Received 14 July 2004; received in revised form 26 October 2004; accepted 12 November 2004
Available online 6 January 2005
Abstract
Thin film metal oxide materials exhibit a bell-shaped variation of the gas sensitivity with sensor operation temperature. With respect
to the temperature TM at which a sensitivity maximum occurs, the distribution of the gas sensitivity is asymmetric exhibiting a relatively
steep increase below TM and a more moderate drop-off above TM . In this paper a rate equation approach is described, which successfully
reproduces temperature- and gas-concentration dependent sensitivity distributions S(T, cgas ) experimentally determined for a number of
reducing analyte gas molecules. We show that such distributions are determined by two energetic parameters, which are specific for the
special adsorbate/adsorbent system involved. These are (i) the strength of adsorption of neutral analyte gas molecules Eads and (ii) the kinetic
barrier Ea that needs to be overcome to induce a surface combustion event involving an adsorbed analyte gas molecule and a surface oxygen
ion.
© 2004 Elsevier B.V. All rights reserved.
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doi:10.1016/j.snb.2004.11.020
588 S. Ahlers et al. / Sensors and Actuators B 107 (2005) 587–599
Fig. 3. PVD deposition of noble metal doped thin film sensors. A sandwich
consisting of 10 nm tin and 5 nm catalyst layers is first evaporated onto the
substrate. Subsequently the layer stack is subjected to thermal oxidation
in ambient air, resulting in a catalytically enhanced tin oxide sensor with Fig. 4. Maximum response SM of a compact (dark grey) and a porous (light
granular morphology. grey) tin dioxide layer to reducing gases. Whereas a compact film morphol-
ogy reduces the gas sensitivity, it is more convenient to analyse theoretically.
The operating temperature of the sensors is not fixed in this graph, rather the
butions. In order to obtain such doped material, multi-layer optimum is chosen for each gas species.
stacks of tin and dopant materials were evaporated as indi-
cated in Fig. 3 and annealed in ambient air after deposition to charge regions. Such modulation effects, however, are much
obtain SnO2 material containing agglomerates of dispersed more pronounced at the sintering necks of a porous layer
noble metal. because of the associated small cross sections of the current
paths. This matter has already been discussed in considerable
detail in the literature [23,30–32].
3. Results of gas measurements In the following, only results on compact layers will be
considered. Relevant results on such layers are presented in
In the following we will use the terms “response” and Figs. 5–7. Granular layers will be considered in Section 4.2.
“sensitivity” synonymously. Mathematically the response S The sensitivity profiles reported in Figs. 5–7 exhibit sev-
is defined as follows: eral characteristics, which are common to a wide variety of
R0 other metal oxide sensing layers: (i) the sensitivity at room
S= −1 (1)
Rgas temperature and up to about 100 ◦ C is small for all gases and
gas concentrations considered; (ii) with rising temperature
where R0 is the sensor resistance in clean air and Rgas is the the response increases up to a certain temperature TM where
sensor resistance under the influence of a reducing gas.
This formula is used because it produces reasonable values
ranging from 0 for clean air to high positive values for strong
interactions with reducing gas species. The values generated
are consistent with those obtained by the common formula
S = Rgas /R0 − 1 for oxidising gases.
Turning to the results of our gas sensing experiments, we
first compare the gas response of tin dioxide films with a com-
pact and a granular morphology. This response was measured
for various reducing gases over a range of sensor operation
temperatures. Specifically the gases ethene (C2 H4 ), carbon
monoxide (CO) and hydrogen (H2 ) were considered as sum- Fig. 5. Gas response of a compact tin dioxide layer to hydrogen. The bell-
marised in Table 1. shaped variation of the gas sensitivity with sensor operation temperature is
Fig. 4 displays the response of both kinds of layers under typical of metal oxide gas sensors. The maximum response to 10.000 ppm
identical conditions of gas exposure. (=1%) H2 is comparably weak.
Obviously, the response of a porous tin dioxide layer is
larger than that of a compact layer [29]. In both cases – and
independent of the film morphology – gas reactions at the ac-
cessible surface area cause a modulation of the surface space
Table 1
Test gases used
Gas Concentration (ppm)
C2 H4 20–5000
CO 2–500
H2 100–10000 Fig. 6. Gas response of a compact tin dioxide layer to ethene (C2 H4 ).
