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Semicond. Sci. Technol. 4 (1989) 351-359. Printed in the UK

W M Searst, K Colbowt and Franco ConsadoriS

t Energy Research Institute, Physics Department, Simon Fraser University,
Burnaby, BC, Canada V5A IS6
*V6E
Halitec Industries, 400-1 177 West Hastings Street, Vancouver, BC, Canada
2K3

Received 14 November 1988, accepted for publication 6 January 1989

Abstract. Theresponse,measured as conductance, of thermally cycled tin

oxide gassensorswas studied todetermine the potential inherent in this
technique with respect to increased selectivity and sensitivity. It was found that
t h e range of cycle temperature as well as the period of t h e cycle had a critical
effect on the amount of information that could be extracted from the conduc-
tance versustime curves. Significantly different conductance curveshapes were
seen for such gases as propane, carbon monoxide and ethanol when an offset
sinusoidal waveform was used to drive t h e sensor heater. The effect of varying
the concentration of the reducing gas wasexamined both to check the effect on
selectivity between gases and to determinethe functional relationship between
conductance and gas concentration as related to the time in t h e cycle period. It
was found that the conductance change at t h e low-temperature section of the
thermal cycle can vary at a rate faster than linear for low concentrations, and
because the clean air conductance is very low in these sections t h e thermally
cycled sensor is extremely sensitive to reducing gas.

1. Introduction produce annoying false alarms. One method which has

Although various metal oxides have been used as the
basis of semiconductor gas sensors, tin oxide (SnO?) is
by far the most popular. It has been used in both thin
film and sintered powder form [l-31. In both cases the
primary mechanism of operation is through the changes
introduced in thesurface conductivity of thesemi-
conductor by chemicalreactions which occur on the
surface [4,5]. Atmospheric oxygen is chemi-adsorbed
onthesurfaceprimarily as 0- which, as it tiesup
electroniccarriers(n-type semiconductor),decreases
the conductivity of thesensor.Any reducinggases,
which may be present, will remove the chemi-adsorbed
oxygen and restore the conductivity [6-81. Therefore,
any given mixture of atmospheric oxygen and a reduc-
ing gas will produce a unique sensor conductance for
that gas. Forsinteredpowdersthechanges in con-
ductance are greatest at grain boundaries. For thin
films the oxygen induced depletion width can include
theentire film butthick films, wherethisdoes not
occur, may involve a combination of factors [4,9].
One of the main problems with tin oxide as well as
other gas sensors is their relative lack of selectivity; the
chemi-adsorbedoxygentends to react with a wide
spectrum of reducing gases[9,10]. If the gas onewishes
to detect is inflammable, like propane, or toxic, like
carbon monoxide, organic vapourslike ethanol or ace-
tone, to which the sensor is very sensitive, will often
been only briefly examined in the literatureis the use o f
thermal cycling of the sensor element asa technique to
improveselectivity [3,9, 11, 121. However,thishas
been the basis of a number of recent patent applications
[13-171. As different reducing gases react at different
ratesas afunction of catalyst (sensor) temperature,
varying the temperature in a cyclic manner can lead to
uniquesignatures of thegas in question.Another
application of thermal cycling which does not seem to
have appeared in the literature is the great increase in
sensitivity which can be obtained by proper measure-
ment. This latter point will comprise one of the main
points of this paper. We will also examine, in general,
the properties of thermally cycled tin-oxide sensors,
such a s the effect of the maximum temperature scanned
and the effect of the cycle period. The sensor tested
here is one in generalcommercialuse,asintered
powder tin oxide gas sensor manufactured by Figaro
Engineering Inc.
2. Experimental details
Thermal cycling measurements were performed using
the TaguchiGas Sensor #S12 which is manufactured by

