Sensors and Actuators B 135 (2008) 342–351

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Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Development of ultra-low-power consumption MOX sensors with

ppb-level VOC detection capabilities for emerging applications
I. Elmi ∗ , S. Zampolli, E. Cozzani, F. Mancarella, G.C. Cardinali
IMM (Institute for Microelectronics and Microsystems), CNR (National Research Council), Via P. Gobetti 101, 40129 Bologna (BO), Italy

a r t i c l e i n f o a b s t r a c t

Article history: This paper deals with the development of state-of-the-art metal oxide semiconductor (MOX) gas sensors
Received 7 March 2008 based on ultra-low-power (ULP) consumption micro-machined hotplates and targeted to VOC detection at
Received in revised form 2 September 2008 ppb-level. A very simple, single metal, front-side silicon bulk micromachining fabrication technology was
Accepted 2 September 2008
conceived and proposed. Several types of ULP devices, differing in shape and size, have been designed and
Available online 9 September 2008
fabricated to assess both the most efficient layout geometry and optimal fabrication process parameters.
The ULP hotplates functional behavior was thoroughly investigated, and typical results on measurements
Keywords:
of the hotplate temperature vs. applied power are reported. A very satisfactory value of 8.9 mW at 400 ◦ C
Ultra-low-power hotplate
MOX sensors can be highlighted, for a device featuring an innovative self-insulated layout between heater and sensing
Volatile organic compounds layer. Transient temperature responses and evaluation of the hotplate thermal time constant were also
Benzene carried out. On the center of the suspended hotplate structures a thin film of tin oxide has been deposited
ppb-Level by means of modified rheotaxial growth and thermal oxidation (M-RGTO) process. A very controlled
amount of gold nanoparticles is finally sputtered onto the sensing layer to enhance its response to VOC
by catalytic effect. As expected and confirmed by morphological characterization the tin oxide film is
structured in nanoclusters very uniform in size. Results of functional characterizations towards different
gases under different working conditions are reported and prove the capability of detecting volatile organic
compounds (VOC) down to few parts a per billion (ppb).
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
During the last decades, several technologies for the fabrica-
tion of metal oxide (MOX) gas sensors have been proposed. Some
authors [1–3] follow the aim of maximizing gas sensor response,
mainly towards volatile organic compounds (VOC) in particular
benzene, considered the most dangerous compound related to
environmental pollution [4,5]. To supply the high working tempera-
tures needed for MOX chemo-resistive sensors operation, different
solutions are nowadays adopted. In some cases high power con-
sumption massive alumina substrates are used, while in other cases
several types of micro-machined hotplates have been developed to
provide low-power consumption substrates.
The power dissipation of the best performing micro-hotplates
for MOX sensors presented in literature [6–8] ranges from a few
hundreds down to some tens of mW, at the typical working tem-
perature of 400 ◦ C. These values permit to address some important
fields of applications, such as portable and handheld devices. Nev-
ertheless, a further reduction in power consumption at least by one
∗ Corresponding author. Tel.: +39 051 639 9109; fax: +39 051 639 9216.
E-mail address: elmi@bo.imm.cnr.it (I. Elmi).
order of magnitude is still necessary for MOX sensors to enter the
very innovative and fast growing field of wireless sensor networks
and RFID tags [9,10]. Furthermore, high performance portable
analytical instrumentations require detectors with enhanced sen-
sitivity and selectivity.
The aim of this work was to develop a MOX sensor array based
on an ultra-low-power (ULP) hotplate capable of operating at high
temperature with a power consumption lower than 10 mW and
having an extremely high sensitivity towards VOCs. Among these
compounds this paper focuses on aromatic ones like benzene, since
it is demonstrated to be carcinogenic for human beings [11]. Nowa-
days small, reliable, cheap and low-power consumption sensors
to directly detect benzene down to concentration of interest for
outdoor or indoor air quality monitoring are not still available.
To overcome the limitations and the drawbacks of the previously
developed MOX gas sensors and fulfil the above requirements, it has
been necessary to improve both of the basic device components:
the hotplate and the sensing layer. At the design stage a number
of constraints on material properties, device shapes and sizes were
considered. A front-side bulk micromachining technology, based
on a silicon nitride/silicon dioxide structural stack was set up and
several types of suspended hotplates were designed, fabricated and
comparatively characterized. A single Pt layer is used for patterning