590 S. Ahlers et al. / Sensors and Actuators B 107 (2005) 587–599
Fig. 7. Gas response of a compact tin dioxide film to carbon monoxide CO.
Fig. 9. Variation of the C2 H4 sensitivity with sensor operation temperature
for tin dioxide samples with granular morphology containing different types
a sensitivity maximum SM occurs. This temperature depends of noble metal impurities. The test gas mixture applied was 5000 ppm C2 H4
both on the kind and on the concentration of analyte gas ap- in synthetic air.
plied; (iii) at sensor operation temperatures higher than TM
the response drops again, however, more slowly than below
TM . In particular, a vanishing gas response is not reached,
even at the highest temperatures applied.
Considering these results, it is not very surprising to find
that the temperature of maximum response TM is gas-species
dependent. It is perhaps more surprising that TM also depends
on the analyte gas concentration. This is not at all obvious
at first sight. The theoretical considerations in the next sec-
tion, however, indicate that, in principle, TM should exhibit
a much stronger gas concentration dependence than actually
observed.
Fig. 10. Variation of the CO sensitivity with sensor operation temperature
As will be discussed below, the relatively weak depen- for tin dioxide samples with granular morphology containing different types
dence of TM on the gas concentration is evidence for a of noble metal impurities. The test gas mixture applied was 500 ppm CO in
concentration-dependence of the thermodynamic and kinetic synthetic air.
parameters that characterise a particular adsorbent/adsorbate
system. lysts see [3,33–40]. We will see in the discussion below that
Turning to SnO2 layers with a granular surface morphol- the strong effects of noble metal catalysts on the response to
ogy, we demonstrate the effect of incorporating noble metal some gases is reflected in the physical parameters that govern
impurities. Figs. 8–10 display the gas response of granular the sensing behaviour. Especially the lowering of the reac-
SnO2 films with regard to H2 , C2 H4 and CO. In addition, tion activation energy (introduced in Section 4.1.1), which
these plots contain data for materials that were doped by the is commonly associated with catalysts, can be directly ob-
addition of several percent of platinum (Pt) and gold (Au). served.
These latter data vividly demonstrate that noble metal doping
can have a very severe impact on the magnitude of the gas
response S and on the temperature TM at which the sensitivity 4. Modelling the sensing behaviour
maximum SM occurs. For phenomenological and theoretical
considerations about the effects of adding noble metal cata- 4.1. Compact films
that gas diffusion into the sensing layer can be neglected and
that all gas interactions take place at the free surface of the
slab. This also means that there is only one single surface
depletion layer, which can become modulated in response to
the gas/surface interactions. Because of the simple geometry,
the depletion layer can be described by a single parameter,
i.e. the space charge width WSCR .
Changes in the depletion layer width modulate the cur-
rent through the undepleted bulk very much in the same way
as in a depleted thin film transistor. As metal oxide surfaces
can interact with an adjoining gas phase in a chemically re-
versible way, the arrangement of Fig. 11 basically represents
a chemically sensitive thin film transistor. The properties of
such transistors are discussed in more detail below. Fig. 12. Exchange of electronic charge across the surface barrier. In addition
to thermionic emission over the surface barrier hopping through localised
4.1.1. Surface combustion of reducing molecules donor states may occur in the limit of high oxygen vacancy concentrations
Under clean air conditions, the surface of a metal oxide is and thin surface barriers. More details are given in Appendix A.
covered by adsorbed oxygen. Depending on the temperature
of the sensor, there are different forms of adsorbate possi-
ble [4,41]. At typical sensor operation temperatures of above
150 ◦ C the prevailing adsorbate is O− . The surface coverage In this spirit the following rate equation can be written:
with the latter creates a space charge region and thus con-
trols the baseline of the sensor resistance. The surface band d 2(EC + qVs − EF bulk )
bending qVs associated with this space charge region is: NO = κf0 pO2 NC exp −
2
dt kB T
q2 NO2 2(EC − EO minus )
qVs = (2) − κr0 NO2 exp − (4)
2εε0 nD kB T
where NO is the surface density of surface oxygen ions; nD
the donor density; qVs the surface band bending; q the ele- where NO is the surface density of surface oxygen ions; pO2
mentary charge; ε0 and ε the absolute and relative values of is the oxygen partial pressure; κf0 and κr0 are the kinetic
the dielectric constant. parameters for adsorption and desorption.
