J O U R N A L O F M AT E R I A L S S C I E N C E : M AT E R I A L S I N E L E C T RO N I C S 1 1 ( 2 0 0 0 ) 3 6 9 ± 3 7 2
A thin-®lm tin-oxide carbon monoxide sensor for
exhaust gas analysis
E. W. WILLIAMS, N. TOMLINSON, M. T. CHENEY, A. G. KEELING
Physics Department, Keele University, Keele, Staffordshire, ST5 5BG, UK
A sputtered thin-®lm tin oxide:platinum sensor operating at 125  C was successfully used to
detect carbon monoxide gas from a car exhaust. Detection in the range 0.2 to 8% was
demonstrated. Although ohmic contacts to the sensor were achieved, preliminary life tests
showed that corrosion occurs in humid atmospheres. An alternative contact material is
suggested. Further work on the change in response with thickness is required and this should
include porosity studies.
1. Introduction
There are three requirements for carbon monoxide (CO)
sensors for four-wheel petrol-driven cars. The ®rst, and
most urgent, is a requirement for a stand alone
reasonably accurate CO tester for MOT (UK Ministry
of Transport), testing of exhaust emissions. The second is
a CO sensor mounted in the car exhaust to warn the driver
that his catalytic convertor is no longer working. The
third is a CO sensor on the dashboard which warns the
driver and passengers that the CO pollution level in a
certain city is reaching the danger level.
This paper concentrates on research on a CO sensor
that was designed for eventual use in MOT testing. There
are mainly two gases that are measured for this test and
these are CO and hydrocarbons (amount of unburnt fuel
measured in parts per million ( p.p.m.)). Although there
are other gases produced by the process of combustion
such as carbon dioxide, nitrous dioxide and water vapor,
it is CO which is the most hazardous to human health as
Table I shows. The MOT exhaust emission requirements
are shown in Table II.
In Fig. 1 the ratio of 15:1 air petrol is called the
stoichiometric ratio or stoichiometric point because this
produces the most ef®cient combustion. Below this point
the ratio is rich and above this it is lean. Fig. 1 clearly
shows that a lean burn car has less CO but more
hydrocarbous (HC). However, because of different
cylinder head designs this stoichiometric ratio produces
different percentages of CO for different cars.
As Fig. 1 shows, the amount of CO in the car exhaust is
inversely proportional to the air:fuel ratio. Too little
oxygen would cause too rich a mixture so giving a high
level of CO. A very low level of CO in the exhaust would
indicate that there is too much oxygen in the air:fuel
ratio. Where poor combustion exists in a cylinder the CO
level will be reduced so the total CO level in the exhaust
will be reduced.
This paper reports on a thin ®lm platinum-doped tin
oxide sensor that was tested with CO exhaust emissions
of 0 to 8% (volume). The sensor preparation is brie¯y
0957±4522 # 2000 Kluwer Academic Publishers
described since a previous paper on the conduction
processes in these ®lms gave full details [1]. For exhaust
testing the sensor was operated at 125  C to avoid
condensation.
2. Sensor preparation
Platinum-doped tin oxide ®lms were prepared by r.f.
magnetron sputtering using a CVC 601 deposition
system. The sputtering power was maintained at 50 Ws
and the tin oxide ®lms were deposited at room
temperature onto Corning 7059 slides. The tin oxide
layers were deposited using a mixture of argon and
oxygen in the ratio 3:1 at a pressure of approximately
1 Pa (8 mTorr). Sputtering took place for periods of 1 to
3 h, yielding a tin oxide ®lm thickness of approximately
100 nm to 300 nm as measured using a Planar Surfometer
SF200 stylus instrument.
Evaporated copper contacts were made using a
Speedivac coating unit 12E6/1126. A mask was used to
produce two contacts. A contact thickness of 150 nm was
chosen in the light of previous experience.
3. Sensor and car testing
Current±voltage tests were carried out with the applied
voltage varying from 1 to 100 V. For the ®ve samples
prepared the slope of the log±log plot was 1 + 0 1 and
showed perfect linearity. This con®rmed that the contacts
were ohmic.
Ten cars were tested with varying engine size and age
to obtain a view of the range of parameters needed for the
sensors. Table III shows details of the exhaust gas
experiments on the cars. A summary of the range of the
measurements is given below:
(a) The exhaust gas velocity range: 1.3 to 3.1 ms ÿ 1
(b) The temperature 53 to 64  C
(c) Humidity 87 to 97% RH
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T A B L E I The effects of carbon monoxide on the human body (American Conference of Government and Industrial Hygienists, 1990).

CO concentration ( p.p.m.) Description

100 (0.01%) Slight headache within 2±3 h.

400 (0.04%) Headache within 1±2 h.
800 (0.08%) Dizziness within 45 min, unconscious within 2 h.
1600 (0.16%) Headache, dizziness within 20 min, death in under 2 h.
3200 (0.32%) Headache, dizziness within 10 min, death in under 30 min.
6400 (0.64%) Headache, dizziness within 2 min, death in under 15 min.
12800 (1.28%) Death in under 3 min, the output of a good car!

Figure 1 Diagram showing how the exhaust gas content varies with Figure 2 The sensor enclosure, exhaust probe and pump arrangement
air:fuel ratio. for the carbon monoxide feasibility trial.