0925-4005/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2008.09.002
 I. Elmi et al. / Sensors and Actuators B 135 (2008) 342–351
both the heating resistor and the sensing film contacts. Each hot-
plate layout was conceived to optimize the temperature uniformity
on the hot-spot of the suspended structures. Devices with different
hotplate sizes ranging from 54 to 120 ␮m and with various sensing
film contact schemes were designed and simulated using FEM soft-
ware (FEMLAB). To investigate the temperature behavior of the ULP
hotplates, some of them were equipped with specific temperature
sensors, obtained by replacing the sensing film Pt contacts with a
Kelvin resistor patterned on the same metallic layer.
The proposed hotplate fabrication technology was designed to
be compatible with sputtering or drop coating sensing layer depo-
sition processes. In both cases the devices have to withstand the
very high temperatures that are necessary for sensitive material
preparation and stabilization. In this work, a sputtering-based mod-
ified rheotaxial growth and thermal oxidation (M-RGTO) deposition
technique has been used, providing a dimensionally well controlled
nano-structured thin tin oxide sensing layer. A self-aligned process
for the sensing layer deposition on the micro-hotplates was imple-
mented. The sensing layer response towards VOC was specifically
enhanced by adding gold nanoparticles on the tin oxide surface.
Due to gold catalytic activity very low VOC concentrations (down
to ppb) can be measured with stable and reproducible response.
The selectivity of the sensing layer has been tested and proved
against typical interfering gases for environmental application such
as carbon monoxide (CO) and nitrogen dioxide (NO2 ).
The developed gas sensor array includes four functionally inde-
pendent devices integrated on a silicon chip of 1.0 mm × 1.5 mm in
size.
The proposed ULP sensors are therefore implementing several
innovative aspects in order to fulfil the application requirements
and to simplify the sensors’ fabrication process, while maximiz-
ing the sensing performance and reliability. The main innovations
concern:
• The reduction of the MOX sensor power consumption down to
low mW values, to enable addressing some emerging applications
like portable devices, wireless sensor networks or semi-passive
RFID tags.
• The small footprint of the sensor arrays, which results in a high
fabrication throughput and allows for the use of the sensors in
applications with small volume chambers and low gas flow.
• A simplified process flow, requiring a single metallization layer for
both the hotplate heater and sensing layer electrodes. The most
simple fabrication process requires only two lithographic masks
and reduces the device complexity, while increasing reliability
and yield.
• The suspended hotplates with circular symmetry allow for a
self-aligned sensing layer deposition process, with no need for
sensing layer definition using photoresist, chemical etching or
solvents. This simplifies the sensor fabrication process while
avoiding sensing layer poisoning, thus maximizing the sensor
performance.
• The state-of-the-art sensitivity of the ultra-low-power sensors,
which reliably detect low ppb concentrations of benzene in air.
2. Design and technological implementation
2.1. Hotplate design
The designed hotplates are based on suspended dielectric
structures of very small dimensions, released by front-side bulk
micromachining technology and implementing circular platinum
heaters and electrodes. The suspended structures are released on
a pit made by anisotropic etching of the silicon bulk, and the
343
heaters and electrodes are patterned in a single metallic layer. As
well known and extensively reported in literature [12–14] stress
compensation in suspended-arm micro membranes is of crucial
importance. A stress compensated stack composed of a silicon
nitride thin film deposited between two silicon dioxide layers
was chosen to implement the mechanically supporting and ther-
mally insulating structure of the hotplates. Platinum metallizations
feature a satisfactory trade-off between a quite low and stable elec-
trical resistivity and a fairly high thermal reliability.
The use of circular-heated structures, as previously reported by
other authors [15], allows to obtain a good temperature unifor-
mity through the symmetry properties of the device, avoiding the
use of massive silicon or aluminum temperature spreading struc-
tures. Moreover, the electrodes for contacting the MOX film were
designed to have the active sensing layer confined on a thin annular
region of the hotplate, where a good temperature uniformity can
be easily achieved.
The circular-heated structures are suspended on the pit and con-
nected to the silicon bulk by means of arms that provide mechanical
supports and electrical interconnections.
Several types of layouts were designed in order to investigate
the effects of different arm shapes and other specific geometrical
parameters on the thermal behavior and mechanical resilience of
the device.
The list of main parameters considered for the hotplate layout
design is shown in the table of Fig. 1 and reported below:
• the number and shape of the suspending arms: 2 straight arms
(bridge “B”), 2 tapered arms (minimal “M”), 4 tapered arms (extra
arms “E”);
• the number and type of MOX layer contact electrodes: 2 (“nor-
mal sensor”), 2 (“self-insulated layout”), 1 (“single electrode”), 0
(“temperature sensor”);
• the metallization line width and separation (“W”): 4 and 6 ␮m,
causing a variation of the suspended membrane diameter ranging
from 54 to 120 ␮m;
• the size of the etch pit (“P”) below the hotplate, 250 or 400 ␮m,
directly affecting the arms’ length.
To obtain a precise evaluation of the operating temperature as a
function of the heating power, each kind of device has been repli-
cated on the mask layout replacing the electrodes for contacting
the MOX sensing layer with a four contact platinum Kelvin resistor,
to be used as a temperature sensor.
Extensive investigations by means of 2D and 3D FEM simulations
(FEMLAB) based on validated models [16] were performed to assess
the influence of layout geometries and material properties on the
temperature distribution for every hotplate design. Fig. 2a shows
the temperature distribution on the center of the suspended circu-
lar structure. Differences lower than 20 ◦ C in the area between the
contact electrodes has been obtained for an average temperature
of 390 ◦ C.
In Fig. 2b, the results of 3D simulations of the temperature dis-
tribution for the complete suspended structure and its proximity
are shown; the color map illustrates the good thermal insulation
and focused heating capability of the designed device. Further
results obtained by means of 3D simulations, not reported for brief-
ness, show that pits deeper than 150 ␮m are not necessary and
do not provide better insulation, since the heating loss through air
becomes negligible compared to heat conduction through the arms.
Four identical ULP hotplates have been grouped in arrays, result-
ing in an autonomous chip having a dimension of 1.0 mm × 1.5 mm.
The array is composed by four completely independent devices,
using a common track with a balanced resistance distribution to
connect all the array heaters based on paths of variable width; in
344 I. Elmi et al. / Sensors and Actuators B 135 (2008) 342–351