In case reducing analyte gases prevail in the ambient at- Considering the fact that Eq. (4) contains the band bending
mosphere, the areal density of oxygen ions on the surface qVs on the right-hand side and that the band bending in turn
is changed. In this case, surface combustion reactions take depends on the surface ion density NO through Eq. (2), it is
place, transforming the reducing gas species and a corre- clear that (4) is an implicit equation that can only be solved
sponding number of surface oxygen ions into CO2 and H2 O by numerical means.
molecules, which are subsequently desorbed into the gas We now generalise this equation to the case that reducing
phase again [35,42–44]. The electrons formerly trapped at analyte gas molecules are present. In this case reactions take
the surface oxygen ions are returned to the metal oxide con- place which reduce the density of surface oxygen ions NO .
duction band, which causes the space charge layer thickness In order for those reactions to take place, the following steps
to shrink and the sensing layer resistance to decrease. need to be considered: first, reducing gas molecules need to
In order to arrive at a rate-equation formalism able to adsorb on the metal oxide surface. This will lead to a certain
describe gas detection via surface combustion processes, surface coverage with this new kind of adsorbate. A frac-
the rate of adsorption and desorption of oxygen ions at a tion of the adsorbed molecules in turn may exchange charge
metal oxide surface needs to be considered. Starting from the with the metal oxide bulk, but these adsorbates will then be
ionosorption reaction fixed on the surface and therefore likely to be unable to travel
close to one of the surface oxygen ions [43]. Those analyte
O2(g) + 2e− ↔ 2O(s) − , (3)
molecules, which did not exchange charge with the metal ox-
it is seen that ionosorption requires two electrons to be ther- ide surface, are able to diffuse along the surface until they run
mally emitted from the Fermi energy across the surface bar- into a surface oxygen ion, where they are likely to undergo
rier (EC + qVs − EF bulk ) to become trapped at a pair of ad- a catalysed surface combustion event. Triggering such a re-
sorbed oxygen atoms. As the surface oxygen ions formed action, a kinetic barrier, represented by an activation energy
give rise to energy levels whose positions are fixed relative Ea , needs to be overcome. The reaction products – usually
to the position of the band edges, desorption of the surface CO2 or H2 O – will then leave the surface and the electrons
oxygen ions requires re-emission of two electrons across an formerly trapped at surface oxygen ions are released to the
energy barrier of height (EC − EO minus ) (Fig. 12). conduction band.
592 S. Ahlers et al. / Sensors and Actuators B 107 (2005) 587–599
In this spirit Eq. (5) is modified by a reaction term Re to κf0
NO air = pO n 2 (12)
reflect the additional possibility of surface combustion: κr0 2 D
d 2(EC + qVs − EF bulk ) with the value of NO being determined, the width of the space
NO = κf0 pO2 NC exp −
2
dt kB T charge layer can be calculated:
2(EC − EO minus ) NO
− κr0 NO exp −
2
− Re (5) WSCR = (13)
kB T nD
With the total film thickness being D, the actual resistance
Ea
Re = LNO k0 exp − (6) of the metal oxide layer RMOX turns out to be:
kB T
1 Ls
The term Re itself contains a number of important factors: RMOX = (14)
σMOX Bs (Ds − WSCR )
first, a Langmuir relative surface coverage L, which reflects
the adsorption of the reducing gas without charge transfer. σMOX = µn qns (15)
L in turn contains several important parameters [45]:
where Ls is the contact distance; Bs is the contact width; Ds
pgas is the thickness of the metal oxide; WSCR is the width of
L= (7)
pgas + p0 the space charge region; nS is the conduction electron con-
centration (≈nD at elevated temperatures); µn is the electron
kB T Eads
P0 = exp − (8) mobility.
