Talanro,Vol. 38, No. 10, pp. 1169-I 175, 1991 0039-9MO/9I 53.00 + 0.

00
Printed in Great Britain. AI1 rights reserved Copyright0 1991PergamonPressplc

PROMOTION OF TIN OXIDE GAS SENSOR BY

ALUMINUM DOPING

CHAONAN
Xv, JUN TAMAKI,NORIOMIURAand NOB~RUYAMAZOE
Department of Maierials Science and Technology, Graduate School of Engineering Sciences,
Kyushu University 39, Kasuga, Fukuoka 816, Japan

(Received 29 November 1990. Accepted 4 February 1991)

Summary-Effects of Al-doping on tin oxide based elements were investigated in the Al content range
O.OOl-5.000%. Gas sensitivity to H, and i-C,H,, was found to be promoted extensively when 1 or 5%
Al was doped, while promotion was modest with doping up to 0.1% Al. Seebeck coefficients indicated
that carrier concentration decreased with Al-doping, resulting in an increase in Debye length. At the same
time, the crystallite size of tin oxide was found to decrease especially drastically when Al was doped
excessively. It was concluded that the increased Debye lengths and decreased crystallite sixes were
combined to produce the microstructure responsible for extremely high gas sensitivity of 1 and 5%
Al-doped elements.

Gas sensors based on semiconductive oxides,
represented by tin oxide, are very important
devices for detecting the leakage of inflammable
gases. Research on semiconductor gas sensors
is being directed more and more towards
their use in monitoring lower levels of gaseous
components such as odours and harmful gases
generated from various origins. To measure
such low level components, however, the sen-
sors need to be improved in several respects and
gas sensitivity in particular should be promoted.
Our recent investigation has revealed that this
type of sensor is strongly influenced by the
microstructure of sensor elements. The gas
sensitivity (S) of SnO,-based elements increases
steeply as the grain size (D) of SnO, decreases
down to cu. 6 nm. A simple model analysis has
shown that such a grain size effect shows up
when D decreases to be comparable with 2L,
where L is the depth of space charge layer. This
shows the importance of controlling D to a size
comparable with or less than 2L. At the same
time, this also suggests that control of L instead
of D would give rise to a similar effect. It is
known that L of a semiconductor can be con-
trolled by doping impurities inside the lattice.3
In the case of SnO,, L will increase with A13+-
doping, while it will decrease with Sbs+-doping,
for example, according to the vacancy control
principle. In fact, our preliminary study has
confirmed that A13+- or Sbs+-doping leads to a
drastic change in gas sensitivity in accordance
with the expectation. These findings have
1169
prompted us to investigate the doping effects
in more detail. This paper deals with the effects
of Al+-doping on SnO,-based sensors. First
we have examined how the gas sensitivity is
modified with varying extents of AP+-doping
and then we carried out the measurements
of Seebeck coefficients in order to estimate
important parameters for understanding the
doping effects.
EXPERIMENTAL
Hydrous SnOz powder was prepared by
neutralizing a cold solution of SnCl, with
an aqueous ammonia solution, followed by
thorough washing with demineralized water,
drying at 100 and grinding. It was calcined at
a prescribed temperature for 1 hr in air to obtain
undoped SnO, powder. To dope A13+into SnOz
lattice (A13+-SnO,), an aqueous chloride mix-
ture (SnCl, +AlCl,) was treated with an
aqueous ammonia solution. Aluminium content
was varied in the range O.OOl-5.000% in the
atomic composition Al/(Al + Sn). The resulting
coprecipitate was washed, dried and calcined at
a temperature of 1100. The mean size of SnO,
crystallites was evaluated from the width of the
X-ray diffraction (XRD) line of the (101) plane,
based on Scherrers equation.
To fabricate porous sensor elements, each
powder sample prepared above was mixed with
water, and the resulting paste was applied on
an alumina tube with Pt wire electrodes and
1170 CHAONAN
Xv et al.