0268-1242/89/050351
$02.50 + 09 @ 1989 IOP Publishing Ltd 351
W M Sears et a/
Figaro Engineering Inc. [18]. The active ingredient of
thissensor is sinteredtinoxidepowder mixed with
palladium and a binder, and baked onto the outside of
a smallceramictube which is covered by aninter-
digitated gold pattern [ 1, 191. The gold allows measure-
ment of theelectricalconductance of the tin oxide.
Inside the tube is a coiled metal wire which is used to
heat the sensor. The sensor temperature is determined
by the size of the voltage applied across the heater wire.
As direct measurement of the sensor surface tempera-
ture is difficult, the sensor operating temperature will
be expressed in this paper as the 'heater voltage'. The
temperature of the sensor surface in air is expected to
be a direct but non-linear function of the heater vol-
tage. Generally, a 5 V bias is applied to the heater coil
which corresponds to a sensor operating temperature
between 300 and 400 "C [ 1,191. This has been esti-
mated by direct measurements of tin oxidesensor
conductance in a small oven equipped with a thermo-
couple.
The sensor surface temperature is affected not only
by the heater voltage but also by Joule heating caused
by the current used to measure the conductance and by
the exothermic nature of inflammable gases the sensor
is detecting. This makes knowledgeof the exact surface
temperature under all conditions that much more diffi-
cult.
The electrical leads are mounted to metal pins in a
resin container which can be plugged intostandard
sockets. The container has upper and lowerstainless
steelmeshto allow gas to diffuse in buttoprevent
flamesfromspreading outunderconditions of high
concentration of inflammable gas.
After applying the heater voltage the sensor takes a
while to come to an equilibrium conductance. There is
an initial surge in conductance as organic contaminates,
adsorbed gases, and water vapour are burned or driven
off. After a few minutes a lower equilibrium value is
attained. The sensors tested here were all allowed a few
hours to come to equilibrium before testing.
According to Figaro [18], the sensor is designed as
an alcohol or toxic gas detector (e.g. CO) but it will
respond to a number of gases as shown below.
Inourexperimentstheheater was driven by a
HewlettPackardfunctiongenerator(model 3310B)
which allowed theapplication of variouswaveforms,
frequenciesand DC offsets to the heater. The heater
voltage was continuously cycled up and down in tem-
perature in a periodic fashion. For example, an offset
sinusoidal voltage was applied to vary the heater vol-
tage from 0.2 to 6.2 V every 50 S (figure 1).
The changes in conductance of thesensor were
measured at an applied bias of 5 V across the tin oxide.
Digital electrometers were used to simultaneously
measure the voltage and current and this allowed the
real time measurement of conductance changes using a
computer data acquisition system.
The sensorwas tested inside a lOOL box where gases
and vapours were tested by direct injection. Laboratory
air was used as the clean air baseline.
352
1.0
c
2
+
0.2
0.0
Tlme l S I
Figure 1. The conductance of a tin oxide gas sensor as
a function of time under different cycledheater
voltages in 200 PPM ethanol. Maximum heater voltage
is: (A) 5.0 V; (B) 6.2 V; (C) 7.2 V. Curve (D): sinusoidally
varying heater voltage, normalised to 1.0. '
3. Results
3.1. General effects
In figure 1 we see the effect of the maximum heater
voltage and therefore the maximum temperature on the
response of the Taguchi sensor to 200 PPM of ethanol
vapour. The heater voltage for the three curves shown
was varied from a value close to zero to a maximum of
5.0, 6.2,or 7 . 2 V . Thebrokencurve showingthis
sinusoidal variation has been normalised, and only one
period (50 S) of the waveform is shown, as the curves
representasteady-stateresponse which is attained
within two cycles, after the injection of gas. After this
the curves are quite reproducible until the gas concen-
tration is changed again. One may note that the right
and leftmost values on the figure match.
The most obvious trend in the three curves is the
separation into two peaks, one on the heating and one
on the coolingsides of the sinusoidalheating curve.
The valley at about 20s represents loss of response at
higher temperatures. This loss is related to the catalytic
reaction rate of the vapour [ll,20,211. At lower tem-
peratures the reaction rate is low, but rising, and the
partialpressure of the reducingagent in the local
atmosphere is unchanged. This means that the sensor
response (conductance) is limited by the reaction rate.
At the higher temperatures the reaction rate is much
higher and this keepsthe local pressure of reducing
vapour low. In this case the sensor response is limited
by the diffusion of gas towards the tin oxide. It is also
possible that at high temperatures the reducing vapour
begins to burn (combine with oxygen in the air) slightly
removed from the tin oxide surface. This would have
the same effect of decreasing the amount of vapour