As a result of these tests on the exhaust gas it was
decided to operate the sensor at 125  C and take special
precautions to drain off water.
Fig. 2 shows how the sensor sampled the exhaust gases
The sample probe was kept in place in the exhaust with
three springs welded onto the end of the tube. The probe
was connected to the input of the pulse pump from a
``Gunsons Gastester''. The pulse pump removes 90% of
the water from the exhaust gas into a water drain. In
addition, the pump has a vibrating diaphragm which
steadies the air¯ow.
The output from the pump goes through a darkened
tube to the darkened sample enclosure. The sensor is
angled at 45 , upside down, and heated to 125  C to
ensure that any condensed water vapor passing through
the pulse pump does not condense onto the sensor's
surface. Baf¯es in the enclosure ensure that no light falls
onto the sensor since it responds to visible and UV light.

T A B L E I I MOT exhaust emission requirements

Year of manufacture Speci®cations

Until 1975 Excessive smoke

1975 to 1983 Less than 6% CO (volume)
1983 to 1992 Less than 4.5% CO (volume)
1992 on Less than 2% CO (volume)
1975 on 1200 p.p.m. hydrocarbons (HC)

T A B L E I I I Summary of car exhaust measurements of velocity, temperature and humidity

Test car Year cc Vel (m s ÿ 1) Temp (%) HUM(%RH)

1 1983 1300 3.1 57 87

2 1984 1600 1.8 63 92
3 1987 1400 1.3 60 93
4 1987 1300 2.6 53 89
5 1986 1600 1.7 57 94
6 1987 2000 1.4 64 96
7 1986 1300 2.4 54 91
8 1983 1000 2.8 57 92
9 1992 1000 (cat) 2.7 54 97
10 1983 1300 2.6 56 93

370

Figure 3 Circuit diagram of the Keele heater temperature controller.
Figure 4 The thin-®lm sensor carbon monoxide response for sample B
with a thickness of 200 nm.
Figure 5 The thin-®lm sensor carbon monoxide response for sample C
with a thickness of 300 nm.
To heat the sensor, a sputtered tungsten heater with a
resistence of 35 O was used in the circuit shown in Fig. 3.
The thermocouple controls the point at which the power
transister is turned on to control the heater by using a
comparator for ®re control. The warm-up time was
15 min and the temperature control was such that the
temperature was 125.2 + 0.3  C.
4. Carbon monoxide response
The exhaust experiments were all carried out at Stoke-
on-Trent College in the vehicles technology workshop.
The carbon monoxide concentration was measured with
a BEAR MOT approved 4-way gas analyzer which has an
accuracy of + 0.01%.
Fig. 4 shows the CO response of a 200 nm thick thin-
®lm tin oxide.platinum sensor. This clearly shows
saturation occuring at 3% CO and above. The starting
resistance of 9 G O was very high.
Increasing the thickness to 300 nm had a dramatic
effect on the response, as Fig. 5 shows. No saturation is
observed for concentration up to 8% CO. The reduction
in starting resistance to 2 G O is also encouraging.
However, the response is non-linear and slows at 3% CO
and above.
5. Discussion
The feasibility of detecting CO emission from car
exhausts has been demonstrated from 0.2 to
8.0 + 0.1% using a thin-®lm sputtered tin oxide:
platinum detector.
The reaction mechanism is not fully understood. A
number of forms of oxygen may be present during the
CO adsorption process onto the thin-®lm tin oxide
surface. The following equations show three of the
oxygen forms which are thought to contribute to CO
detection [2]:
e7 ‡ O 2 , O 7
2
e7 ‡ O 7
2 ?2O
7
R ‡ O7
2 ?RO2 ‡ e
7
R ‡ O7 ?RO ‡ e7
The interaction of the reducing agent with previously
absorbed oxygen is favored to explain the sensing
mechanisms of tin oxide gas sensors [3, 4]. The electron
that is generated reduces the resistance and the results in
Figs 4 and 5 are explained to some extent by this since
the resistance falls with increasing CO concentration.
Humidity effects were almost certainly eliminated by
operating the sensor at 125  C in an inverted position and
with a water drain in the pump.
Light sensitivity was avoided by the special design of
the sample enclosure and the darkening of the input tube.
Interferences due to hydrocarbons or oxides of
nitrogen were not checked but recent experience with a
thick-®lm sensor [5] indicates that these should not be a
problem.
The dramatic change in the CO detection character-
istics in Figs 4 and 5 is probably due to a change in
surface area with thickness. This change is probably due
to an increase in the porosity with thickness. Obviously,
371
more work on the thickness dependence is required and References
the porosity should also be measured using a standard 1. A. K. HASSAN, R. D. GOULD, A. G. KEELING and E . W.
WILLIAMS, J. Mater. Sci. Mater. Electron. 5 (1994) 310.
liquid intake method backed up by scanning electron
2. S . R . M O R R I S O N , Sens. Actuators 12 (1987) 425.
microscopy studies. 3. S . R . M O R R I S O N , ibid. 2 (1982) 329.
Finally, the use of copper contacts, even though they 4. P. G . H A R R I S O N and M . J . W I L L E T T , Nature 332 (1988) 337.
are ohmic, is not ideal. Preliminary life tests on the ®rst 5. E . W. W I L L I A M S and A . G . K E E L I N G (to be published).
®ve sensors that were made has shown that humidity
causes corrosion and the eventual breakdown of the Received 17 May 1999
contacts. Screen-printed platinum contacts, on the other and accepted 8 February 2000
hand, do not corrode and a one year life has already been
demonstrated with thick ®lm sensors [5].

Acknowledgment
Thanks are due to Stoke College for the use of their car
test facilities and gas analyzers.

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