TL

,oo _ A =JPP~ H,
v lOOOppmI-C4HIQ
Pt-Rhr
,E
0
d 108 -
furnace
5
s;
0 107 -
a

I I 8
lo
16' 10-Z IO-' 100 IO'
Amount of Al.%

Fig. 2. Electrical resistance and gas sensitivity towards 800

-~
; \
gas out c
91066
Fig. 1. Apparatus for Seebeck effect measurements. T, and
HL denote temperatures at the high and low temperature
ends of the specimen.
sintered at 700 for 4 hr in air unless otherwise
stated. The gas sensing properties of each
element were examined in a heated chamber
through which air or a sample gas was allowed
to flow at a rate of 150 cm3/min. The gas
sensitivity was defined as the ratio of electric
resistance in air (R,) to that in the sample gas
(R,).
Measurement of the Seebeck effect was
carried out in an apparatus shown in Fig. 1.
Each powder sample was pressed into a ribbon-
shaped specimen (3 x 15 x 0.3 mm) under a
pressure of 1000 kg/cm2, and calcined at 800 or
1100. The two ends of the specimen were fixed
onto a quartz rod with silver paste, together
with two Pt/Pt-Rh thermocouples as shown
in Fig. 1. The assembly was set in a quartz
chamber located inside an electric furnace. The
temperature difference of the specimen was
measured with the two thermocouples, while the
difference in electric potential (thermoelectric
motive force) was measured between the Pt
ppm H, and 1000 ppm i-C,H,, correlated with the amount
~
of Al doped into SnO, elements.
sample
wire electrodes of the thermocouples in a flow of
dry air.
RESULTS AND DISCUSSION
Properties of Al-doped sensors
Figure 2 shows the electric resistance (R,,)
of the sensor elements at 300 in dry air as
a function of Al content. R, increased with
increasing Al content up to 1% Al, above which
R, was saturated. This behaviour suggests that
the solubility of Al in SnO, is 1% or less under
these conditions. On the other hand, gas sensi-
tivity (S) showed quite different dependence on
Al content. As also shown in Fig. 2, S to both
H2 (800 ppm) and i-C4HI0 (1000 ppm) increased
only slightly up to 0.1% Al, and then increased
dramatically. These properties of doped
elements are summarized in Table 1, together
with the data of the undoped one. The gas
sensitivity could be promoted greatly when Al
was doped by 1 and 5%.
We have reported that for undoped SnO,
elements the crystallite size of SnO, (D)
seriously affects the electric resistance and gas
sensitivity. The crystallite size data for the pre-
sent elements are also shown in Table 1. It is
seen that D decreases with an increase in Al