available to react with chemi-adsorbed oxygen on the
tin oxide surface.
The conductance of thesensorreachesan initial
peak at approximately the same temperature for the
threecurves:atabout 5.0 V forthe 5 V maximum
 General characteristics of thermally cycled Sn02gas sensors
curve, 5.2V for the 6 . 2 V maximum curve, and 5.3V
for the 7.2 V maximum curve. The peak on the down
side of the heating curve is expected from the explana-
tion above but this peak does not occur at 5 V, but at
2.5, 1.8 and 1.7V for the three curves A , B and C in
figure 1. This and the structure seen on the first peak
shows that the tin oxide surface changes significantly
throughout the cycle. We expect that the amount of
water vapour (hydroxyl groups) adsorbed on the sur-
face plays a large role in this [22-241. As the surface is
'cleaned'atthetop of the cycle thiswouldexplain
differences of the conductance curves on the heating
and cooling sides. The loss in absolute response of the
7.2Vcurve (C) mightalsobe dueto this high-
temperature cleaning, in which case one expectsthis
difference to be dependent on the type of gas or vapour
tested.
One shouldnotethatfromthepoint ofviewof
sensorselectivity the6.2V cycle hasadvantages; it
shows more features than at 5.0 V and has a higher
conductance than at 7.2 V.
In figure 2 we examine the effect of the cycle period
on the gas sensor response. The vapour being tested is
again 200 PPM ethanol. The heater voltage varies sinu-
soidally from 0.2 to 6.2 V, and the different periods
have all been normalised to fit a common scale. This
makes it easier to compare the different features with
respect totheir position in the cycle, which forthe
lower frequencies is directly correlated to the sensor
temperature.
Curve A in figure 2 shows onlyone feature, near the
maximum heater voltage. For a 10s period the sensor
response may not be able to follow the heater voltage
changes and the response becomes smeared out. The
asymmetry of the peak may be due to an asymmetryin
cooling versus heating rates. The sensor also does not
have time to completely cool as seen by the fact that the
conductance does not fall below 4 x lO-'S.
As the period is lengthened more features appear
and there is a continuous shift of both the heating and
l 5 I 7
Tlrne (arbitrary unltsl
Figure 2. The conductance of a tin oxide gas sensor as
a function of relative time for various cycle periods in
200 PPM ethanol. (A) 10 S period; (B) 25 S period; (C)
50 S period; (D) 100 S period; (E) 200 S period; (F)
sinusoidal heater voltage, 6.2 V maximum.
LI I l l 17
0 100 200 300 400
Tlrne l S l
Figure 3. The conductance of a tin oxide gas sensor as
a function of time for various reducinggases and
showing two periods of a 200 S thermal cycle.
(A) 1000 PPM methane; (B) 200 PPM propane;
(C)500 PPM carbon monoxide; (D) sinusoidal heater
voltage, 6.2 V maximum.
coolingpeaks to shorter relativetimes in the cycle.
Moving from curve B to C to D to E one observes that
the heater voltage corresponding to the heating peak
position on curveFmovesfrom 5.9 to 5.2 to 4.5 to
3.8 V whereas the cooling peak moves from 1.2 to 1.9
to 2.7 to 3.1 V. Thus, as the period is lengthened the
heating and cooling peaks approach the same value.
Therate of heater voltagechange persecond of
increased period change steadily decreases. One there-
fore expects an asymptote near 3.5 V which is close to
the average of the two peaks for the various periods.
This is to be expected since for an infinite period the
thermal history of the peaks should be the same and
therefore the surface conditions of the tin oxide should
be the same on heating and cooling. The size of the
peaks should also approach each other, although thisis
less obvious from the data. These results point out the
fact that complete chemical equilibrium of the tin oxide
surface takes significantly longer to reach than the time
requiredfor bulk thermalequilibrium.This will be
even more apparent for gas a such as carbon monoxide.
Thiseffect representsthe main'speed of response'
limitation in the use of tin oxide gas sensors.
Intheoperation of aselective gas sensora 50s
period represents a campromise between the desired
sharpening of features and the needof a quick response
to changing conditions in the air space being tested.
In figures 3 and4 we examinethe differences
between the response of a thermally cycled sensor to
variousgasesandvapours. An approximately 200 S
period is used to give distinctive features. The maxi-
mum heater voltageused was again6.2 Vandtwo
cycles are shown to emphasise thereproducibility of the
curves once steady state is reached.
For methane (1000 PPM) and propane (200 PPM),in
figure 3, there is no well defined peak structure as there
is for the othergases. The maximum response for these
gases occurs at the maximum heater voltage (6.2V).
This is true even when a maximum heater voltage of
353
W M Sears er a/
I
2 6
0 3g
+
$
U
4 <
0
v
2 -
2 average as seen before) and there is a shoulder on the
1
0 Interestingly, this shoulder is at the same position as
0 100 200 300 4 00
Time I s 1
