Sensors and Actuators B 114 (2006) 507–512

An ozone monitoring instrument based on the tungsten

trioxide (WO3) semiconductor
S.R. Utembe a,∗ , G.M. Hansford a , M.G. Sanderson b , R.A. Freshwater a ,
K.F.E. Pratt c , D.E. Williams d , R.A. Cox a , R.L. Jones a
a Chemistry Department, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK
b Met Office, Fitzroy Road, Exeter EX13PB, UK
c Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK
d Unipath Ltd., Priory Business Park, Bedford MK44 3UP, UK

Received 1 February 2005; received in revised form 11 April 2005; accepted 11 April 2005
Available online 10 August 2005

Abstract

Novel sensors based on tungsten trioxide (WO3 ) semiconductors have been found to hold much promise as a cheaper alternative for ozone
monitoring. The sensitivity of the metal oxide to ozone is owed to the presence of surface oxygen vacancies. The filling of oxygen vacancies
by the decomposing ozone traps free charge carriers with consequent measurable increase in resistance. A Langmuir-type model simulating
the fundamental surface reactions has been found to reproduce the measured sensor response. Using a temperature-cycling technique in which
the temperature of the sensor is alternated between 600 and 530 ◦ C representing scrubbing and measurement resistances, respectively, ozone
measurements have been obtained from several urban sites. Results from eight sensors show that the sensors have adequate sensitivity and
response time with measurements comparable to ozone measured by UV absorption spectrometer (r.m.s. of variances up to 7 ppbv). Problems
of apparent changes in sensor sensitivity in the course of field measurements have been explained by inadequate ‘burn-in’ period prior to
calibration and field deployment. The sensors should be run in ambient conditions for about a week before calibration.
© 2005 Elsevier B.V. All rights reserved.

Keywords: WO3 ; Ozone; Temperature cycling; Pre-measurement calibration; Post-measurement calibration

1. Introduction sensor based on the WO3 semiconductor has been found

The monitoring of ground-based ozone is normally done
by using spectroscopic methods. While these techniques have
been found to be stable and reliable, their applicability is
somewhat limited by the fact that the instruments are usually
both expensive and bulky. There is now increased interest
in alternative cheaper and more portable instruments [1]. In
this paper, we present results from a portable and lightweight
ozone monitoring instrument which utilises changes in the
well established electronic properties of WO3 [2]. An ozone
to exhibit excellent sensitivity and selectivity [3]. Recent
research in the use of tungstic trioxide semiconductor has
focused on characterising its detailed response to the pres-
ence of ozone [4]. In this paper, we present a comparison of
the performance of the WO3 sensor instrument with a con-
ventional UV technique.
2. Characterisation and understanding of the sensor
response

∗
There has been good progress in establishing whether
Corresponding author at: Department of Environmental Science and
Technology, Imperial College, Silwood Park, Ascot, Berkshire SL5 7PY,
the response of the WO3 sensor can be characterised
UK. Tel.: +44 207 5942466; fax: +44 207 5942308. quantitatively in terms of fundamental reactions at the
E-mail address: s.utembe@imperial.ac.uk (S.R. Utembe). gas/semiconductor interface. The basic model that emerges

0925-4005/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2005.04.049
508 S.R. Utembe et al. / Sensors and Actuators B 114 (2006) 507–512