VQ kB T As one is usually not so much interested in the baseline
1.5 resistance of the sensor itself, but in its gas response, we use
2πh̄
VQ = (9)
Mgas M0 kB Tgas Rair
S= −1 (16)
Rgas
where VQ is the quantum volume of the reducing gas; pgas
is the partial pressure of the reducing gas; Tgas is the gas to deduce from Eq. (14) a final formula for the gas response:
temperature (300 K); T is the sensor operation temperature;
Eads is the binding energy of adsorbate; M0 is the atomic mass DS − WSCR gas
S(T, cgas ) = −1 (17)
unit (1.67 × 10−27 kg); Mgas is the relative atomic mass of the DS − WSCR air
reducing gas (e.g. 28 for CO and 2 for H2 ).
where WSCR air is the space charge region width in clean air;
Assuming that a situation of dynamical equilibrium holds,
WSCR gas is the space charge region width in the presence of
the time rate of change of the oxygen ion density vanishes
reducing gas; Ds is the metal oxide layer thickness.
and Eq. (5) can be solved to obtain the density of surface
In this latter formula the electrical parameters µn and nD
oxygen ions both under clean-air as well as under reducing
of the sensing layer cancel out.
analyte gas conditions. Again Eq. (5) is an implicit equation
Combining Eqs. (7)–(9), (11), (13) and (17), an explicit ex-
that can only be solved by numerical means. A more straight-
pression S(T, cgas ) for the gas response of a metal oxide layer
forward analytical solution, however, can be obtained when
can be given. This expression is very lengthy and not very
more restrictive assumptions are made. For reasons detailed
enlightening. Rather than presenting it, simulated response
in Appendix A, we will consider the barriers at the surface to
patterns are displayed in Section 5 below (see Fig. 15).
be transparent for tunnelling by electrons. In this latter case,
It is relevant to note that the bell-shaped variation of the
Eq. (4) reduces to the form put forth by Barsan et al. in [4],
gas sensitivity with sensor operation temperature is deter-
either (Eq. (2) in [4]) without a reaction term, or (Eq. (31) in
mined by the cooperation of the Langmuir adsorption and
[4]) with a reaction term.
the first-order reaction terms in Eq. (6). This latter fact is
Assuming steady-state conditions, an equation for the
illustrated by the data plotted in Figs. 13 and 14. Whereas
areal density of surface oxygen ions can then written:
the first plot shows how these terms vary with temperature
Ea individually, the second plot illustrates how both terms co-
0 = κf0 pO2 nD − κr0 NO − LNO k0 exp −
2 2
(10) operate in reproducing the peculiar form of the gas response.
kB T
The striking fact brought out by Fig. 14 is that due to the
This latter equation can be analytically solved to obtain the properties of the Langmuir adsorption term, the sensitivity
surface oxygen ion density both under reducing analyte gas maximum should shift towards higher sensor operation tem-
and clean air conditions (clean air conditions are represented
peratures once higher gas concentrations are applied. We will
by cgas = 0, and therefore L = 0):
see in Section 5 that this latter effect is not observed in reality
2 and that the absence of a major shift in the sensitivity maxima
Lk0 exp − kEB aT + Lk0 exp − kEB aT + 4κr0 κf0 pO2 n2D
is due to a decrease of the adsorption energy Eads of analyte
NO = (11)
2κr0 molecules with increasing surface coverage.
S. Ahlers et al. / Sensors and Actuators B 107 (2005) 587–599 593
5. Extraction of adsorbate/adsorbent-specific
parameters
Table 2
Parameters entering the fit equation S = f(T, cgas ) which stands for the sensor response as a function of sensor operation temperature and gas concentration
pgas Reducing gas partial pressure Fit variable
T Sensor operation temperature Fit variable
Ea Reaction activation energy; analyte-gas-dependent Fit parameter
Eads Binding energy of reducing gas upon chemisorption; Fit parameter
analyte-gas-dependent
κf0 , κr0 Unknown; ratio κf0 /κr0 fixed by clean air oxygen Fit parameter
coverage; independent of reducing gas type
NO clean Clean air oxygen coverage 2.6 × 1012 cm−2 [46]
PO2 Atmospheric oxygen partial pressure 2 × 104 Pa
Tgas Gas temperature 300 K
Mgas Relative mass of the reducing gas MH2 = 2; MCO = MC2 H4 = 28
ma Atomic mass unit (AMU) 1.67 × 10−27 kg
k0 Surface phonon frequency, reaction attempt frequency 1013 Hz [43]
nD Doping concentration of the metal oxide bulk 1018 cm−3 [4,47]
kB Boltzmann constant 8.617 × 10−5 eV/K
A Sensitivity enhancement factor Fit parameter in porous layers,
fixed to 1 for the compact layers
Fig. 15. Gas response of a compact tin oxide layer to carbon monoxide Fig. 16. Fitted values for the strength of adsorption (top) and the reaction
(CO) as a function of the sensor operation temperature. The symbols stand activation energy (bottom) for the pure tin dioxide film and 20–5000 ppm
for measured sensitivity values; the lines are fits to the function S(T, cgas ) ethene as reducing gas. The magnitude of both energies drops with increasing
(Eq. (17)). analyte gas concentration.