Figure 4. As figure 3 with (A) 500 PPM hydrogen;
(B) 200 PPM ethanol; (C)200 PPM acetone;
(D) sinusoidal heater voltage, 6.2 V maximum.
7.2 Vis used and reflects the high temperatures needed
to oxidise these gases. There is some structure, how-
ever, consisting of a shoulder at about 5.2 V in the two
gases. Forpropane,thisshoulder is of thesame
strengthastherest of thepeak giving anear flat
response over a range of temperatures.
Carbon monoxide (500 PPM) produces more struc-
ture (figure 3, curve C) namely a heating peak at 2.0 V
and a cooling peak at 3.1 V. This gives an average of
2.6 V and represents the lowest temperature (highest
reaction rate) of all gases tested. This is also reflected
by the fact that the conductance of the sensor at its
lowest temperature is only slightly lower thanthe
cooling peak which is in sharp contrast to all the other
gaseswhoseresponsealmostvanishesas the sensor
cools toroomtemperature.The tin oxidesensor,
havingjust beenthermallycleaned, will respond to
CO at very low temperatures (near room temperature
in fact) for a very long time, but eventually adsorbed
gases and water vapour will poison the surface. Thus
the sensor cannot be used reliably at low temperature
for extended times and many commercial C O sensors
involve thermal cycling.
There are also features at 4.4 and 1.7 V of the CO
response. This complexity must relate to the changing
nature of the catalytic reaction of CO on the tin oxide
surface,and possibly tointeractions with adsorbed
water vapour.
In figure 4 we have three very similar curves, which
imply a similar degree of catalytic reaction for hydro-
gen (500 PPM)andtheorganicvapoursinvolved,
200 PPM ethanol and 200 PPM acetone. They all have
strong well defined heating and cooling peaks.
For hydrogen these peaks occur at 4.7 and 3.8V
with an average of 4.2 V. Acetone gives almost identi-
cal positions at4.7 and 3.7 V with an average also about
4.2 V . The most significant difference between them,
besidestheirabsolute sensitivity ontheTaguchi gas
sensor, is the relative response at the maximum heater
temperatureandtheintensityratiobetweenheating
and cooling peaks.Thehydrogenresponseremains
relatively high between the peaks suggesting that there
354
is less loss of partial pressure near the surface at higher
temperatures as the catalyticreaction rateincreases.
This may be due to a higher diffusion rate, related to
the average molecularvelocity, for hydrogen compared
to organic vapours. The cooling peak intensity is also
unusually high compared to the heating peak, possibly
2 reflecting the increased value of the valley.
- The ethanol response occurs at slightly lower tem-
peratures (3.9V heating, 3.1V cooling and 3.5V
heating peak
notseen
for
the
other twogases.
theheatingpeaks of hydrogenandacetone.These
features can serve as selection criteria in the use of tin
oxide gas sensors.
The type of waveform used in the thermal cycling of
the gas sensor can also have a significant effect on the
selective nature of theresponsealthoughthe main
featuresjust discussed remain. For
propanethe
reponseafterthe initialheating tendsto follow the
shape of the heater voltagewaveform.Forasquare
wave (0.2 to 6.2V switching, 50s period) we observe
thatafteran initialheatingperiod of about 8 S the
response becomes flat and remains so until the heater is
turnedoff.Thestructure,admittedlysmall,seenfor
the sine wave largely vanishes. This flatness is due to
the high reaction temperatures needed for the complete
oxidation of propane combined with the uniform tem-
perature of the square wave over much of its cycle. A
triangular waveform shows much the same response as
the sine wave but with a well defined peak for propane
at the maximum temperature in the cycle.
For the gases and vapours reacting at lower tem-
peraturesthechangesduetothewaveformare less
dramatic. As the sine wavehas no sharp edges, the
temperature can more easily follow the heater voltage
(the relationship is, of course, not linear) and is more
useful for the discrimination of identifying features. It
might be useful to design a waveform that would give a
linear ramp in temperature, by compensating for the
non-linearrelationshipbetweenheatervoltageand
sensor temperature. The square wave has the advan-
tage of ease of generation and usefulness in the selec-
tivedetection of gasessuchas propaneandcarbon
monoxide.
3.2. Concentration dependence
Figures 5 to 9 display the concentration dependence of
sensor response to different reducing gases. The heater
voltage (broken curve) is varied sinusoidally between
0.2 and 6.2V. The responsesrepresenttheperiodic
(50 S period)butsteady-statevariation of thecon-
ductance of the sensor in the presence of the various
concentrations stated. Curve Ain the five figures repre-
sents the conductance due to laboratory air, before test
gas has been injected. Table1 lists conducatance values
takenfromthese figures, andothersnotshown,for
variousgasesandconcentrations.Laboratoryair is
listed as zero concentration (G,)).
 General characteristics of thermally cycled SnO, gas sensors

