ICSE2006 Proc.

2006, Kuala Lumpur, Malaysia

The Gas Sensing Potential of Nanocrystalline SnO2 and In203

Powders Prepared by Mechanical Milling
Goib Wiranto, Member IEEE, Adiseno, I Dewa P Hermida, Roberth V. Manurung, Slamet Widodo,
and Masbah R. T. Siregar
Research Centre for Electronics and Telecommunications
Indonesian Institute of Sciences (LIPI)
Jl. Sangkuriang, Bandung 40135
Ph. 62 22 250 4661 Fax. 62 22 250 4659
Email.
Abstract - The use of nanocrystalline metal Examples are Figaro TGS series gas sensors for
oxide powders to increase the sensitivity of gas the detection of CO, NH3, H2S, CO2, and air
sensors has been the subject of this research. contaminants.
Of particular interest to our application in A lot of work, however, still needs to be done
environmental monitoring is 1n203 and SnO2, to improve the sensitivity of gas sensors based on
which are known, respectively, to have a high metal oxide semiconductors. In previous works,
sensitivity to oxidising polutan gases such as many have shown that the use of nanosized
NO2 and 03, and reducing polutant gases such particles in the fabrication of thick-film gas
as CO and NH3. Preparation of undoped sensors have significantly increased their
nanocrystalline SnO2 and 1n203 powders by sensitivity [3-5]. Although the detection limit can
mechanical milling via centrifugal action have be decreased to below the allowable threshold set
been conducted. The technique used has by international standards, the reproducibility of
allowed the reduction of grain sizes from 3 - 5 nanoparticles regarding their chemical
,um to below 100 nm with no contaminating composition and surface contamination remains
carbon content, as confirmed by SEM and problematic. On the other hand, the perfect
EDS spectra analysis. Furthermore, the FTIR control of nanoparticles surface as well as a good
spectra indicated that the SnO2 nanopowders knowledge on the chemistry of the gas-solid
had a strong band at 671 cm-' and 1n203 at interface are important in optimising the gas
601 cm-. The resulting nanowpowders were sensor performances.
then mixed with oc-based terpinol to produce a The use of nanocrystalline metal oxide powders
thick film paste as an active material of gas consisting of In2O3 and SnO2 for gas sensors has
sensors, and applied to an alumina platform been the subject of this research. Thick film
consisting of AgPt heater and electrode tracks. technology will be used in the fabrication of the
sensor structure, including the metal oxide paste
I. INTRODUCTION and the subsequent screen printing of the heater,
electrode, and sensitive layer on an alumina
ONLINE monitoring of gaseous pollutants is substrate. In this paper, the preparation of the
becoming more and more important as the need nanocrystalline In203 and SnO2 powders using
for high quality outdoor air is increasing. Such mechanical milling will be presented, taking into
monitoring requires gas sensors and telemetric account the effect of rotation speed, time, and
system capable of delivering information about sintering temperature.
pollutant parameters at real time from the
designated measurement stations [1]. Among II. THEORETICAL BACKGROUND
other types, perhaps gas sensors based on metal
oxide semiconductors have been the most widely It has been known that the mechanism of gas
studied and applied in such environmental detection by sensors based on semiconducting
monitoring [2]. This is usually due to their materials is due to variation in electrical
simplicity and reliability. In addition, the conductivity caused by adsorption of gases on
availability of thick film technology has made the semiconductor surface [6]. Thus, the surface
their fabrication process very cost-effective, and of the semiconducting materials plays a major
thus many commercially available gas sensors role compared to the bulk. Its reactivity to gases
have been produced using this technology. can be increased by increasing the spesific