slightly higher temperatures TM as larger gas concentrations particular, the temperature TM , at which the sensitivity maxi-
are applied. Sticking to a constant sensor operation temper- mum SM occurs, was shown to coincide with the temperature
ature close to TM , it is further revealed that the gas response at which the Langmuir isobar starts to fall from a relative
S increases in a sub-linear manner with increasing cgas . All surface coverage of Θ = 1 towards Θ = 0. As, due to the prop-
these characteristics are quite generally observed in all kinds erties of the Langmuir isobar this temperature is strongly
of metal oxide materials. concentration-dependent, the maximum of S(T, cgas ) is ex-
From the fits above, values for the energy parameters Ea pected to experience a considerable shift towards higher sen-
and Eads can be obtained. The next series of graphs display sor operation temperatures as long as constant values of Eads
those values of Ea and Eads that were determined from these are assumed (see Fig. 14). In view of the relatively constant
fits. The most striking feature in these data is that both energy values of TM that emerge from the data of Figs. 5–7, sim-
parameters turn out to be concentration-dependent. On the
whole these data show that reaction thresholds with surface
oxygen ions are lowered and that the strength of adsorption
of the analyte gases is reduced as higher analyte gas concen-
trations are applied (Figs. 16–18).
This concentration-dependence of the two energy param-
eters deserves more attention. In Section 4.1, where the func-
tion S(T, cgas ) was derived, it was shown that the bell-shaped
variation of the gas sensitivity arises from the cooperation of
two opposing effects: (i) an increasing probability of trigger-
ing detection reactions as the sensor operation temperature is
raised and (ii) an increasing probability of adsorbed analyte Fig. 17. Fitted values for the strength of adsorption (top) and the reaction
gas molecules to desorb prior to suffering a detection reaction activation energy (bottom) for the pure tin dioxide film and 2–500 ppm CO
as the sensor operation temperature is further increased. In as reducing analyte gas.
S. Ahlers et al. / Sensors and Actuators B 107 (2005) 587–599 595
Table 3
Measured and fitted results for 1% H2
1% H2 Temperature of max- Maximum sens- Reaction activ- Adsorption energy Eads (eV)
imum sensitivity TM (◦ C) itivity SM at TM ation energy Ea (eV)
Pre tin oxide 400 15 0.44 1.07
(smooth)
Pre tin oxide 370 85 0.57 0.96
(granular)
Tin oxide:Pt 220 2100 0.31 0.66
Tin 370 43 0.42 0.89
oxide:Au
Catalyst doping influences the directly measurable parameters SM and TM . Changes in these parameters are reflected in the fitted energy parameters Ea and
Eads .
596 S. Ahlers et al. / Sensors and Actuators B 107 (2005) 587–599
Table 4
Measured and fitted results for 0.5% ethene (C2 H4 )
5000 ppm Ethene Temperature of maximum Maximum sensitivity Reaction activation Adsorption energy
sensitivity TM (◦ C) SM at TM energy Ea (eV) Eads (eV)
Pure tin oxide 400 4 0.53 1.3
Pure tin oxide (granular) 490 14 0.78 1.4
Tin oxide:Pt 290 314 0.52 1.0
Tin oxide:Au 490 24 0.61 1.4
The influence of the catalysts on the ethene response resembles that on the H2 one.