Table 1. Sensitivity of a thermally scanned tin oxide sensor.

0 to 5 s 7 to 12 S 18 to 22 S 27 to 32 S 43 to 47 S
Concentration
(PPM) AG
AGIG,,
AG AGIGo AG AGIGo AG AGIGoAGf AG Go
Propane
0 0.18 - 22.3 - 36.1 - 6.2 - 0.01 -
10 0.0 0.0 0.6 0.03 0.2 7.6 4.3 0.7 0.0 0.0
50 0.38 2.1 24.6 1.1 28.4 0.8 14.0 2.3 0.0 0.0
200 1.46 8.1 63.5 2.9 66.9 1.9 34.2 5.5 0.09 9.0
1000 4.45 25 131 5.9 146 4.1 74 12 0.40 40
CO
0 0.1 - 5.0 - 18.0 - 3.0 - 0.1 -
10 2.5 25 42 8.4 18.0 1.0 4.8 1.6 0.0 0.0
50 45 450 100 20 39 2.2 23.5 7.8 6.4 64
200 167 167037 186 78 4.3 84 28 64 640
500 317 317059 295 115 6.4 157 52 142 1420
H?
0 0.1 - 5.0 - 18.0 - 3.0 - 0.1 -
10 4.9 49 87 17.4 43 2.4 10.230.7 0.5 5.0
50 38.3 383 203 40.6 106 5.9 117 39 9.0 90
200 106 106082 408 241 13.4 306 102 35 350
500 166 1660 651 130 426 24 555 185 62 620
1000 223 2230 815 163 588 33 767 256 90 900
Ethanol
0 0.1 - 5.0 - 18.0 - 3.0 - 0.1 -
1 0.3 3 25 5.0 12 0.7 3.0 1.0 0.0 0.0
5 5.2 52 78 15.6 32 1.8 14.3 4.8 0.25 2.5
20 40 400 179 35.8 60 3.4 49 16.3 3.5 35
100 208 2080 656 131 139 7.7 218 73 35.1 351
200 340 3400 886 177 192 10.7 339 113 66.7 667
500 680 6800 1897 379 321 17.8 839 280 172 1750
Acetone
0 0.1 - 5.0 - 18.0 - 3.0 - 0.1 -
1 0.0 0.0 20 4.0 11.0 0.6 2.0 0.7 0.0 0.0
5 0.7 7 92 18.4 33 1.8 14.0 4.7 0.0 0.0
20 5.8 58 249 49.8 68 3.8 50 16.7 0.9 9
100 33.2 332 743 149 144 8.0 193 64 7.8 78
200 75 750 1153 231 195 10.8 350 117 20 200
500 139 1390 1580 316 319 17.7 665 222 46 460
Note: Go is the base conductance at zero concentration of reducing gas and AG is the increase in conductance
observed when gas is added. The units used in the table are ,USand represent the maximum value in the cycle
time range shown.