0-7803-9731-2/06/$20.00 ©2006 IEEE 83

 ICSE2006 Proc. 2006, Kuala Lumpur, Malaysia
surface area of the semiconducting materials. By
reducing the particle size of the semiconducting
materials down to nanometer scale, a large
increase in the spesific surface area can be
obtained [7].
In thick film technology, the sensing layer is
very porous and consists of numerous
interconnected metal oxide grains in the form of
single crystals or polycrystalline agglomerates.
However, the high porosity enables the ambient
gases to access the intergranular connections. As
a results, the gas interaction can take place at the
surface of individual grains, at the boundaries
between grains, and at the interface between
grains and electrode and substrates.
There are two kinds of reactivity that may take
place at the semiconductor surface with the
presence of gases. The first reactivity is due to
the presence of oxidising gases such NO2 and O3,
in which case oxygen adsorption at the
semiconductor surface forms negatively charged
oxygen species. As a result, the electrical
conductivity of n-type semiconductor decreases.
The second reactivity is due to the presence of
reducing gases such as H2, NH3, CO, and
hydrocarbon in which case oxygen adsorption at
the semiconductor surface causes electron
injection to the conduction band. As a result,
electrical conductivity of n-type semiconductor
increases. This oxygen adsorbtion in ionic form
can be described in the following reactions
02 + 2e -* 20 ads
02 + e -* 02ads
III. EXPERIMENTAL
2.1 Powder preparation
Nanosized SnO2 and In203 powders were
prepared by mechanicall ball milling process of
centrifugal-type. The process was done at room
temperature. Initially, each semiconducting metal
oxide powder, with average grain size of 3 - 5
pm, was mixed with acetone. The amount of
SnO2 powder was 35 g, and that of In203 was 15
g. The milling process was then performed with
stainless steel balls with diameter of 12 mm. The
number of balls used was 12, and the speed of
rotation was maintained at 250 rpm. The milling
process was done for 15 hours with 15 minutes
paused after every hour.
Upon completion of the milling process, the
nanopowder was let to dry in air and then half of
each powder was sintered at 700 °C for 8 hours.
Analysis of the nanopowders was then performed
using SEM, EDS, and FTIR. To make a printable
metal oxide paste, the nanopowders were mixed
with a-based terpinol. To obtain a suitable
viscosity, the a-based terpinol was added
dropwise to the nanopowders followed by
constant stirring. Figure 1 shows the steps
involved in the preparation of the thick film paste
based on the metal oxide nanopowders.
MIX WITH a
MIX WITH BASED
ACETONE TERPINOL
BALL MILLING
SEM EDS
ANALYSIS
FTIR
DRYING 1 SINTERING
Fig. 1 The flowchart summarising the steps in
the preparation of the thick film paste
based on SnO2 and 1n203 nanopowders
(1) 25 mm
(2) A
Fig 2. Layout of the gas sensor platform on
A1203 substrate
2.2 Fabrication of the gas sensor platform
The gas sensor platform has been fabricated on
an alumina (96% A1203) substrate. The size of
the alumina substrate was 2 x 2 inch with a thick
ness of 0.7 mm on which up to 10 sensor
platform can be fitted with dimension as shown
on Figure 2. Each platform consists of an
interdigitated AgPt electrode for measuring the
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 ICSE2006 Proc. 2006, Kuala Lumpur, Malaysia

sensor resistance and heater track for keeping the
sensor at the operating temperature.
Initially, the alumina substrate was
mechanically drilled on each pad as a means for
the sensor interconnection with the electronic
circuitry. The high operating temperature of the
sensor has restricted the use of solder-based
interconnection. An AgPt paste was then screen
printed, dried, and fired.
The fact that the original SnO2 powders were
mixed with acetone before the milling process
has made the resulting nanopowders have a high
carbon content even after drying. The EDS
spectra in Figure 5 shows that the SnO2
nanopowders contain 16.82% of C. After
sintering at 700 °C for 8 hours, all the C content
can be completely removed. This is shown in the
EDS spectra on Figure 6.

Fig 4. SEM picture of SnO2 nanopowders with

Fig 3. SEM picture of SnO2 nanopowders, the same average grainsizes but showing
with an average nanograin size of less the formation of agglomerates
than 100 nm

IV. RESULTS AND DISCUSSION

4.1 Tin oxide nanoparticles

'2100

Figure 3 and 4 show the SEM pictures of the

SnO2 powders before and after sintering at 700 S{O-
°C. As can be seen, an average grain size of less Element (;keV~) mass%f Error%O ,At% ompound
-I
1- I.-

than 100 nm has been achieved. Although a

mass% Cation
C K4 0,277 l 6.82 0.1 6 49,59 2.2643
O K4 0 525 l 3.37 1 .46 29,58 5,2337

complete particle reduction to nanoscale can not Sn L 3B.442 Eig.81

00.00
1.04 20.82
001.00
82.5020

be obtained, but still a significant reduction of

more than 97% from its original grain size of 3-5 Fig 5. EDS spectra of the SnO2 nanopowders before
sintering at 700 °C
ptm is achievable with this technique. The actual
quality of the nanopowder depends on many
factors, such as the size of the original grain, the
weight of the powder, ball-to-powder mass ratio,
rotation speed, angle of collision, milling
atmosphere, milling time, and milling
temperature [8]. usoo~~~~~~~~- I

The effect of sintering at 700 °C on the SnO2

powders is apparent from the formation of
agglomarates on the nanopowders. This is in Element (ke\o mass% Error%6 At% Compound mass% Cation K
accordance with the previous work [9], which O
Fe K
Sn L
6.398
3.442
21.25
0.85
77.91
1.12
1.06
2.26
97.74
FeO
SnOr
1.09
98.91
0.27
11.86
1.0988
98.9012
showed that increasing the temperature and time Total 1 00.00 1 00.00 1 00.00 1 2.1 4

of sintering process will increase the average

grain size, although the effect of sintering time is Fig 6. EDS spectra of the SnO2 nanopowders with
the C content completely removed
not significant at high temperatures above 600
OC.