Table 1. Properties of the Al-doped SnO,

Gas sensitivity
Amount Calcination Grain size log &/ohm
of Al conditions D}nm (3OW I-4 i-C,H,,
0 (undoped) 8OOC.4 hr 25 5.30 30 41
0.001% llOOC.3 hr >60 5.63 37 41
0.01% l100C.3 hr >60 6.34 50 45
0.1% llOOC.3 hr 60 7.74 69 48
1% llOOC~3 hr 43 8.93 118 145
5% llOOC*3 hr 19 8.84 204 201
 Promotion of tin oxide gas sensor by aluminum doping
content. This suggests that the properties of
Al-doped elements are affected not only by the
dissolution of Al into the lattice of SnO, but also
by a change in D. As seen in Table 1, D was
as small as 43 and 19 nm at Al contents of 1
and 5%, respectively, even under the severe
calcination conditions applied. For those
particular samples, the part of Al content
in excess of solubility limit seems to have acted
as a stabilizer of the ultrafine crystallites of
SnO, .
In order to examine the crystallite size effect
in Al-doped elements, the resistance (R,) and
the gas sensitivity (S) to 800 ppm Hz are shown
as a function of D in Fig. 3 together with the
data of undoped elements already reported.
Only two elements doped with 1 and 5% Al
were available for this correlation because the
other elements had D values too large to be
determined from XRD. The R, us. D relation for
undoped elements is divided into two regions:
R, decreases steeply with increasing D in the
small D region, while R, increases slightly in the
large D region. As has already been pointed
out, such D dependency of R, results from
whether D is smaller or larger than twice the
depth of space charge layer (2L). From the D
value bordering the two regions, L is estimated
to be cu. 3 nm for the undoped SnO,. For 1 and
(a)
100 A-.-.-.-.4-
t Al-doped
E two points of a semiconductor when a tempera-
t Ii, __
---
0 IO -
d The Seebeck coefficient (Q) is defined as a
f 10,
SnO,
a i-
IO_ : tween the two points, Q can be obtained as the
4 1 1 I 1 I 1 I
0 IO 20 30 40
Crystallite rire,nm
Crystallite size,nm
Fig. 3. Influence of crystallite size in Al-doped and undoped
elements on (a) electric resistance and (b) gas sensitivity
towards 800 ppm H,.
1171
5% Al doped elements, on the other hand, R.
was very large (lo9 ohm) and exhibited no such
dependency on D. As shown in Fig. 3(b), the gas
sensitivity (S) of undoped elements increases
drastically when D decreases down to 6 nm or
less. When compared with these elements, the
gas sensitivity of Al-doped elements was still
very high at D as large as 20 nm or more. These
data clearly show that both crystallite size (D)
and impurity levels of SnO, bulk are important
in determining S of Al-doped elements.
Seebeck coeficients
The valence control principle predicts that
when trivalent ions (A13+) are partially intro-
duced into the lattice, the carrier concentration
(n) of SnO, will decrease, leading to an increase
in Debye length. In addition to such a change in
the electronic structure in the bulk, however,
actual Al-doped elements showed a change in
the size of SnO, crystallites depending on Al
content, as just mentioned. Furthermore, one
cannot know a priori what portion of doped Al
ions would in fact have entered the SnOz lattice.
Under such conditions it seems imperative to
separate the electronic structure factor from the
microstructure factor for a basic understanding
of the effect of Al-doping. For this purpose, we
tried for the first time to evaluate the electronic
structure of polycrystalline SnO, from the
measurements of Seebeck effect.
The Seebeck effect is defined as the generation
of a thermo-emf (electromotive force) between
ture difference is applied between these points.4
temperature derivative of thermoelectric poten-
tial (V). Under the condition that both electric
field and temperature gradient are uniform be-
I ratio of emf (AV) to the temperature difference
50
(AT).
dV AV
Q =dT=rT (1)
Thus Q was evaluated by measuring AV
while applying AT between the two ends of the
ribbon-like specimen. In all measurements, the
lower temperature end was fixed to 300 and AT
was set to be 10 or less. Prior to each measure-
ment, the specimen was heat-treated at 500 for
30 min in dry air to eliminate possible surface
contaminants like water and C02, and then kept
at the temperature of measurement for 2 hr for
stabilization.
1172 CHA~NAN Xv et al.

Table 2. Seebeck coefficients and related characteristics of Al-doped

sno,
Amount
of Al AV,mV AT,"C Q, pV/K n, cm- L,, nm
0 (undoped) -2.045 10 -205 4x 108 2.8
0.001% - 2.302 9 -256 2x 108 4.0
0.01% - 3.052 -339 8x 10 6.4
0.1% -4.600 8 -575 5x 106 25.0
1% -6.400 8 -800 (4 x IO) (88.5)