Thetable splits thethermal cycle upinto five
regions or windows. The conductancesused in the
calculation of variables in the table represent themaxi-
mumvaluewithineachwindow. AG is listed as the
change in conductance (conductance at a set concen-
tration minus the value at zero) for the various concen-
trations except zero where G,, is listed instead. AG/Go
is the ratio of this change to the zero concentration
value.
Examining the sensor response for propane (figure
5 and table 1) we see that there is very little change in
shape of the conductancecurvefrom low to high
concentrations.Theresponse follows the increasing
temperature,asrepresented by theheatervoltage
curve, with a slight shift to the cooling side. There is
also a widening of the response; the wings are increas-
ing faster than the centre. The latter can be seen more
clearly in table 1 although the effect is slight for pro-
pane.
Althoughtheabsoluteconductancechangesare
larger at peak response, the sensitivity ratio AG/Go is
muchlarger in the wings duetothe very low con-
ductance of the sensorin laboratory air in this region of
the cycle.
Figure 6 shows the response to concentration varia-
tions of carbon monoxide. In contrast to propane, the
build-up of response in the wings, the areas of negli-
gible clean air response, is dramatic for carbon monox-
ide with a significant change in shape with concentra-
tion. This shift in shape makes identification of carbon
monoxide difficult at low concentrationsalthoughat
higherconcentrationsthe large low-temperature res-
ponse is areliableindication. The rapidincreases in
responsefortheheatingpeakas well asthe low-
temperature regions is reflected in table 1 in the very
large sensitivities shown, as high as a conductance ratio
of 3000. This means that thermally cycling the Taguchi
sensorcangreatlyincreasethesensitivity(measured
early in the cycle) and the selectivity (measured late in
the cycle).
Theconcentrationvariation of hydrogen gas in
figure 7, also shows enhanced sensitivity in the wings.