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 ICSE2006 Proc. 2006, Kuala Lumpur, Malaysia

The main problem of using the centrifugal ball

milling process is related with powder
contamination. The EDS spectra on Figure 6
shows that a small amount of Fe (0.85%) present
in the SnO2 nanopowder after sintering. The
present of Fe in the form of FeO (1.09%) could
be due to particles left in the oven chamber. The
addition of FeO in SnO2 and its effect to the
sensor response to gases will be interesting as
indicated in the previous work [10].

Fig 8. SEM picture of the In203 nanopowders

milled at 250 rpm for 15 h

Fig 7. FTIR transmission spectrum of the SnO2

nanopowders without sintering at 700 °C

Further analysis of the SnO2 nanopowders has

Fig 9. SEM picture of the In203 nanopowders
been performed using Fourier Transform Infrared sintered at 700 °C for 8 h
(FTIR) transmission spectroscopy. FTIR analysis
brings information on the interatomic bonds
constituting the bulk, the chemical nature of the
surface bonds, the possible presence of
contaminating species on the surface, the nature
of the adsorption sites, the free carrier density,
etc [11]. As such, it is possible to correlate the
surface reactions with the changes in electrical
conductivity of the nanopowders upon reaction
with gases, and this can be an important analysis
to obtain the gas sensing potentiality of the
nanopowders.
Figure 7 shows the FTIR spectrum of SnO2
nanopowders before sintering process at 700 °C. Fig 10. Infrared transmission spectrum of the
The main chemical species present on the surface In203nanoparticles
of the SnO2 nanopowders are hydroxyl (OH)
groups. They adsorb in the highest wave number
region (peak at 3448.5 cm-1) of the spectrum. The 4.2 Indium oxide nanoparticles
lower bands with the peaks at 1060.8 cm-1,
1380.9 cm-1, and 1635.5 cm-1 are problably Figure 8 shows the SEM picture of 1n203
attributed to hydroxide, molecular water, and Sn- powders after ball milling at 250 rpm for 15 h.
O-Sn bonds. The SnO2 bands have the peaks Unlike the case of SnO2, the resulting particle
around 671.2 cm-1. The FTIR spectrum of SnO2 sizes vary from less than 100 nm to 1 rtm. It is
powders after sintering at 700 °C did not show a suspected that the difference is caused by the
significant difference with that before sintering. higher grain size of the starting In2O3materials.
The effect of sintering the at 700 0C for 8 hours

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ICSE2006 Proc. 2006, Kuala Lumpur, Malaysia

is similar to SnO2. As shown in Figure 9, the AgPt thick film heater. Notice that in order to
nanopowders begin to agglomerate. maintain the heater temperature between 100 -
The FTIR spectrum of the In203 particles is 300 °C, the amount of power required is around 3
presented in Figure 10. Like the case of SnO2, - 9 Watts, which is typical for thick film

the band in high wavenumber (peak at 3467.8 technology.

cm-1) area correspond to surface hydroxyl (OH)
groups. Several peaks at the lower wave numbers V. CONCLUSION
(from 1026.1 to 1624.0 cm-1) are due to the
surface reaction of the nanoparticles with the In this paper, the preparation of SnO2 and In203
atmosphere. nanopowders for gas sensing application has
been described. The method of preparation has
been based on the use of ball milling process of
14
r16
centrifugal type. With the rotaion speed of 250
12
rpm for 15 h, the grain sizes of both metal oxide
powders were able to be reduced to less than 100
10 nm. Despite the presence of very small
§~8-
79-6
contaminating species, the EDS and Infrared
0-* 6. 24
spectra showed that the chemical nature of both
0L 6
nanopowders were stable, even after sintering at
--4. 75
4 700 °C for 8 h. Thus, the method of producing
3.454
25
such nanopowders is potentially useful for gas
2
sensor fabrication.
29 42 61 89 130 215 318
Temperature deg C
VI. FUTURE WORK

Fig 11. Temperature versus power characteristics The work presented in this paper is the first
of the AgPt thick film heater step towards the design and fabrication of gas
sensor system for environmental monitoring, in
which the main parts consist of gas sensors and
4.3 Characteristics of the thickfilm heater on-line telemetric system. Therefore many
aspects still need to be done including
One of the requirements for metal oxide based characterisation of these nanomaterials for their
gas sensors is their high operating temperature, responses to polutant gases, and the use of
which is normally between 100 - 300 °C. The MEMs technology in the fabrication of the
temperature of gas sensors influences their sensor platform. The work on this particular
sensitivity, selectivity, and response time. In this aspect is still in progress, and the results will be
research, the choice of using AgPt as the heater published elsewhere.
and electrode materials have been based on the
trade-off between cost and performance. An ideal ACKNOWLEDGEMENT
heater and electrode materials would be platinum
and gold, respectively. However, the cost of This work is financially supported by LIPI
platinum and gold pastes for thick film Competitif Project No. 27.04/SK/KPPI/II/2006
technology is almost ten times that of silver. on Development of New Methods in the Design
Unfortunately, silver is known to have an and Fabrication of Gas Sensor System for
electromigration at high temperatures. Therefore Environmental Monitoring.
for many applications, AgPt paste seems to be a
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