is that the conductivity is controlled by the (temperature-

dependent) conductivity of the bulk WO3 , but also by oxygen
vacancies which can form at the interface. Vacancies are gen-
erated thermally (1) and can be destroyed by reaction with
both O3 and O2 (via (2) and (3), respectively) as shown by
reactions below, where V represents a vacancy:
k−1
Oo −→V + 0.5O2
k1
V + O3 −→Oo + O2
k2
V + O2 −→Oo + 0.5O2
Under steady state conditions (constant O2 and O3 ), the
coverage of surface vacancies can be represented using the
Langmuir isotherm [5]. However of more relevance to the
detection of ambient O3 concentrations is the time-dependent
sensor response. Considering only O3 and assuming zero
initial coverage, casting the Langmuir isotherm in a time
dependent manner leads to the following generic expression
for surface vacancy coverage, θv (t), following the introduc-
tion of an O3 concentration [O3 ]:
k−1 + k1 [O3 ]e−(k−1 +k1 [O3 ])t
θv (t) =
k−1 + k1 [O3 ]
The time dependent resistance of the device is then given
by:
Ω(t) = (Ci + 2θv (t))−1
where Ci is the (temperature dependent) intrinsic carrier con-
centration. This formalism can be readily expanded to include
the effects of O2 by inclusion of additional terms of the form
k2 [O2 ] in Eq. (4).
In practice, to reproduce in detail the observed response,
which shows a slow response superposed on a more rapid
one (see Fig. 1), it is necessary to include two distinct rate
constants. The effect has its origin in the effects of sensor
(1)
(2)
(3)
Fig. 2. Comparison of model (solid lines) and observed sensor response to
43 ppb ozone at operating temperatures of 500 and 530 ◦ C shows differ-
ent sensitivities and sensor responses. The observed sensor resistance is a
response following a switch in temperature from 600 ◦ C (scrubbing phase)
to the operating (measurement phase) temperatures of 500 and 530 ◦ C while
exposing the sensors to air samples of constant ozone concentrations.
microstructure on the response characteristics: the interior of
(4) the tungsten oxide crystallites that comprise the sensor acts as
a gas-insensitive shunt that damps the response [6]. In Fig. 1
is shown a comparison of the model (solid) with measure-
ments (symbols) using a WO3 sensor operated at 530 ◦ C for
(5) O3 concentrations between 13 and 68 ppbv, representative of
typical surface ozone concentrations, using each rate constant
k1 , k−1 and k3 as a global adjustable parameter independent
of O3 concentration.
The model reproduces well the effects of different O3 con-
centrations measured at a sensor operating temperature of
530 ◦ C. Lowering the operating temperature (for example to
500 ◦ C, see Figs. 2 and 3) has the effect of increasing sensitiv-
ity although the response time is now too slow (∼300 s). The
reasons for the apparent changes in sensitivity and response
time with operating temperature are fully explained in [3]