355
W M Sears et a/

20

0
0
Time ( S ) Time l S )

Figure 5. The conductance of a tin oxide gas sensor Figure 8. As figure 5 for ethanol. (A) clean air;
as a function of time (50 S period) for various (B) 20 PPM; (C) 100 PPM; (D) 500 PPM; (E) heater voltage.
concentrations of propane under an applied sinusoidal
heater voltage (6.2 V maximum). (A) clean air;
(B) 50 PPM; (C) 200 PPM; (D) 1000 PPM; (E) heater
voltage. the response due to carbon monoxide. This problem in
selectivitycan bealleviatedsomewhat by theuse of
responseratios of theconductancesat two or more
points in the thermal cycle.
Figures 8 and 9, giving the response of ethanol and
5 i 3
acetone respectively, are very similar. They both have
* strongheatingpeaksfollowed by deep valleys and
significantly weaker cooling peaks. The difference in
W
g 2 overall shape caused by the rapid rise of the cooling
c
U
peak with concentration is also common to both. Thisis
v
0
-< reflected in the sensitivities listed in table 1.
U
2 -
1 The maindifference is thelowertemperature of
1 reaction of ethanol vapour which results in higher wing
sensitivities. The significantly higher low-temperature
0 response of ethanol also means that it will interfere
0 10 20 30 40 50
Time l S )
more seriously with the selective detection of carbon
monoxide in that region.
Figure 6. As figure 5 for carbon monoxide. (A) clean In figure 10 we examine in more detail the issue of
air; (B)50 PPM; ( C ) 200 PPM; (D) 500 PPM; (E) heater
voltage. sensitivity
variation
fromregion to region in the
thermal cycle. Plotted is the log to the base ten of the
change in conductance to added ethanol vapour versus
Although the response atlow sensor temperatures (the
the log of the concentration of the added vapour. This
45 S mark) is relatively low compared to the rest of the
is done as it is often found that the conductance change
response, at high hydrogen concentrations it can rival

I I I l 17

Ll
i6 20 I

-
I

,
I *
E
-\
'
I I I 17

*, \
P 6
I \
0
/ \ 1
d l.
0
c

v
S 4
0
U

2
1

0
0 10 20 30 40 50
Time (S)

Tlme Is1
Figure 7. As figure 5 for hydrogen. (A) clean air;
(B) 50 PPM; (C) 200 PPM; (D) 1000 PPM; (E) heater Figure 9. As figure 5 for acetone. (A) clean air;
voltage. (B) 20 PPM; (C) 100 PPM; (D) 500 PPM; (E) heater voltage.