Fig. 1. Different layout parameters considered in ULP hotplates design.

this way the heater resistance is not affected by the distance to the
bonding pads.
Due to the small footprint of complete device, more than 4000
sensor arrays are obtained from a 4-in. wafer, which results in a
high fabrication throughput.
2.2. Fabrication process
A three-mask, front-side bulk silicon micromachining process
flow was set up for fabricating the hotplates on 4 in. single side
polished 300 ␮m thick Si wafers. The main steps are shown in Fig. 3,
where all the layer materials and thicknesses are also reported.
The process starts with the deposition of the structural stack
(SiO2 /Si3 N4 /SiO2 ) which is patterned by reactive ion etching.
The platinum deposition and definition is performed by a selec-
tive lift-off, defining in a single metallization layer both heaters
and contacts. This solution results in a simplified technological
implementation and in an increased device reliability, avoiding
overlapping metal tracks which would require dielectric insulating
layers able to withstand repeated thermal cycles at high temper-
ature. In order to promote the platinum adhesion a very thin TiN
layer is interposed between the metal and the silicon dioxide.
On top of the platinum metallizations a silicon dioxide passi-
vation layer is deposited for electrical insulation of the sensing
layer from the heater. This passivation layer is not required for
some of the designed hotplates, depending on the electrode layout:
the “self-insulating” layout (as shown in Fig. 1) does not require
passivation. This kind of devices can be fabricated with a further
 I. Elmi et al. / Sensors and Actuators B 135 (2008) 342–351
Fig. 2. 2D and 3D simulated temperature distributions: (a) on the central suspended
structure of ULP hotplate and (b) of complete ULP hotplate.
simplified technological process composed by only two masks and
six steps.
Finally the silicon beneath the hotplates is selectively removed
using a tetramethylammonium hydroxide (TMAH) solution. In
Fig. 4, SEM micrographs of released hotplates with and without
the passivation layer are shown.
The hotplates can withstand the very high temperatures that are
necessary for sensing layer processing and stabilization. In fact the
material properties were thoroughly studied and both the suspend-
ing dielectric stack and metallizations can be heated in furnaces at
temperatures as high as 800 ◦ C for several hours, while the hotplate
can successfully undergo a continuous operating temperature of
650 ◦ C using the integrated platinum heater. The choice of platinum
as heater material allows to obtain devices which are electrically
stable for very long time periods at high working temperatures (up
to 650 ◦ C) required for MOX sensor hotplate operation.
A micrograph showing a complete four ULP hotplate array chip
is reported in Fig. 5, together with a 1 eurocent coin for size com-
parison.
2.3. Sensing layer deposition process
The sensing layers of the ULP devices are SnO2 thin films
deposited using a modified [17] rheotaxial growth and thermal
oxidation (RGTO) technique [18]. In this new technique the sens-
ing layer is composed by a stack of two overlapping thin films.
Each single film is made by sputtering metallic Sn on the substrate
while kept at a temperature higher than the Sn melting point, fol-
lowed by an oxidation in a 1:1 N2 :O2 atmosphere as in the classic
RGTO technique. Substrate temperature, duration and temperature
of the oxidation process have been chosen among values reported
in previous studies performed by other authors [19–21]. The single
345
film thickness ranges from 15–30 nm before oxidation to 20–40 nm
after oxidation, depending on the amount of sputtered material.
The overall sensing layer thickness at the end of the deposition
process, composed by the two oxidized layers, ranges from 40 to
100 nm.
This particular morphology, provided by the overlapping of the
two clustered layers, is rich of cavities and meanders, which make
the complete removal of any photoresist or solvent traces very dif-
ficult. For this reason, in order to avoid sensing layer poisoning, the
use of shadow masks has been chosen to define the sensing layer.
The shadow mask definition technique, as opposed to lithographic
processes like lift-off or thin film etching masked by photoresist,
relies on physically masking the area where no sensing layer thin
film is to be deposited by means of a shadow mask, which covers
those areas and avoids the material deposition. For this application,
being the feature sizes very small and not suitable for a metallic
shadow mask, an apposite silicon shadow mask micro-machined
by deep reactive ion etching (D-RIE) of a 4-in. Si wafer has been fab-
ricated. This mask, having holes in correspondence of the hotplates’
etch-pits, allows to avoid sensing layer deposition on the bonding
pads. The suspended structures, together with the layout of the
self-insulated devices or the passivation on normal devices, pro-
vide a self-aligning process for the sensing layer deposition on the
micro-hotplate. By means of those solutions the only sensing mate-
rial being read and providing the transduction signal is enclosed by
the two contact electrodes; this self-aligned sensing layer has an
open circular ring shape with widths, corresponding to the distance
between the sensing electrodes, of 4 and 6 ␮m and circumference
lengths of 120 and 270 ␮m, respectively.
To target our sensors towards VOCs detection, after the sensing
layer deposition, a very small amount of gold is added by sputtering
deposition (5–10 wt.%) using the same shadow mask. This small
quantity of gold on the SnO2 thin film, in the form of nanometric
clusters, acts as a catalyst for reaction of the VOCs on the sensing
layer surface, thus enhancing sensitivity towards those compounds
and improving the sensor selectivity.
3. Hotplate thermal and electrical characterization
The thermal characterization of ULP hotplates was performed in
three main steps:
(1) Precise evaluation of the temperature coefficient of resistance
(TCR) of the platinum metallization, using an environmental
chamber with high precision temperature control.
(2) Evaluation of the temperature as a function of the supplied
electrical power by means of the Kelvin temperature sensor
integrated on some devices, using the TCR as determined in
step 1.
(3) Evaluation of the thermal time constant by means of fall tran-
sient measurement of a ULP hotplate.
At this point we would like to point out that the integration of a
Kelvin Pt temperature sensor, through the precise evaluation of the
TCR of the sputtered Pt, allows to actually measure the temperature
in the central part of the hotplate. This measured temperature can
be compared to the results of the FEM simulations, allowing for a
validation of the thermoelectrical simulation.
3.1. Determination of the platinum TCR
The temperature coefficient of resistance of the metallizations
was exactly determined on different wafers. The TCR of thin films of
platinum are expected to differ from the values found in literature
346 I. Elmi et al. / Sensors and Actuators B 135 (2008) 342–351