Fig. 1. Comparison of model and observed sensor response at 530 ◦ C. Model

is represented by solid lines (see text for details). The observed sensor resis-
tance is a response following a switch in temperature from 600 ◦ C (scrubbing
phase) to the operating (measurement phase) temperature of 530 ◦ C while Fig. 3. Sensor resistance (at different operating temperatures) against ozone
exposing the sensors to air samples of constant ozone concentrations. shows increased sensitivity for the lower temperature of 500 ◦ C.
 S.R. Utembe et al. / Sensors and Actuators B 114 (2006) 507–512
and [4]. These measurements allowed a WO3 band gap of
−200 kJ/mol to be determined, comparable to literature val-
ues (264 kJ/mol, see [7]).
3. Instrument design
The design goal was to develop a small, lightweight and
weatherproof instrument capable of making frequent ground-
level measurements with minimal regular maintenance. The
instrument consists of an air sampling line and control elec-
tronics housed in a tough plastic/aluminium box, conforming
to the IP66 protection standard and to EMC regulations [8].
Each instrument weighs approximately 1.5 kg and has dimen-
sions 25 cm × 18 cm × 9 cm. Two ozone sensors are used
within each instrument to improve reliability.
The flow line was made up of Teflon tubing and nylon
fittings to minimise the loss of ozone on exposed surfaces,
and an inverted funnel was attached to the inlet to prevent
ingress of rain droplets. Air was drawn through the line by
a miniature rotary pump (ASF Thomas model G12/02-4E)
at a rate of approximately 3 lpm. The flow was split in two
and passed over the two sensors, each mounted in a Teflon
chamber, before recombining and flowing over a thermistor
and capacitative humidity sensor, also mounted in a Teflon
housing. The temperature and humidity measurements were
made when the sensor heaters were off to minimise interfer-
ence. The pump was positioned downstream of the sensors,
and the exhaust air was vented on the opposite side of the box
to the inlet.
The details of the design of the ozone sensor control elec-
tronics are very similar to those published before [9]. One
difference is that potentiometers were used in the Wheatstone
bridge. The temperature sensitivity of these components is
less important for ground-based instruments, which experi-
ence much smaller temperature ranges than the balloon-borne
devices. Signal voltages were digitised with a Burr-Brown
ADS7825 a/d-convertor, and a TDS2020 Triangle Digital
Services embedded computer was used for data logging and
control. For a typical logging cycle in which one measure-
ment is made every 10 min, there is sufficient onboard flash
memory for unattended operation up to one month. In the
event of a power failure, the instrument will automatically
restart when power is restored.
3.1. The WO3 sensor
The sensing element (City Technology Ltd., UK) con-
sists of a WO3 film mounted on one side of a 2 mm × 2 mm,
250 ␮m thick alumina substrate. A platinum heater and gold
electrode are screen-printed onto the substrate. The platinum
element is used for heating the sensor to a specified elec-
tronically controlled temperature since the sensor operates
at temperatures above ambient conditions. A picture of the
WO3 sensing element deposited on a gold electrode structure
is shown in Fig. 4.
509
Fig. 4. Picture of the sensing element (WO3 ) deposited on a gold electrode
structure (used by permission of City Technology Ltd., UK).
3.2. Temperature cycling
The two-temperature mode of operation has been found
to be the best way of operating the sensor. In this mode, the
operating temperature of the sensor is cycled between a high
temperature of 600 ◦ C and a low temperature of 530 ◦ C repre-
senting ‘scrubbing’ and ‘measurement’ phases, respectively.
During the high temperature phase (at which the sensitivity
of the sensor to ozone is insignificant), the surface of the sen-
sor is ‘reset’ in readiness for the subsequent low temperature
phase during which the ozone measurement is conducted.
The observed sensor resistance (shown in Figs. 1 and 2) is
a response following a switch in temperature from 600 ◦ C
(scrubbing phase) to the operating (measurement phase) tem-
peratures of 500 ◦ C or 530 ◦ C while exposing the sensors to
air samples of constant ozone concentrations.
3.3. Calibration and use of the WO3 sensor
The calibration procedure for the sensors has been done
by flowing given constant levels of ozone over the sensors
and recording the resistance at 2 min in the low temperature
measurement phase. The ozone used to calibrate the sensors
was generated by a Dasibi Multi-Gas Calibrator (series 5008)
manufactured by Dasibi Environmental Corporation Ltd. The
calibration was repeated three times for each ozone concen-
tration.
4. Comparison of ozone measured by WO3 sensor
and UV absorption spectrometer
The WO3 sensor has now been used by a Cambridge Uni-
versity (UK) research group in a wide range of studies in the
urban planetary boundary layer.