The values of AV, AT and Seebeck coefficient,
Q, obtained are listed for each specimen in
Table 2. For an n-type semiconductor, Q is
known to be negative in sign. All the specimens
showed negative coefficients and the absolute
values were larger for larger amounts of Al-dop-
ing. For 5% Al-doped specimen this measure-
ment was not possible because of too large a
noise.
It should be noted that in the above
procedure the assumption of a uniform electric
field is an important approximation. For a
polycrystalline system, this assumption may not
always be verified because of the surface barrier.
This matter will be discussed later.
Carrier concentration
For an n-type semiconductor of a single
carrier system, the carrier concentration (n) is
assumed to obey a Boltzmann distribution,
n = NC *exp[ - (EC - E,)/k], where EC and EF
are the electronic potentials at the conduction
band edge and Fermi level, respectively, and NC
is the density of states in the conduction band.
Then Q can be related with n by the following
equation.5*6
n = Nc/exp[-(eQ/kT) -A]
Here A is a constant associated with the trans-
port of energy and e is elementary electric
charge. For a non-degenerate semiconductor,
A = 2 and NC = 2(2nm*kT/hZ)32, where m* is
the ratio of effective mass to mass of electron
evaluation of n from Seebeck coefficients. The
decrease of n with Al-doping is in accordance
with the valence control principle. When it is
assumed that each Al ion introduced in the
lattice of SnO, traps a conduction electron, the
observed decreases in n suggest that all Al ions
enter the SnO, lattice up to 0.01% Al-doping,
while only small portions of Al ions do so for
larger amounts of Al-doping.
Debye length and the depth of space charge layer
When an n-type semiconductor has a carrier
concentration of n, the Debye length is given as
follows.
L, = (EkT/e2n) (3)
Here L is the dielectric constant of the semi-
conductor and is ca. lo- F/cm for Sn02.12
Thus LD can be directly derived from the data
of n, as shown in Table 2 and Fig. 4. An increase
in Al content is seen to increase L, drastically;
while LD was 3 nm for undoped Sn02, it
was 25 nm at 0.1% Al. The L, value at 1% Al
(88 nm) apparently far exceeded one half of the
crystallite size (43 nm), but because the various
assumptions used for deriving it may not always
be justified under such conditions this is not
(2) definite. Nevertheless, it can be concluded
clearly that Lo is rather close to l/2 D at 0.1 O/O
l
/
,
I

I
and ca. 0.2 for Sn02.~*

2
In this way, one can evaluate the concen- - -
tration of carriers from Q data by using
equation (2). Resulting carrier concentrations
(n) are shown in Table 2 and Fig. 4. It is seen \
\
that n decreases steeply with an increase in \\
doping amount of Al 3+, from 4 x lOI* (cme3) v
for undoped SnO, to 4 x 10 (cm-) for 1%
A13+ doped sample. The n value of undoped
L
SnO, coincides well with that reported for 10-a 10-e IO-' IW IC