Fig. 3. ULP fabrication process flow.

for bulk platinum, especially when using sputtering as deposition 3.2. Evaluation of ULP temperature vs. applied power
technique.
For the evaluation of the TCR of Pt, specific Kelvin resistor test The variation of the ULP hotplate temperature in its central
structures were used, which were replicated on every die within the part (active area) as a function of the applied power was mea-
wafer. For each wafer accurate four-probe resistance measurements sured, together with other electrical parameters like the heater
were performed on several test structures at different tempera- resistance and the heater voltage drop. Different devices were
tures (50, 100, 150, and 200 ◦ C) inside an environmental chamber considered, in order to evaluate the effects of the different lay-
(Sun Systems EC11, maximum temperature 200 ◦ C, maximum tem- outs.
perature gradient inside the chamber 1 ◦ C) using a Keithley 2410 In Fig. 6 the plots of the hotplate temperature as a function of
multimeter. The values of the resistance R as a function of temper- the applied power are comparatively reported for several combina-
ature T (◦ C) were logged, allowing to estimate the TCR defined as tions of the design parameters reported above, in order to evaluate
the effects of the different implementations. The plots report the
1
 R(T ) 
TCR = −1 (1) average values of 11 identical devices spread throughout the wafer,
T R (0 ◦ C)
which were all characterized.
In Table 1, the results for the TCR are reported for two different Fig. 6a allows to estimate the effects of the different metalliza-
wafers. tion widths W as well as the effects of the different membrane
shape, while the other parameters are fixed. As can be disclosed,
Table 1
TCR measured values the smaller membranes (W = 4 ␮m) have the lowest power con-
sumption, and the minor number of arms and width help lowering
Wafer name TCR (K−1 )
the power consumption.
U10 0.003236 On the other hand, the effects of thermal insulation provided
W4 0.003177 by a wider pit can be extracted from Fig. 6b for the different mem-
 I. Elmi et al. / Sensors and Actuators B 135 (2008) 342–351 347

Fig. 4. SEM micrographs of ULP hotplate with passivation (top picture) and without
passivation (bottom picture).

branes shape, while all the other parameters are fixed. In this plot,
a low contribution due to the increase of the pit dimensions can be
disclosed; this means that the loss of heat towards the surrounding
silicon bulk is minimal already with the lower pit dimension.
In Fig. 6c the effects of the presence of the passivation layer,
which adds another 380 nm of silicon oxide to the overall stack
of membrane material, can be disclosed: as it is possible to see,
the increase in power needed to heat the passivation is higher
than the differences in power provided by different membrane
shapes.
All the results of this figure indicate how the shape of the
membrane and the width of pit only slightly affect the power con-
sumption, which is mainly due to irradiation and convection rather
than to heat conduction through the dielectric membrane.
High reproducibility has been found measuring the temperature
behavior of each device type throughout the wafer. Fig. 7 shows the

Fig. 6. Plot of the hotplate temperature vs. applied power for the three different
hotplate shapes and (a) varying metallization widths W (fixed parameters: no pas-
sivation; pit = 400 ␮m); (b) varying pit widths (fixed parameters: no passivation,
W = 4 ␮m); (c) presence of passivation (fixed parameters: pit = 400 ␮m, W = 4 ␮m).

spread of the ULP temperature vs. applied power for 11 different

devices measured throughout the wafer. The temperature reached
by each ULP hotplate differs from the average temperature value
less than 2.5%.