Table 5
Measured and fitted results for 500 ppm CO
500 ppm CO Temperature of maximum Maximum sensitivity Reaction activation Adsorption energy
sensitivity TM (◦ C) SM at TM energy Ea (eV) Eads (eV)
Pure tin oxide 330 2 0.52 1.3
Pure tin oxide (granular) 410 0.8 1.45
Tin oxide:Pt 420 1 0.87 1.3
Tin oxide:Au 550 4 0.82 1.7
The influence of the catalyst doping on the CO response differs strongly from that on the C2 H4 and H2 one.
in the case of NO2 and O3 , which are less stable oxidising flected in concomitant changes in the two energy parame-
gases [50]. ters.
Considering undoped material first and comparing the data The case of CO is somewhat different. In this latter case,
obtained for the three reducing gases, it is seen that the sensi- the effect on the experimentally accessible quantities SM and
tivity profiles are quite similar, exhibiting different absolute TM is marginal (Pt doping) or even counter-productive in the
values of the gas sensitivity S only. This similarity is reflected sense that detection reactions are inhibited rather than be-
in the fitted energy parameters, which are similar in all three ing promoted (Au doping). As far as the consistency of our
gases. According to these, the gas with the highest response model is concerned, the changes in the measurable quanti-
value (H2 ) also exhibits the lowest activation barrier with ties SM and TM are also reflected in concomitant changes in
regard to detection. the fitted values of the energy parameters Ea and Eads . In the
Noble-metal-doped sensors, on the other hand, exhibit case of Au doping, in particular, the inhibition of detection
quite different behaviour. The data in Tables 3–5 clearly re- reactions is reflected in increased values of Ea and Eads . At
veal a similar impact on the two energy parameters both for this point, however, it should be noted that the two energy
H2 and for C2 H4 . Both catalysts vastly enhance the reaction values do not simply reflect material properties of Pt or Au,
with hydrogen, thereby reducing the maximum temperature respectively. Considering the fact that significant enhance-
TM and raising the maximum sensitivity SM . The ethene sen- ments in the CO sensitivity can be obtained by evaporation
sitivity is also promoted, although this effect is not as strong of dispersed clusters of Au onto granular SnO2 surfaces [54],
as in the case of H2 . it is demonstrated that the fitted values of Ea and Eads are
Pt is the noble metal catalyst most widely used in industrial more representative of the manner of introducing, dispersing
applications. Examples are automobile exhaust gas cleaning, and binding the catalytic impurities at the metal oxide sen-
ammonia oxidation and petrochemical applications like fab- sor surface than representing simple material properties of Pt
rication of plastics from natural oil [50,51]. On a Pt surface or Au.
H2 molecules tend to dissociate into single hydrogen atoms.
Such single atoms are more likely to react with other adsor-
bents, which reduces the activation energy Ea . Concomitantly
the adsorption energy Eads is also reduced. This latter reduc- 6. Conclusions
tion is very important for the functioning of a catalyst: in
order to be able to promote heterogeneous surface reactions, A new approach has been presented that is able to explain
reactant molecules must neither be bound too loosely, as this the gas sensitivity of thin film metal oxide materials towards
would not mediate any reactivity, nor too strongly, as this reducing gases.
would slow down surface diffusion and thus inhibit any fur- This approach satisfactorily explains the bell-shaped vari-
ther reaction. This is also known as the Sabatier principle ation of the gas sensitivity S with the sensor operation temper-
[52,53]. ature T. In particular, the derived function S(T, cgas ) explains
Although Au as a catalyst is not widely used in indus- the asymmetric deformation of the sensitivity profile with
try, it nevertheless acts as a reaction promoter in SnO2 . The respect to the sensitivity maximum SM occurring at the tem-
effects of Au are not as strong as those of Pt, but still TM perature TM as well as the sub-linear variation of S with the
for the H2 detection is lowered somewhat, which is also re- analyte gas concentration cgas .
S. Ahlers et al. / Sensors and Actuators B 107 (2005) 587–599 597
The experimentally accessible parameters SM and TM , was that under equilibrium conditions, mobile donors should
which characterise the sensitivity distributions, are related give rise to a narrowing of the space charge zones. More quan-
to the microscopic energy parameters Eads and Ea . The first titatively these authors propose that the usual parabolic band
of these parameters describes the strength of the analyte gas bending profile should be replaced by a logarithmic one. In
binding on the metal oxide surface and the second the ki- this way, the distance to the surface, that needs to be traversed
netic barrier that needs to be overcome to induce a surface by a tunnelling electron, is reduced.
combustion event.