356
 General characteristics of thermally cycled SnO, gas sensors
I I I 4. Discussion
l I I l
-1 0 1 2 3
Log([ (PPM))
Figure 10. The logarithm of the change in conductance
(AG)in ,USfor data taken from table 1 versus the
logarithm of the concentration of ethanol vapour in
parts per million. (A) 0 to 5 S of cycle period, lower
slope is 1.64, upper slope is 0.74; (B) 7 to 12 S, slope is
0.69; (C)18 to 22 S, slope is 0.52; (D) 27 to 32 S , slope
is 0.90; (E) 43 to 47 S , lower slope is 1.90, upper slope
is 0.99.
(AG) and vapour concentration (C) are related by a
power-law dependence [7]
AG = AC" (1)
where logA is the intercept and n is the slope of the
log-log plot.CurveC in the figure representsdata
takenfromthe 18 to 22s region of the cycle.This
region represents the valley oftheethanolresponse
shown in figure 8 as well asthepeak in cleanair
response. We would also expect that this region would
most closely correspond to theDC sensor response. The
log-log slope is 0.52 from figure 10, representing the
square-rootdependence very commonlyobserved in
the DC operation of tin oxide sensors.
Curve D, representing the cooling peak region at27
to 32 S , has a slopeof 0.90. This represents a near-linear
response,unusual in theoperation of gas sensors.
Curve A which comes from data taken from the very
beginning of the heating peakregion (0 to 5 S ) does not
showasimplepower law response. The low concen-
tration part of the data gives a slope of 1.64 reflecting
the very quick build-up of response in this region. At
high concentration this slope falls to 0.74. This change
may reflect the movement of the heating peak to lower
times in the cycle at higher concentrations.This is
partly confirmed by the log-log slope of curve B (the
heating peak region at 7 to 12 S) which is 0.69, close to
the high concentration value of region 1. The log-log
slopes of curve E (43 to 47 S ) which are 0.99 for the
upperregionand1.90forthelower, showasimilar
overlap with the cooling peak(curve D). Allthis
implies major differences in chemistry occurring in the
different regions of the cycle. The other gases tested
give similar slope variations in the five regions.
Theease with which variousgasesandvapoursare
oxidised by the catalyticprocesses onthe tinoxide
sensor is given by the average peak heater voltages:
carbon monoxide (2.6 V), ethanol (3.5 V ) , hydrogen
andacetone(4.2 V), andmethaneandpropane
( > 7 V). Fromtheliterature[3,9,11, 121 theCO
averagepeakheatervoltageshouldcorrespondto
about 100 "C, the hydrogen value to about 300 "C, and
the methane value to 500 "C surface temperature. By
varying the temperature of the sensor, three classes of
gasescanbedistinguished: those that oxidiseatlow,
medium and high temperatures. It is important to cycle
the sensor heater to approximately 6 V to clarify struc-
tural differences between the response to variousgases
and vapours. The sensor is nominally rated for 5 V but
can be safely run at higher temperatures for extended
periods, with the possible exception of the presence of
high concentrations of stronglyreducinggases. The
period of thermal cycling must be long enough to allow
thesensortemperatureto follow theappliedheater
voltage, but it is not necessary to have complete chemi-
cal equilibrium.
The structure of the periodic conductance changes
which occurwhenthesensor is exposedtoreducing
gases can be used to improve selectivity and sensitivity
of detection. By measuringtheconductanceatthe
lowest temperature of the cycle. carbon monoxide can
be selectively detected whereas measuring the flatness
of response at thehigh temperatures will select propane
over other gases. The sensor also shows an increased
sensitivity early in the heating cycle as the response to
injected gases increases more rapidly with temperature
than the base conductance. The cycled response of the
sensorcanbethought of asthermallyprogrammed
desorption which reflects both the catalytic sites on the
tin oxide as well as the reacting gases.
The chemistry which occurs on the surface of a gas
sensor like tin oxide involves two main reactions.In the
first atmospheric oxygen ( 0 2becomes
) chemi-adsorbed
to the surface (0-),tying up electronic carriers (e-).
2e- +0 2 3 2 0 - . (2)
kl
Since the carrier density in the semiconductor (n-type)
is decreased the conductivity decreases. This effect is
largest at the constricted contacts between the grains of
a sintered powder. In general, 0; will also be chemi-
adsorbed on the surface. We neglect it because it is not
expected to react significantly with the reducing gas and
at moderate temperatures will desorb or change to 0-
[6,10,19]. The concentration of 0'- is expected to be
much lower than 0- and we neglect its effect here. We
are assuming that equation (2) is irreversible (second
order) with k , being the rate constant of the reaction.
The presence of reducing gases (R) in the atmos-
phere will produce a counter reaction.
R+O-JRO+e-. (3)
k?
357
W M Sears et a/
We assume this reaction is also irreversible, with a rate
constantk2, as theproduct(RO) will desorb. In
equation (3) the reducing gas removes chemi-adsorbed
oxygen,frees upanelectroniccarrier,andthereby
increases the conductivity of thesemiconductor gas
sensor. The two reactions (equations (2) and (3)) there-
fore act in opposite directions and for a given concen-
tration of reactants will reach a steady state, involving
the continuous consumption of oxygen andreducing
gas.
Using the law of mass action we can rewrite these
equations as currents
11= k,Nt[O,l (4)
I , = 21, (6)
and therefore
whereNe is theconcentration of electronsandthe
square brackets denote the concentration of enclosed
compounds.Wecandirectlyidentify Ne with the
conductance change A G (within a constant of propor-
tionality and assuming no changes in carrier mobility)
as theabovetreatment gives zerocarriersforzero
concentration of reducing gas. [R] can also be directly
related to volume gas concentration expressed as parts
per million.
We will now examine the effect of equation (7) on
the log-log slope of conductance versus concentration
in equation (1) (A log N J A log[R] = n ) under various
conditionsandassumptions.First we assume that k,
and k, are constant (fixed temperature), that [O-] is
constant (relatively low concentration of [R]), and that
[O,] is constant (the atmosphere represents an infinite
source). For this case we find that n = 0.5. This repre-
sents the situation for the valley section of the ethanol
data (figure 10, curve C).
If we allow [O-] to be a function of the reducing
vapour concentration, which we expect to happen at
very high concentrations due to the rapid consumption
of chemi-adsorbed oxygen, we obtain
Withincreasing [R], [ O - ] decreasesand A log[O-]
becomesnegativeandthus n becomes less than 0.5.
This effect is not seen in the results presented here.
As equation(3) is an exothermic reactionwe expect
the temperature of the tin oxide sensor to be afunction
of the concentration of the reducing vapour, especially
at high concentrations. In addition Joule heating, due
to the voltage applied across the tin oxide in measuring
theconduction, will becomemore significant as the
concentration and conductance increase also resulting
in a rise in temperature (power = V 2 G , although if the
358
voltagedecreasesbecause of arelatively high series
resistance this effect is less certain).
This affects our equation as the rate constants are a
function of temperature. We can write
k = ko exp ( - E,/ KBT) (9)
where ko is the value at infinite temperature, E , is an
activation energy, K B is the Boltzmann constant and T
is the temperature. This leads to
A Ink E,
" --
(10)
AT KBT'
which shows that with increasing temperature the rate
of change of the log of the rate constantwith respect to
temperaturedecreases,although it always remains
positive. Given that we suspect a direct, although non-
linear dependence of the temperature on the reducing
vapourconcentration,therate of change of k with
respect to [R] should also decrease with increasing [R]
and should always be positive.
So given that the rate constants are function
a of [R]
we can write
A log k, A log k,
n=o*5(Alog[R]-Al~g[R]+1)' (11)
From the above argument, with increasing [R] the first
term increases n but the second tends to decrease it.
Assuming that the temperature variation of the rate
constantduetothe reducingagent dominates, we
obtainslopes greaterthan 0.5 and possibly much
greaterthan 1. Duetothe effect of equation (lo),
however, at higher temperatures the slopemay start to
decrease,although still remainhigherthan 0.5. This
effectshouldbegreatestfor high [R] but low or
moderate temperature and therefore should explain the
high slopes seen in the wings of the conductance curves.
Withincreasing
concentration of reducing
gas
another effect is seen. Because of the higher reaction
rate the concentration of the reducinggas at the tin
oxide surface begins to drop with increasing tempera-
ture, as the gas is consumed faster thanit can diffuse in;
it is also possible thatthe gas begins toburnsome
distance removed from the surface. In both cases the
effect is to decrease the amountof vapour able to react
with chemi-adsorbed oxygen on the tin oxide surface at
the higher temperatures. Therefore we can write
where [Rd] is the difference in concentration between
the gas in the atmosphere, [R], and the gas near the
surface. [Rd] is a function of [R], both are functions of
temperature, and so this explains the valleys seen in the
response of many of the gases tested.Itmustbe
emphasised thatthis is mostly a temperatureeffect seen
as thesensor is heating,theabsoluteconcentration
near the surface continues to increase but at a rate less
 General characteristics of thermally cycled SnO, gas sensors
than at low gas concentrations. This will have a slight
tendency to reduce the log-log slope.
We thus see that as well as the obvious advantages
of thermal scanning with respect to selectivity (shape)
thereare also greatadvantages of sensitivity if the
measurement is performed at the correct point in the
cycle.
Acknowledgments
We wish to thank Halitec Industries for their sponsor-
ship of this research and in particular Vern Moen for
many valuable and encouraging suggestions. We also
acknowledge the financial support of an IRAP Grant
from the National Research Council of Canada.
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