3.3. Evaluation of the thermal time constant

To evaluate the fall time of the ULP hotplate temperature, a dig-

Fig. 5. ULP hotplate array picture and comparison with a 1 eurocent coin. ital oscilloscope LeCroy 6100A was used to trace the decrease of
348 I. Elmi et al. / Sensors and Actuators B 135 (2008) 342–351
Fig. 7. ULP temperature vs. applied power spread for 11 different devices measured
throughout the wafer.
the heater resistance. A small readout current of about 0.3 mA was
applied while hotplate temperature has been changed from 400 ◦ C
to room temperature breaking down the 8.9 mW of power supply
to 20 ␮W, corresponding to the dissipated power of the readout
current. The decay of the heater resistance is reported in Fig. 8,
and a very short thermal time constant of 1.5 ms results from the
exponential fit.
4. Sensing layer characterization
4.1. Structural characterization
In Fig. 9 two SEM micrographs of a SnO2 M-RGTO thin film with-
out (on the left) and with (on the right) Au catalyst nanoclusters are
shown.
The SnO2 morphology shown in Fig. 9 consists of a double layer
of nanometric SnO2 clusters with average diameters ranging from
Fig. 9. SEM micrographs of M-RGTO SnO2 thin film: without (left) and with (right) gold nanoparticles.
Fig. 8. Resistance decay of the heater during a 400 ◦ C to room temperature cooling.
20 to 40 nm. This kind of morphology combines a very high specific
surface with a quite uniform and very small cluster size, comparable
to the width of the depletion region at the MOX grain boundaries.
Those morphological characteristics are optimal for the MOX trans-
duction principle [22] and allow for the detection of gases in trace
concentrations down to few ppb, with good responses despite the
small sensing layer active area, which has a surface of only 480 or
1620 ␮m2 , depending on device. On the top of the SnO2 layer, nano-
metric gold particles with a quite uniform spatial distribution act
as a catalyst for the reaction of the VOCs. Analyses performed with
energy-dispersive X-ray spectroscopy (EDX) evaluate the average
presence of gold to be approximately 10 wt.%.
4.2. Functional characterization
The uniformity of the sensing layer deposition process has been
evaluated at wafer level by means of an automated probing station,
 I. Elmi et al. / Sensors and Actuators B 135 (2008) 342–351
Fig. 10. Wafer level ULP MOX sensor sensing layers conductance spatial distribution
on the wafer. The dies’ positions on the 4 in. wafer are placed on a grid of 27 rows
(identified by characters) and 27 columns (identified by numbers).
acquiring the conductance of 28 identical ULP sensor sensing lay-
ers uniformly distributed on the wafer surface, when heated at a
temperature of about 400 ◦ C. In Fig. 10 the distribution map of the
acquired measures is reported.
As can be disclosed from the values reported in Fig. 10, con-
ductance ranges from about 1 to 5 ␮S with a mean value of
(2.6 ± 0.9) ␮S. This result has been obtained measuring the samples
in lab air, where local changes in the atmosphere composition may
have caused some fluctuations on the sensing film conductance,
which is expected to be even more reproducible under controlled
conditions.
Some of the sensor arrays have been measured in a stainless steel
cylindrical test chamber having an internal volume of 0.5 cm3 . The
gas inlet and outlet are small holes located along the longitudinal
axis in the center of the upper base and along a radial direction in
the middle of the lateral surface, respectively. The sensors chip is
bonded on a TO8 package which makes up the base of the cylindrical
chamber.
The chamber is connected to a gas distribution system capa-
ble to generate high precision gas concentration mixtures adding
predetermined amounts of target gases to a suitably modulated
synthetic air flow. The sensors responses to benzene (C6 H6 ), one
of the most harmful VOCs in outdoor and indoor polluted air,
have been acquired. To estimate the sensor response selectivity
for VOCs, the responses towards some other interfering gases have
been measured as well. In particular, among the most important
air pollution tracers, carbon monoxide (CO) and nitrogen dioxide
(NO2 ) have been chosen as representative interferents. The mea-
surements have been performed under dynamic conditions, at a
constant flow of 30 sccm with relative humidity equal to 30% at
22 ◦ C.
To evaluate the response of ULP MOX gas sensors we measure
the current through the sensing layer when a 1 V bias is applied,
defining this current as the baseline I0 if the sensor is exposed to
synthetic air containing only humidity or signal current Igas if the
sensor is exposed to an atmosphere containing also pollutants, but
at the same humidity concentration.
In Fig. 11 a typical current signal provided by a circular shape (C),
minimal arms (M), self-insulated electrodes (I), 4 ␮m metallization
widths (W) and 400 ␮m width pit ULP MOX sensor is reported.
It is easy to disclose that those sensors have very high detection
capabilities towards low, ppb-level VOC concentrations. Defining
the sensor response as:
|Igas − I0 |
Response =
Imin
349
Fig. 11. ULP MOX sensors typical current signal to increasing concentrations of ben-