Fig. 5 is a correlation plot showing typical performance of
the WO3 sensor compared to a commercial UV absorption
spectrometer operated in such a mode. The measurements
were made for over 30 days at a site in Sandwell (UK).
The level of agreement obtained, with an r.m.s. deviation of
around 5 ppbv, is excellent, illustrating clearly the potential
of the WO3 sensor methodology.
510 S.R. Utembe et al. / Sensors and Actuators B 114 (2006) 507–512
Fig. 5. Comparison of performance of a WO3 sensor with UV absorption
spectrometer for ozone measurements that were collected for a period of
over 30 days in urban conditions at Sandwell (UK).
Fig. 6 shows the corresponding time series plotted along
with the differences in ozone measured by the two techniques.
Clearly, the WO3 sensor is responding well to the ozone struc-
ture caused by diurnal variations.
A more general assessment of the WO3 sensor is shown
in a correlation plot of data collected from eight sensors from
various urban sites (Fig. 7). The data is over a 30-day period
and is taken from a NERC funded field campaign held at
several urban sites in the West Midlands (central UK). Given
that the ozone measurements were taken for a period of over
30 days for each sensor, this level of correlation is acceptable
(r.m.s. of the ozone differences is around 7 ppbv). Neverthe-
less, the relatively high degree of scatter in the correlation plot
can be improved. One of the causes of the high scatter is the
apparent change in sensor sensitivity (for some sensors) with
time and drifting sensor scrubbing-phase resistance. Fig. 8
shows differences in sensor calibration curves for two WO3
sensors, which were obtained immediately before and after
a 30-day measurement period. Why one sensor should be
Fig. 6. Time series of ozone measured by a WO3 sensor and an UV absorp-
tion spectrometer in urban conditions at Sandwell (UK).
Fig. 7. Comparison of performance of eight WO3 sensors with UV absorp-
tion spectrometer for measurements that were collected for a period of over
30 days in urban conditions in the West Midlands (Central UK).
better than another is not obvious, but it may be caused by
some non-uniformity in the sensor production process. These
sensitivity and scrubbing-phase resistance changes can be
corrected for by conducting another sensor calibration after
the field measurement period.
4.1. Pre-measurement and post-measurement
calibration concept
In this concept, an additional calibration is conducted after
a measurement campaign. This data can then be used to anal-
yse the measurements. Fig. 9 shows a time series of ozone
measured by one sensor but analysed with both the pre- and
post-measurement calibration data.
Obviously, for the first few days, the pre-measurement
calibration data gives better ozone comparison (with ozone
measured by a UV absorption spectrometer) than the post-
measurement calibration data. After about a week of mea-
surements, the sensitivity of the sensor has changed so that
Fig. 8. Calibration curves from WO3 sensor calibrations conducted before
and after a 30-day measurement period shows changing sensor sensitivity.
 S.R. Utembe et al. / Sensors and Actuators B 114 (2006) 507–512
Fig. 9. Time series of WO3 sensor ozone measurements calculated by cal-
ibrations conducted before (solid thick line) and after (solid thin line) a 30
day field measurement campaign.
after this period, the calibration data that gives the best results
is the one that is done after the measurement period.
This observation has been found to be the case for most
of the sensors used in this study. Thus, it has been neces-
sary to use only the post-measurement calibration data to
calculate the ozone concentrations from the measured sensor
resistances.
The fact that the sensor sensitivity seems to change so soon
after the start of the field measurements seems to suggest that
it is necessary to burn-in the sensors before commencement of
the field measurements, if the post-measurement calibration
is to be used. We recommend about a week of burning-in as
a minimum. During this period, the sensors should be run in
ambient ozone concentrations before calibration.
5. Conclusion
An ozone instrument based on the WO3 sensor is showing
a lot of potential as a cost-effective alternative to conventional
ozone measuring instruments. Based on the fundamental
reactions occurring at the surface of the oxide, a Langmuir-
type model is able to characterise the response of the sensor
to changes in ozone concentrations.
For the first time, urban ozone measurements made by a
WO3 solid-state sensor have been compared with those mea-
sured by a conventional UV absorption instrument. Results
from over 30 days of data obtained from eight WO3 sensors
have shown good correlation with ozone measurements from
a UV absorption spectrometer, with an r.m.s. of the variance
of about 7 ppbv. The results have shown that the performance
of the sensor depends on the sensor behaviour in the course
of the measurement period. Apparent changes in sensor sen-