porous SnO, thin films which falls in the range Amount of Al. %
of 10s-109 (cme3) depending on the prep- Fig. 4. Influence of Al content on carrier concentration and
aration methods. This seems to verify the Debye length of Al-doped SnO,.
 Promotion of tin oxide gas sensor by aluminum doping
conduction electrons lotwed donors
G According to our previous study with TEM
t5
(b) Ev ~,,,,,,
E j
s tured as composed of three dimensional arrays
c I I W
X L
Fig. 5. Idealized model for oxygen adsorption on an n-type
semiconductor. (a) Charge distribution. (b) Energy band
structure.
Al while it is far larger than l/2 D at 1% and
5% Al.
Lo is an important parameter in determining
the depth of space charge layer (L) when a
semiconductor interacts with a gas. In our case,
oxygen would be adsorbed on the surface of
SnOr crystallites. Figure 5 shows carrier distri-
bution and energy band structure schematically,
in the surface region. In the simplest case where
all donors are ionized and all conduction elec-
trons in the space charge layer are depleted, to
be trapped by surface states (adsorbed oxygen),
L is proportional to L, with a proportionality
constant being determined by surface potential
(eVs) and thermal energy as follows.3
L = (2eVs/kT)* L, (4)
Thus one needs the surface potential data for
estimating L, but unfortunately no reliable data
are available for SnO, . At 300, the proportion-
ality constant of equation (4) is close to unity for
eIs = 0.03 eV and increases with the square
root of increasing eIs. Considering that the
surface potentials are often of the order of
0.1 eV for other oxides,13-15L does not seem to
be much different from L, for SnO,. It is noted
that for undoped SnO, , L, (3 nm) coincides well
with the empirical value of L (3 nm) estimated
from Fig. 3(a).
Polycrystalline state of SnO,
Equation (1) used for the measurements of
Seebeck coefficients, assumes the uniformity
of both temperature gradient and electric
field between the two measuring points. These
requirements would be easily satisfied with a
1173
single crystal or a densely sintered specimen but
not with a porously sintered specimen, as used
in the present study, because of the surface
potential. Nevertheless, the measurements were
found to bring about rather reasonable values
of carrier concentration and Debye length,
especially for tmdoped SnO,. This suggests
that the specimens, though porous and poly-
crystalline, have a microstructure which some-
how meets the requirements.
observation and other techniques,16 the micro-
structure of SnO,-based elements can be pic-
of SnO, crystallites. Each crystallite is co-ordi-
nated with 4 neighbours, on average, through
necks of a diameter of 0.8 D (D = crystallite
diameter), whereas a far fewer number of grain
boundary contacts are also included in the
array. For simplicity, such a microstructure
can be reduced to a one-dimensional chain as
schematically shown in Fig. 6. The connections
between neighbouring crystallites are provided
almost exclusively by necks and only scarcely by
grain boundary contacts. If D is larger than 2L,
the space charge layer forms only in the surface
region of each crystallite. The core region,
undisturbed by the surface effect, can extend
through necks in the chain until it terminates at
the grain boundary contacts. When a tempera-
ture gradient is applied in the chain direction the
resulting electric field inside the core region can
be uniform as long as neck contacts are avail-
able. In this situation, therefore, the Seebeck
effect can be measured without being disturbed
by the surface effect if grain boundary contacts
are scarce compared with neck contacts. This
situation was probably achieved in the present
specimens when Al contents were low. For
1 and 5% Al-doped samples which had D
smaller than 2L, however, Seebeck effects could
possibly be seriously disturbed by the surface
effect.
Implication of Al-doping for gas sensitivity
As mentioned above, the gas sensitivity of
SnO,-based elements towards H, (and i-C,H,,)
T+AT
I ID ,L I
i 1
Fig. 6. One dimensional model for interconnection of Sn02
crystallites in polycrystalline elements.
1174
could be promoted with Al-doping, with best
results at Al contents of 1 and 5%. Sub-
sequent analyses revealed that Al-doping had
two effects on the elements: the increase of
Debye length of Sn02 as a result of valence
control and the stabilization of microcrystalline
particles of SnO, . Both effects are quite favour-
able from the viewpoint of gas sensitivity, since
gas sensitivity has been shown to increase when
the crystallite size of SnOz is comparable with or
smaller than twice the depth of space charge
layer.
It is often asserted that gas sensitivity should
increase with increasing electric resistance of the
element on the grounds that a change in con-
duction electron concentration would bring
about a larger resistance change with increasing
resistance. Figure 7 shows the relation between
electric resistance (R,) and gas sensitivity (S) for
Al-doped SnO, in the present experiments.
Although S tends to increase with an increase in
R,, the relation does not seem to be as simple
as the above assertion. The increase of S is only
gradual in the R, range below lo8 ohm, while it
is quite steep above it. This tendency is well
coincident with whether D > 2L (gradual in-
crease) or D < 2L (steep increase), in agreement
with what was observed for undoped SnO*. This
strongly suggests that the observed increase of
S with Al-doping should be understood on the
basis of microstructure of the elements rather
than R,.
The present study indicates that the doping of
impurities in semiconductive oxides can be
an important method for promoting semi-
conductor gas sensors. As illustrated above, the
doping affects not only the electronic structure
but also the microstructure of the elements,
D>2L / lF2L
200-
IOQ-
I
0.001% I I
I I
0'
IO' IO'
Id Id
Fig. 7. Relationship between electric resistance in air and gas
sensitivity to 808 ppm H, at 300 for Al-doped elements.
Figures attached indicates Al contents.
CHAONAN Xv et al.
both being critically important for gas sensing
properties. There are many oxides which exhibit
semiconductive properties, but very few of them
have actually been used for gas sensors. As
the doping method can modify the properties
of oxides rather drastically, it is possible that
new sensing materials are developed by this
method. Although this method has hardly
been applied so far, research in this direction
is desired for further development of gas
sensors.
CONCLUSION
The effects of Al-doping on SnOz
elements were investigated with respect to
gas sensing properties as well as electronic
and physical structure of the elements. Gas
sensitivity to H2 and i-C4HI0 is promoted
tremendously when Al is doped by 1 and
5% although promotion remains slight up to
0.1% Al. Seebeck effect measurements indicate
that Debye length increases with Al-doping,
while XRD shows that SnO, crystallite size
(D) decreases with Al-doping. As a result
of these two effects, the relation D < 2L
(L = the depth of space charge layer) is achieved
when 1% or more Al is doped and this is a
reason for the high gas sensitivity of these
elements.
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