zene and CO. In the inset a zoom of the current signal provided for 10 ppb of benzene
is shown.
where Imin is the minor between I0 and Igas (to take into account
reducing gases as NO2 ), Fig. 11 shows a response of 300% to 5 ppb
of benzene, comparable to those provided for 10 ppm of CO.
In literature several works on solid state gas sensors based on
sensing layers made with different metal oxide semiconductor
materials investigate responses towards VOCs, but a vast major-
ity considers very high gas concentrations ranging from some
to several thousands of ppm [3,23,24]; only a few authors [2]
have reported sensors able to detect, with significant signal-to-
noise ratios, VOCs concentrations lower than 1 ppm. Only Kanda
and Maekawa [1] report sensor responses to some tens of ppb of
toluene (in particular response about 100% to 10 ppb of toluene).
The responses presented in this work are referred to few ppb of
benzene (which generally provides lower signals than toluene and
xylene on MOX sensors, as shown in Ref. [25] using SnO2 sensors
with Au catalyst) and can therefore be considered an exceptional
result. In particular, it is worth considering that generally in the lit-
erature [26,27] the use of preconcentration systems is assumed to
be able to detect similar concentrations.
The inset of Fig. 11 shows a time magnification of the sensor
response transient due to 10 ppb of benzene. We can evaluate that
ULP MOX sensors show a rise and recovery time of about 50 s under
the above described measurement conditions.
In Fig. 12 the processed responses provided by ULP MOX sensors
towards 5 ppb of C6 H6 (target gas), 10 ppm of CO and 100 ppb of
NO2 (interferent gases) when the sensor is operated at different
constant working temperatures are shown. A change in the sensor
selectivity with temperatures around 320 ◦ C can be pointed out;
above this value the sensor has a higher sensitivity towards C6 H6
and CO rather than NO2 , and below 320 ◦ C the opposite behavior is
shown. It is interesting to point out that similar responses towards
C6 H6 and CO provided by ULP MOX sensors are relative to 5 ppb and
10 ppm, respectively; VOC and CO sensor responses are comparable
despite VOC concentrations are about 2000 times lower than the
CO concentrations. This behavior is the evidence of a high sensor
selectivity.
The low thermal mass of the ULP sensors allows to operate our
MOX sensors also in fast pulsed temperature (FPT) operation mode
[28]. In this operative mode the sensing layer is heated only for a
short interval at each measurement event. In Fig. 13 the responses
provided by an ULP MOX sensor heated in FPT mode at different
(2)
temperatures applied for 100 ms every 5 s are reported. Under these
350 I. Elmi et al. / Sensors and Actuators B 135 (2008) 342–351
Fig. 12. Responses towards different compounds at different constant working tem-
peratures.
Fig. 13. Responses towards different compounds in fast pulse temperature oper-
ation mode at different temperatures. The average power consumption is in the
sub-mW range.
operating conditions, the average ULP sensor consumption is in the
sub-mW region, but it is not possible to detect VOC at ppb concen-
tration. Response is still provided with good sensitivity towards
NO2 but comparable [29,30] or better results [31,32] have been
already reported in literature for this gas.
The results confirm that the FPT mode can be used to
lower power consumption while changing the ULP MOX sensors
selectivity, as reported also by other authors [33–35]. Further char-
acterization will be necessary to tune the pulse parameters in
order to obtain an optimal trade-off between power and selectivity
towards the specific compounds of interest.
5. Conclusions
ULP hotplates for gas sensing applications were presented. The
design, the process flow as well as a thorough characterization of
the fabricated ULP hotplates was reported. With a 78-␮m diameter
circular hotplate, only 8.9 mW are necessary to reach the typi-
cal 400 ◦ C operating temperature. Transient temperature response
evaluation has shown a very low thermal time constant of only
1.5 ms.
On those ULP hotplates, complete ULP MOX sensors with high
sensitivity to ppb-level VOC concentrations have been fabricated.
The sensing layer deposition process as well as a functional char-
acterization was reported. Responses of 300% to 5 ppb of C6 H6 in
synthetic air with a relative humidity of 30% have been obtained
operating the sensor at a constant temperature of 415 ◦ C, with a
response time of 50 s. The ability to enhance selectivity towards var-
ious compounds by working under different operating conditions
has been preliminarily demonstrated.
The excellent results in terms of ultra-low-power consump-
tion and thermal behavior support the design choices in terms
of hotplate layout and technological implementation. The very
high sensitivity achieved by the developed devices combined with
ultra-low-power consumption confirm the potentiality of ULP MOX
sensors for addressing a large number of innovative ultra-low-
power applications.
The ULP sensors fabricated are therefore implementing several
innovative aspects, summarized in the following items:
• A series of design and technological solutions which allow the
fabrication of ULP sensors with a simplified process flow fea-