Fits to experimental gas sensitivity data for the gas species A.2. Fermi-energy dependence of the oxygen vacancy
CO, C2 H4 and H2 indicate that Eads and Ea tend to depend on concentration
the analyte gas concentration and thus on the surface coverage
of analyte molecules on the sensor surface. Additionally, the concentration of oxygen vacancies is un-
A comparison of undoped and noble-metal-doped SnO2 likely to be constant throughout the space charge zone. Start-
films illustrates that the addition of catalysts, in general, pro- ing out from the undepleted bulk material, an upward band
motes surface reactions by changes in both energy parame- bending causes the Fermi energy to retreat more and more
ters. from the conduction band edge as the free surface is ap-
proached. According to Hellmich [56] a change in the Fermi
energy relative to the band edges causes the vacancy concen-
Acknowledgement tration to increase. In [56] the reason for this increase has
been traced to the fact that part of the formation energy of an
Part of this work has been financed by the Bundesminis- oxygen vacancy–interstitial pair is regained by statistically
terium for Education and Research (BMBF) under the con- dropping the two valence electrons trapped at an oxygen va-
tracts 16SV1129/5 (MISSY) and 16SV 1532 (IESSICA). cancy onto the Fermi energy. As an upward band bending
lowers the Fermi energy with respect to the conduction band
edge, the density of oxygen vacancies should steeply increase
Appendix A. Efficiency of electron tunnelling as the free surface is approached. This effect in turn reduces
through metal oxide surface barriers the extent of the space charge region, so that in an equilibrated
state, it is likely to extend only a few nm into the metal oxide
The function for the temperature- and concentration- bulk.
dependent gas response of metal oxide materials S(T, cgas )
presented in Section 4, was derived by assuming tunnelling A.3. Tunnelling through dopant states
transparency through the adsorption-induced surface band
bending profile. In this Appendix A we should like to present Oxygen vacancies act as the main donors in tin oxide
more supporting evidence in favour of this assumption. Our and other pure metal oxides. These vacancies give rise to
arguments rely on three items, which are specific for metal localised levels below the conduction band edge of about 30
oxide semiconductors: and 150 meV [46]. The shallower one of these can be ex-
pected to be emptied at common operating temperatures of
A.1. Narrowed band bending due to oxygen vacancy more than 300 ◦ C (about 50 meV thermal energy). When the
mobility band bending near the surface rises above 0.15 eV the deeper
state will also become emptied, resulting in a situation as
The surface band bending in a semiconductor with bound sketched in Fig. 12 above.
surface charges can be determined by solving Poisson’s This latter figure displays a situation of a highly doped
equation. The standard solution to this problem results in metal oxide layer. In a typical metal oxide gas sensor, an
a parabolic band bending profile extending from the surface electron can travel from one state to another via thermally
into the undepleted bulk material. The assumptions made to activated hopping to arrive at the free surface [57]. Fig. 12
arrive at this standard solution are: zero mobile charge den- shows that much smaller amounts of thermal energy need
sity within the space charge region and a fixed concentration to be expended to arrive at the free surface by proceeding
of doping atoms within the semiconductor crystal. The first through a series of hops over localised bandgap states than
assumption is generally not true, especially in the case of by direct thermionic emission over the surface barrier. The
shallow band bending profiles. The second is usually correct, rate of charge transfer between bulk and surface will there-
but in the special case of metal oxides, where donor impu- fore depend much less on temperature in the case of hopping
rities are relatively mobile oxygen vacancies, the validity of as in direct thermionic emission over the barrier. In order to
this latter assumption is likely to break down. arrive at mathematically tractable equations we therefore de-
The subject of oxygen vacancy motion has been thor- cided to neglect the smaller temperature dependence of the
oughly investigated by Kamp [55]. Rantala et al. [47] have hopping transport with regard to the much larger impact that
investigated the influence of this effect on the shape of the reaction activation and adsorption energies have on the reac-
near-surface band bending profile. The conclusion reached tion kinetics and the sensitivity of a metal oxide gas sensor.
598 S. Ahlers et al. / Sensors and Actuators B 107 (2005) 587–599
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