Sensors and Actuators B 93 (2003) 175–180

A room temperature indium tin oxide/quartz crystal

microbalance gas sensor for nitric oxide
Jianqiao Hua, Furong Zhua, Jian Zhanga, Hao Gongb,*
a
Institute of Materials Research and Engineering, 3 Research Link, Singapore 117602, Singapore
b
Department of Materials Science, National University of Singapore, Lower Kent Ridge,
Singapore 119260, Singapore

Abstract

Nitric oxide (NO) gas sensor using a combination of indium tin oxide (ITO) and quartz crystal microbalance is fabricated. The sensor is
made from the polished AT-cut quartz crystal on which the ITO thin film is deposited using radio frequency magnetron sputtering. The sensor
is sensitive to NO gas at room temperature and avoids the problems related to elevated-temperature sensors. It is shown that the sensor has a
distinct negative frequency shift of 110 Hz within 600 s when it is exposed to 60 ppm of NO. The frequency-changing rate is also found to
increase with NO concentration. The chemical status of elements on the ITO surface before and after NO adsorption is investigated by X-ray
photoelectron spectroscopy (XPS). Possible gas sensing mechanisms are discussed.
# 2003 Elsevier Science B.V. All rights reserved.

Keywords: Indium tin oxide; Quartz crystal; Gas sensing mechanisms

1. Introduction surface [17]. The corresponding frequency shift can be

Sensors for toxic gases have attracted much attention due
to the growing concern of environmental protection and
safety. A number of semiconductor oxides such as ZnO,
SnO2, In2O3 and indium tin oxide (ITO) are used for
different gas sensors [1–4]. Most of these sensors are based
on the resistance variation when the semiconductor oxide
films are exposed to target gases. Normally, the conventional
resistance-type sensors are operated at an elevated tempera-
ture, usually within the range of 250–300 8C [4–8]. The
requirement for user-friendly sensors drives the effort to
develop more portable, sensitive and cost-effective devices.
In addition, it is desirable to develop sensors working at
room temperature.
QCM has been used widely to monitor the change in mass
loadings by measuring the shift of its resonant frequency [9].
A QCM-based sensor consists of a quartz crystal and the
sensing material. A good sensing material can selectively
adsorb the target species/gases. QCM devices made with
metal electrodes of Pt, Au, Ag, etc. for sensor applications
have been reported [10–16]. The resonant frequency of a
QCM decreases when gas is adsorbed on the electrode
*
Corresponding author. Tel.: þ65-8746598; fax: þ65-7763604.
E-mail address: masgongh@nus.edu.sg (H. Gong).
described by the following empirical equation [10]:
Df ¼ Cf02 Dm=A; (1)
where f0 is the resonant frequency of the unperturbed quartz,
Df the QCM frequency shift due to the added mass, C a
constant, Dm the added mass and A the area of the sensing
material. For example, the sensitivity of QCM having a
resonant frequency of 10 MHz, made with gold electrode of
diameter 8 mm, is approximately 0.226 cm2 Hz/ng.
In this work, we developed gas sensors with a combina-
tion of ITO and QCM and used them for nitric oxide (NO)
gas sensing in atmospheric environment. Such sensors have
simple layer configuration and can be operated at room
temperature. The sensitivity and repeatability of the sensors
are investigated. The possible sensing mechanisms are also
discussed.
2. Experimental
ITO films were prepared at room temperature by radio
frequency magnetron sputtering using an oxidized target
with In2O3 and SnO2 in a weight proportion of 9:1. The base
pressure in the system was approximately 5:0  108 Torr.
The total pressure of the sputtering gas mixture of argon and