turing only two lithographic masks and a self-aligned sensing
layer deposition process to avoid any possibility of sensing layer
poisoning.
• The decrease of the MOX sensor power consumption down to a
few mW values together with the reduction of footprint to only
1.5 mm × 1.0 mm for a four sensors array chip, to enable address-
ing some emerging applications like portable devices, wireless
sensor networks or semi-passive RFID tags.
• The state-of-the-art sensitivity of the ultra-low-power sensors,
which reliably detect low ppb concentrations of benzene in air.
Acknowledgments
This work was funded by the EC 6FP IP “GoodFood” and the
Italian MIUR research project FIRB RBME019TMF.
The technical support of Fabrizio Tamarri, Giulio Pizzochero,
Michele Sanmartin, Paolo Negrini, Luca Masini and Antonio Zani,
is also gratefully acknowledged.
References
[1] K. Kanda, T. Maekawa, Development of a WO3 thick-film-based sensor for the
detection of VOC, Sens. Actuators B 108 (2005) 97–101.
[2] E.J. Wolfrum, R.M. Meglen, D. Peterson, J. Sluiter, Metal oxide sensor arrays
for the detection, differentiation, and quantification of volatile organic com-
pounds at sub-parts-per-million concentration levels, Sens. Actuators B 115
(2006) 322–329.
[3] D.-S. Lee, J.-K. Jung, J.-W. Lim, J.S. Huh, D.-D. Lee, Recognition of volatile organic
compounds using SnO2 sensors array and pattern recognition analysis, Sens.
Actuators B 77 (2001) 228–236.
[4] A.T. Hodgson, H. Levin, Volatile Organic Compounds in Indoor Air: A Review
of Concentrations Measured in North America Since 1990, Lawrence Berkeley
National Laboratory, 2003, p. 31.
[5] P. Wolkoff, G.D. Nielsen, Organic compounds in indoor air—their relevance for
perceived indoor air quality, Atmos. Environ. 35 (2001) 4407–4417.
[6] S. Semancik, Microhotplate platform for chemical sensors research, Sens. Actu-
ators B 77 (2001) 579–591.
[7] P.C.H. Chan, G. Yan, L. Sheng, R.K. Sharma, Z. Tang, J.K.O. Sin, I.-M. Hising, Y.
Wang, An integrated gas sensor technology using surface micromachining,
Sens. Actuators B 82 (2002) 277–283.
[8] J. Wollenstein, J.A. Plaza, C. Canè, Y. Min, H. Bottner, H.L. Tuller, A novel single
chip thin film metal oxide array, Sens. Actuators B 93 (2003) 350–355.
[9] S. Zampolli, I. Elmi, E. Cozzani, G.C. Cardinali, Ultra-low-power components for
an RFID Tag with physical and chemical sensors, Microsyst. Technol. 14 (2008)
581–588.
 I. Elmi et al. / Sensors and Actuators B 135 (2008) 342–351
[10] E. Abad, S. Zampolli, S. Marco, A. Scorzoni, B. Mazzolai, A. Juarros, D. Gómez,
I. Elmi, G.C. Cardinali, J.M. Gómez, F. Palacio, M. Cicioni, A. Mondini, T. Becker,
I. Sayhan, Flexible tag microlab development: gas sensors integration in RFID
flexible tags for food logistic, Sens. Actuators B 127 (2007) 2–7.
[11] Carcinogenic effects of benzene: an update, EPA/600/P-97/001F April 1998.
[12] N. Maluf, An Introduction to Microelectromechanical Systems Engineering,
Artech House, Norwood, 2000.
[13] P. Rai-Choudhury (Ed.), MEMS and MOEMS. Technology and Applications, SPIE,
Washington, 2000.
[14] M.F. Ashby, Materials Selection in Mechanical Design, 2nd ed., Butterworth–
Heinemann, 1999.
[15] P.K. Guha, S.Z. Ali, C.C.C. Lee, F. Udrea, W.I. Milne, T. Iwaki, J.A. Covington, J.W.
Gardner, Novel design and characterisation of SOI CMOS micro-hotplates for
high temperature gas sensors, Sens. Actuators B 127 (2007) 260–266.
[16] E. Cozzani, A. Roncaglia, S. Zampolli, I. Elmi, F. Mancarella, F. Tamarri, G.C.
Cardinali, Material properties measurement and numerical simulation for char-
acterization of ultra-low-power consumption hotplate, in: Proceedings of the
Transducer ‘07 & Eurosensors XXI, Lyon, France, June 2007, 2007.
[17] I. Elmi, S. Zampolli, G.C. Cardinali, Optimization of a wafer-level process for the
fabrication of highly reproducible thin-film MOX sensors, Sens. Actuators B 131
(2008) 548–555.
[18] G. Sberveglieri, G. Faglia, S. Groppelli, P. Nelli, A. Camanzi, A new technique
for growing large surface area SnO2 thin film (RGTO technique), Semicond. Sci.
Technol. 5 (1990) 1231–1233.
[19] G. Sberveglieri, Classical and novel techniques for the preparation of SnO, thin-
film gas sensors, Sens. Actuators B 6 (1992) 239–247.
[20] W. Hellmich, Ch. Bosch-v. Braunmiihl, G. Miiller, G. Sberveglieri, M. Berti, C.
Perego, The kinetics of formation of gas-sensitive RGTO-SnO2 films, Thin Solid
Films 263 (1995) 231–237.
[21] A. Dieguez, A. Romano-Rodrıguez, J.R. Morante, L. Sangaletti, L.E. Depero, E.
Comini, G. Faglia, G. Sberveglieri, Influence of the completion of oxidation on
the long-term response of RGTO SnO2 gas sensors, Sens. Actuators B 66 (2000)
40–42.
[22] C. Xu, J. Tamaki, N. Miura, N. Yamazoe, Grain size effects on gas sensitivity of
porous SnO2 -based elements, Sens. Actuators B 3 (1991) 147–155.
[23] B.L. Zhu, C.S. Xie, W.Y. Wang, K.J. Huang, J.H. Hu, Improvement in gas sensitivity
of ZnO thick film to volatile organic compounds (VOCs) by adding TiO2 , Mater.
Lett. 58 (2004) 624–629.
[24] A. Szczurek, M. Maciejewska, Recognition of benzene, toluene and xylene using
TGS array integrated with linear and non-linear classifier, Talanta 64 (2004)
609–617.
[25] S. Zampolli, I. Elmi, J. Sturmann, S. Nicoletti, L. Dori, G.C. Cardinali, Selectivity
