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Machine Olfaction Device (MOD) Sensors

(Part One)

There are a number of different types of sensors which can be used


as essential components in different designs for machine olfaction
systems.

1. Electrochemical sensors
2. Metal oxide semiconductors
3. Schottky diode-based sensors
4. Calorimetric sensors
5. Quartz crystal microbalances
6. Optical sensors

Electronic Nose (or eNose) sensors fall into five categories [1]:
conductivity sensors, piezoelectric sensors, Metal Oxide Field Effect
Transistors (MOSFETs), optical sensors, and these employing
spectrometry-based sensing methods.

Conductivity sensors may be composed of metal oxide and polymer


elements, both of which exhibit a change in resistance when exposed
to Volatile Organic Compounds (VOCs) [1].

In this report only Metal Oxide Semi-conductor (MOS), Conducting


Polymer (CP) and Quartz Crystal Microbalance (QCM) will be
examined, as they are well researched, documented and established
as important element for various types of machine olfaction devices.
The application, where the proposed device will be trained on to
analyse, will greatly influence the choice of sensor.

The response of the sensor is a two part process [3]:

1. The vapour pressure of the analyte usually dictates how many


molecules are present in the gas phase and consequently how
many of them will be at the sensor(s).
2. When the gas-phase molecules are at the sensor(s), these
molecules need to be able to react with the sensor(s) in order
to produce a response.

Sensors types used in any machine olfaction device can be mass


transducers e.g. QMB "Quartz microbalance" or chemoresistors i.e.
based on metal- oxide or conducting polymers. In some cases, arrays
may contain both of the above two types of sensors [4].

Metal-Oxide Semiconductors

These sensors were originally produced in Japan in the 1960s and


used in "gas alarm" devices.

Metal oxide semiconductors (MOS) have been used more extensively


in electronic nose instruments and are widely available commercially
[1].
MOS are made of a ceramic element heated by a heating wire and
coated by a semiconducting film. They can sense gases by
monitoring changes in the conductance during the interaction of a
chemically sensitive material with molecules that need to be
detected in the gas phase. Out of many MOS, the material which has
been experimented with the most is tin dioxide (SnO2) - this is
because of its stability and sensitivity at lower temperatures.
Different types of MOS may include oxides of tin, zinc, titanium,
tungsten, and iridium, doped with a noble metal catalyst such as
platinum or palladium.

MOS are subdivided into two types [4]: Thick Film and Thin Film

Limitation of Thick Film MOS: Less sensitive (poor selectivity), it


require a longer time to stabilize, higher power consumption. This
type of MOS is easier to produce and therefore, cost less to purchase.

Limitation of Thin Film MOS: unstable, difficult to produce and


therefore, more expensive to purchase. On the other hand, it has
much higher sensitivity, and much lower power consumption than
the thick film MOS device [5].

a. Manufacturing process [5]

Polycrystalline is the most common porous material used for thick


film sensors. It is usually prepared in a "sol-gel" process [5]:

Tin tetrachloride (SnCl4) is prepared in an aqueous solution, to


which is added ammonia (NH3). This precipitates tin tetra hydroxide
which is dried and calcined at 500 - 1000°C to produce tin dioxide
(SnO2). This is later ground and mixed with dopands (usually metal
chlorides) and then heated to recover the pure metal as a powder.

For the purpose of screen printing, a paste is made up from the


powder. Finally, in a layer of few hundred microns, the paste will be
left to cool (e.g. on a alumina tube or plain substrate).

b. Sensing Mechanism

Change of "conductance" in the MOS is the basic principle of the


operation in the sensor itself. A change in conductance takes place
when an interaction with a gas happens, the conductance varying
depending on the concentration of the gas itself.

Metal oxide sensors fall into two types [2]:

1. n-type (zinc oxide (ZnO), tin dioxide (SnO2), titanium dioxide


(TiO2) iron (III) oxide (Fe2O3)
2. p-type (nickel oxide (Ni2O3), cobalt oxide (CoO)

The n type usually responds to "reducing" gases, while the p-type


responds to "oxidizing" vapours.
Operation (n-type) [2]: As the current applied between the two
electrodes, via "the metal oxide", oxygen in the air start to react
with the surface and accumulate on the surface of the sensor,
consequently "trapping free electrons on the surface from the
conduction band" [2]. In this way, the electrical conductance
decreases as resistance in these areas increase due to lack of
carriers (i.e. increase resistance to current), as there will be a
"potential barriers" between the grains (particles) themselves.

When the sensor exposed to reducing gases (e.g. CO) then the
resistance drop, as the gas usually react with the oxygen and
therefore, an electron will be released. Consequently, the release of
the electron increase the conductivity as it will reduce "the potential
barriers" and let the electrons to start to flow [2].

Operation (p-type): Oxidising gases (e.g. O2, NO2) usually remove


electrons from the surface of the sensor, and consequently, as a
result of this charge carriers will be produced.

c. Limitation of MOS sensors [4]

1. Poor Selectivity - In particular when a thick film MOS device is


used. The poor selectivity can be reduced by the deposition of a
suitable catalyst layer of noble metals like Pd, Pt, Au and Ag
2. MOS need high temperatures (around 300°c) to operate
efficiently; this result higher power consumption
3. Sensitive to humidity and to compounds such as ethanol and CO2

d. Advantages [4]

1. Widely available in a variety of types and sensitivities


2. Very sensitive to a number of organic vapours (e.g. oil)
3. Fast response, usually less than 10 seconds

Najib Altawell © Altawell 2008

References

[1] Nagle, H. T., Schiffman, S. S., Gutierrez-Osuna, R. (1998) The How and
Why of Electronic Noses. IEEE Spectrum September 1998, Volume 35,
Number 9, pp. 22-34.
[2] Arshak K., Moore E., Lyons G.M., Harris J., Clifford S. (2004) A review of
gas sensors employed in electronicnose applications
[3] Hurst, W. J. (1999) Electronic Noses & Sensory Array Based Systems.
Technomic Publishing Company, ISBN No. 1-56676-780-6.
[4] Sberveglieri D. (1999) Metal-Oxide Semicondictors. ASTEQ Technologies
for sensors.
[5] Nose Office (2003) NOSE II - The Second Network on Artificial Olfactory
Sensing