Temperature Modulated MEMS Metal Oxide Gas Sensors
Tu Xiang Zheng
Metal oxide sensors are very popular as a consequence of their
reasonable price and good durability. However,
they are lack of selectivity and response drift, which is why are used in low
cost alarm-level gas monitors for domestic and industrial applications. It is
important to propose new methods, which are able to improve the
state-of-the-art in gas sensing. In order to do so, the temperature modulation
of sensors has been proposed.
From electron spin
resonance (ESR) measurements it has been proposed that adsorbed oxygen can be
present in various chemical species transferring electrons from gas sensing
oxide to the chemisorbed oxygen according to the following process:
O2(gas)⇔O2(ad)⇔O2−⇔O−(ad)⇔O2−(ad)⇔O2−(lattice)
The temperature
dependence of the different species has been examined. It states that an oxygen
transition temperature is at 150 °C. Below 150 °C oxygen is mainly present as O2- and above chemisorbed oxygen in the forms
of O- or O2- is present. This change in chemistry
was correlated to a decrease in sample conductivity that occurred at around 160
°C. From these dependences the following basic mechanism for detection of
combustible gases seems plausible: If the gas sensor is operated under ambient
conditions it can be assumed that chemically adsorbed oxygen species are
present at the surface. Combustible gases may react with these oxygen species
and thus result in depletion of charged surface oxygen which in turn increases
the conductivity of the gas sensing material. In this way combustible gases may
not directly interact with the gas sensing material but its presence controls
the concentration of pre-adsorbed oxygen, which controls the surface charge and
thus the conductivity of the gas sensor.
According to this mechanism,
it can be concluded that the modulation of a metal oxide sensor working
temperature alters the kinetics of adsorption and reaction that occur at the
sensor surface in the presence of atmospheric oxygen and other reducing or
oxidizing species. It is reasonable to inference that sensor response patterns
are characteristic of the species present in the gas mixture. Actually, many works
have demonstrated that modulating the operating temperature of the sensors can
achieve a high degree of selectivity. As an example, two components in a
mixture of CO and NO2 in air has been simultaneously and accurately quantified by
processing the response dynamics of a single micromachined tin oxide sensor
operated in a temperature-modulated mode.
Similar to the above example, the MEMS
metal oxide gas sensors proposed by the present author have their operating temperature modulated in a more
efficient way. As well known, the thermal time constant of screen-printed
sensors is quite large. As a result, up to now the temperature modulation
frequency (20 MHz) has been too low and the corresponding principle-related
response time (50 s) has been too high for many applications. With a
special design, the thermal response of the MEMS
metal oxide gas sensors is as low as 0.8 ms, as shown in the above figure. It compares much
favorably with the thermal response of seconds found in conventional
sensors.
The MEMS metal oxide gas sensor is based on a silicon wafer and
fabricated utilizing CMOS technologies. Since the sensor is required to be
operated at an elevated temperature a thermal insulating base is formed in the
silicon wafer which is used to support the sensor body. Both a resistor for
heating and a thermopile for temperature sensing are formed on the thermal
insulating pad. Then depositing an electrical insulating layer and laying a tin
dioxide layer is formed thereon. By employing such device structure with good
thermal insulation to the silicon wafer, the sensor presents a series of
advantages such as miniaturized size, low power consumption, and fast response.
In operation, the MEMS
metal oxide sensor is exposed to a gas mixture, using a fully automated test
setup, which consisted of computer driven mass flow controllers, a sensor
chamber, and a data acquisition system for measurements in the millisecond
range. The temperature of the sensor is varied by applying a modulate voltage
to the heating resistor. Temperature range and frequency have been optimized.