sitivity can be accounted for by calibrating the sensors after
approximately 1 week of ‘burn-in’ in ambient ozone condi-
tions. Alternatively, it has been found that conducting another
calibration immediately after a field measurement campaign
511
helps to correct for any changes in sensitivity and scrubbing-
phase resistance.
Acknowledgements
The authors gratefully acknowledge the support of Bob
Appleby of Birmingham (UK) City Council Environmental
Services for his helpful information on measurement sites
and UV absorption ozone measurements, and the UK Nat-
ural Environment Research Council (NERC) for financial
support.
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Biographies
Steven Robert Utembe: Steven Utembe’s honours degree in chemistry
was awarded at Chancellor College, University of Malawi in 1996. His
PhD, which was obtained in 2000 at the University of Cambridge involved
both tropospheric modelling studies and measurement studies of urban
ozone concentrations using a novel WO3 sensor. His major interests are
in modelling studies of tropospheric chemistry. He is currently conducting
research work in photochemical pollution modelling studies at Imperial
College London.
Graeme Hansford: Graeme Hansford obtained a BA degree in natu-
ral sciences (chemistry), and a PhD in infrared laser spectroscopy at
the University of Cambridge, UK. Currently working at the Centre for
Atmospheric Science, Chemistry Department, University of Cambridge,
research interests include instrumentation for balloon- or aircraft-borne
operation, particularly for the measurement of ozone and water vapour.
512 S.R. Utembe et al. / Sensors and Actuators B 114 (2006) 507–512
Michael Sanderson: Michael Sanderson, Bsc(Hons) in chemistry,
awarded 1991, and DPhil in chemistry, awarded 1995, both from the
University of York. He is currently at the Met Office. His interests are
how trace gases, particularly surface ozone levels, are affected by climate
change, and atmosphere–vegetation interactions.
Ray Freshwater: Ray Freshwater obtained his BSc with honours in
physics and electronics at Brunel University in1986. He is currently
employed as a technical officer in the Department of chemistry at the
University of Cambridge. His current field of interest is in aircraft and
balloon borne atmospheric instrumentation for ozone and water vapour
measurements.
Keith Pratt: Keith Pratt’s first degree was in chemistry with computer
based technology, at the University of Warwick. His PhD in electro-
chemistry was awarded at the University of Southampton in 1994. He
subsequently worked on gas sensor R&D, both in industry and academia,
for 10 years. He is currently Principal Scientist at City Technology Ltd.
working on novel gas sensor technologies.
David Edward Williams: David Williams is currently chief scientist
at Inverness Medical Innovations, based at Unipath Ltd., Bedford, UK.
Previously (1991–2002) he was professor of physical chemistry and head
of department of chemistry at University College London. He started
his career in chemical sensor research and development in 1981 at the
Harwell Laboratory of the UK Atomic Energy Authority.
Richard Anthony Cox: adjunct reader in atmospheric chemistry, Univer-
sity of Cambridge. Dr. R.A. Cox, has had 36 years research experience
in air pollution research, firstly at the UKAEA Harwell laboratory and
since 1995 at the department of chemistry. During that time Dr. Cox
has made many pioneering laboratory studies of the kinetics and mech-
anisms of reactions involved in stratospheric and tropospheric chemistry,
and measurements of ozone and other atmospheric pollutants. Dr. Cox
has acted as co-ordinator of the CEC Combustion Kinetics Programme
between 1988 and 1990, and several EC projects in the atmospheric
chemistry area, including the current fifth Framework project: ‘Tropo-
spheric Halogens—Effect On Ozone—(THALOZ)’. Since joining Cam-
bridge University nine years ago he established new facilities for studies
of heterogeneous atmospheric processes and a website containing the
IUPAC evaluation of kinetic data for atmospheric chemistry.
Roderic Lewis Jones: reader in atmospheric science, department of
chemistry, University of Cambridge. Dr. R.L. Jones has over 25 years
experience in atmospheric science research. He obtained his D Phil at the
(then) department of atmospheric physics, Oxford for studies of the struc-
ture and composition of the stratosphere from satellites, which provided
some of the early insights on atmospheric circulation and the strato-
spheric water vapour budget. In 1984 he moved to the UK Meteorological
Office where he became involved with observational studies of tropopheric
composition using aircraft and the pioneering airborne investigations of
stratospheric ozone loss in polar regions. In 1990 he took up his cur-
rent post where he has been involved with a wide range of observational
studies of atmospheric composition and the development of a range of
measurement methods including lidars, cavity ringdown spectroscopy and
solid state gas sensors.