, the dielectric constant and
doping level there are insufficient Cr3+ acceptor sites to loss are reduced (at both 33 and 100 Hz). The combi-
act as a significant trap for the holes in comparison with nation of these electrical properties produces 33 Hz
the intrinsic hole trapping sites. For the other samples pyroelectric FOM’s as follows: FV peaks at 3.810
2 m2
with higher Cr doping levels, the lower activation C
1 and FD peaks at 1.210
5 Pa
1/2. The dopant
concentration dependent behaviour of the FOM and the
electrical resistivity have been explained in terms of the
changes in TC and the behaviour of the Sb dopant as a
donor ion which reduces oxygen vacancy concentration,
but which does not contribute electrons to the conduc-
tion process. Cr acts as an acceptor dopant, having little
effect on the Curie temperature, but reducing the dielec-
tric constant and loss and markedly reducing the pyro-
electric coefficient. Above 0.5 at.% Cr, the resistivity
reduces rapidly. The pyroelectric FOM calculations give:
FV peaking at 3.610
2 m2 C
1 and FD at 1.910
5 Pa
1/
2
. The behaviour of Cr as a dopant has been explained in
terms of it acting as an acceptor dopant with conduction
mediated by the hopping of holes between Cr3+ sites.

Acknowledgements

The financial support of EPSRC through grant num-

ber GR/L91436/01 is gratefully acknowledged. R.W.W.
Fig. 11. Loge(DC resistivity) vs 1/T for the Cr-doped ceramics. The gratefully acknowledges the financial support of the
legend indicates the doping level for each specimen in at.%. Royal Academy of Engineering.
728 R.W. Whatmore et al. / Journal of the European Ceramic Society 23 (2003) 721–728

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