enhancement of metal oxide gas sensors using a micromachined gas chromato-
graphic column, Sens. Actuators B 105 (2005) 400–406.
[26] I. Gracia, P. Ivanov, F. Blanco, N. Sabate, X. Vilanova, X. Correig, L. Fonseca, E.
Figueras, J. Santander, C. Canè, Sub-ppm gas sensor detection via spiral ␮-
preconcentrator, Sens. Actuators B 132 (2008) 149–154.
[27] I. Voiculescu, M. Zaghloul, N. Narasimhan, Microfabricated chemical precon-
centrators for gas-phase microanalytical detection systems, Trends Anal. Chem.
27 (April (4)) (2008) 327–343.
[28] I. Elmi, S. Nicoletti, G.C. Cardinali, L. Dori, M. Masini, S. Zampolli, E. Gandolfi, Fast
pulsed temperature mode operation: a viable way to improve the sensitivity
and selectivity in metal oxide gas sensors, in: Proceedings of the Eurosensors
XIV, Copenhagen, Denmark, August 2000, 2000.
[29] J. Brunet, V. Parra Garcia, A. Pauly, C. Varenne, B. Lauron, An optimised gas sensor
microsystem for accurate and real-time measurement of nitrogen dioxide at
ppb level, Sens. Actuators B 134 (2008) 632–639.
[30] G. Barillaro, L.M. Strambini, An integrated CMOS sensing chip for NO2 detection,
Sens. Actuators B 134 (2008) 585–590.
[31] M.I. Mazurenka, B.L. Fawcett, J.M.F. Elks, D.E. Shallcross, A.J. Orr-Ewing, 410-nm
diode laser cavity ring-down spectroscopy for trace detection of NO2 , Chem.
Phys. Lett. 367 (2003) 1–9.
351
[32] H.D. Osthoff, S.S. Brown, T.B. Ryerson, T.J. Fortin, B.M. Lerner, E.J. Williams, A.
Pettersson, T. Baynard, W.P. Dube, S.J. Ciciora, A.R. Ravishankara, Measurement
of atmospheric NO2 by pulsed cavity ring-down spectroscopy, J. Geophys. Res.
111, D12305, doi:10.1029/2005JD006942.
[33] P. Kreisl, A. Helwig, G. Müller, E. Obermeier, S. Sotier, Detection of hydrocarbon
species using silicon MOS field-effect transistors operated in a non-stationary
temperature-pulse mode, Sens. Actuators B 106 (2005) 442–449.
[34] M. Schweizer-Berberich, M. Zdralek, U. Weimar, W. Göpel, T. Viard, D. Martinez,
A. Seube, A.P. Lavigne, Pulsed mode of operation and artificial neural network
evaluation for improving the CO selectivity of SnO2 gas sensors, Sens. Actuators
B (2000) 91–93.
[35] M. Schweizer-Berberich, S. Strathmann, U. Weimar, R. Sharma, A. Seube, A.
Peyre-Lavigne, W. Göpel, Strategies to avoid VOC cross-sensitivity of SnO2 -
based CO sensors, Sens. Actuators B 58 (1999) 318–324.
Biographies
Ivan Elmi graduated in physics at the University of Bologna in 1998, discussing a
thesis on characterization of sensors for benzene detection. Since April 1999 he is
working as grant student at CNR-IMM, Bologna within the sensor and microsystem
R&D program, primarily developing a system for environmental monitoring and
characterizing gas sensors and miniaturized GC systems. Recent activities include
design and fabrication processes for MEMS. Recent research projects include FP5
CleanAir, FP6 Goodfood as well as Italian national and regional research projects.
Recent collaborations with industries include Italian SMEs as well as LMEs from
USA.
Stefano Zampolli graduated in physics at the University of Bologna in 2000, dis-
cussing a thesis on the application of fuzzy logic for detection of buried landmines.
He is a grant student at CNR-IMM, Bologna since April 2000, working primarily on
gas sensor characterization and data processing within the sensor and microsystem
R&D program. Since 2005 he is researcher in the sensors and microsystem group
at CNR-IMM, designing and developing gas sensors and gas sensing Microsystems
for environmental monitoring and agrofood applications. He has participated to the
FP5 Clean-Air and FP6 GoodFood projects as well as to several national and regional
research projects and industrial collaborations.
Enrico Cozzani received a degree in electronic engineering from the University of
Parma, Italy, in 2005. Since 2006 he has been working as grant student at CNR-IMM
(Bologna section) within the sensors and microsystems group, working primarily
on gas sensors characterization and electro-thermal finite elements simulations.
Fulvio Mancarella received a MSc degree in electrical engineering and PhD degree
in electronics and computing science in 2002 and 2005, respectively, both from
Bologna University. Since 2003, he has been working at the Institute of Microelec-
tronics and Microsystems (IMM) of the Italian National Research Council (CNR).
His research interests include MEMS technology and silicon processing, focusing
his experimental activities on dry etching processing. He has also dealt with sub-
micrometric MOSFET compact model.
Gian Carlo Cardinali received a degree in electronic engineering from the University
of Bologna, Italy, in 1979. Since 1982 he has been working at the CNR-IMM Institute.
His scientific interests are in the areas of design, fabrication, and testing of electronic
devices and microsystems. From 1996 onwards he has been involved in research
projects dealing with the implementation of systems for air quality monitoring
based on micro gas sensors, and is the head of the CNR-IMM sensors and microsys-
tems group. He is also dealing with the development of dedicated microelectronic
processes suitable for integration into microsystems, with a specific interest for
applications in the field of ink-jet print heads.