0925-4005/03/$ – see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0925-4005(03)00186-2
176 J. Hu et al. / Sensors and Actuators B 93 (2003) 175–180
Fig. 1. Schematic diagram of a gas testing system for NO detection.
hydrogen was adjusted to 3:0  103 Torr during the film
deposition. In a previous work, we have shown that the
presence of hydrogen during the film deposition can alter the
electrical properties of ITO films [18]. In order to study the
correlation between the ITO conductivity and the sensing
sensitivity, we have made a set of ITO-QCM sensors with
ITO electrodes prepared at the different hydrogen flow rates
of 0, 1.0, 1.5 sccm in this study.
AT-cut rectangular quartz blanks with dimension of
10 mm  10 mm  0:1 mm are used. The corresponding
resonant frequency of the quartz substrate is about
17 MHz. An ITO-QCM sensor was fabricated using the
lift-off photolithography process. The photoresist moulds
were generated by lithography before ITO deposition. The
thickness of ITO film obtained was 110 nm. A similar
process was repeated to form the ITO electrode on the other
side of the quartz crystal.
Fig. 2. Typical time-dependent frequency shift of an ITO-QCM gas sensor (#2) as a function of NO concentration.
Gas sensing experiments were performed in a system as
shown in Fig. 1 [19]. In this study, all measurements were
performed at room temperature in atmospheric environment.
The sensor was loaded into the main chamber and connected
to a Saunders & Associate network analyzer. The frequency
resolution of the analyzer is 50 Hz. The target nitric oxide
gas was introduced into the test chamber using a calibrated
syringe of minimum volume of 0.1 ml. In atmosphere, the
concentration of the test gas, c, in parts per million (ppm),
can be estimated as:
Vg Vg
c ðppmÞ ¼  106   106 ; (2)
Vg þ V V
where Vg is the volume of introduced gas, and V the volume
of the chamber. We have varied the gas concentration from
60 to 2000 ppm in this work. During the testing process, in
order to ensure the cleanness of the sensor surface and the
accurate gas concentration, the system was pumped down to
7:5  102 Torr and then purged at least three times before
each new cycle of NO measurement. The time-dependent
sensor responses were recorded at room temperature.
The chemical status of elements on the ITO surface before
and after NO adsorption was investigated by ex situ X-ray
photoelectron spectroscopy (XPS). The XPS experiments
were performed in a VG ESCALAB 220i-XL instrument
with an Al Ka X-ray source (1486.6 eV) operated at a power
of 150 W. The electron energy analyzer was set at a constant
analyzer mode at pass energy of 20 eV for high-resolution
spectra acquisition. The electrical properties of as-deposited
ITO films were obtained by Hall effect measurement.
3. Results and discussion
Three types of gas sensors, labeled as #1, #2, #3, were
used for the NO detection. The ITO electrodes of the sensors
#1, #2, and #3 were deposited at the hydrogen flow rates of 0,
 J. Hu et al. / Sensors and Actuators B 93 (2003) 175–180 177

Fig. 3. Frequency sensitivity, Sf, as a function of NO concentration.

1.0, 1.5 sccm, respectively. There is no observed change in
the resonant frequency of the sensors in air. When NO was
introduced into the test chamber, the frequency started to
shift. Fig. 2 shows the time-dependent frequency shift of
sensor #2 exposed in different NO concentrations. It can be
seen that the negative frequency shift increases with increas-
ing NO gas concentration. The frequency shift shows an
approximate linear relationship with the exposure time. The
sensor has a negative frequency shift of 110 Hz within 600 s
when it is exposed to a concentration of 60 ppm NO gas.
We define the frequency-changing rate, Sf ¼ jDf =Dtj, or
slopes of Df–Dt curves, as the parameter to reflect the sensor
sensitivity [19]. The larger Sf value means the bigger
frequency shift per unit time and thus the higher sensitivity.
Fig. 3 shows the corresponding relationship between
Sf and the NO gas concentration. It is obvious that the
frequency-changing rate increases with increasing NO
concentration.
The sensors are sensitive to NO gas with good repeat-
ability of Df although the starting frequency varies in
different measurements. Fig. 4 shows the repeatability
experimental results for sensor #2 testing at an identical
NO concentration of 590 ppm. A clear negative frequency
shift was always observed when NO was introduced to the
system. Similar frequency-changing rate (jDf =Dtj) of about
0.6 Hz/s was found in three replicate tests within the first
250 s, which indicates a promising reproducibility of the
device. We have found that the frequency-changing rate of
0.6 Hz/s is slightly lower than 0.7 Hz/s of the fresh sample
tested. This is probably due to the dissipation of some active
sites on ITO surface after the first exposure to NO gas. From
Fig. 4, diverse frequency-changing rates from 0.6 to 0.8 Hz/s
are observed after the first 300 s. It should be noticed that
we pumped out the gases in the chamber and flushed with air
prior to each test. Although this procedure could remove
the residual NO gas in the chamber, it might not remove all

Fig. 4. The repeatability of ITO-QCM (gas sensor #2) frequency shift exposed to the NO.
178 J. Hu et al. / Sensors and Actuators B 93 (2003) 175–180

Fig. 5. Time-dependent frequency shifts of QCM using ITO films deposited under different hydrogen flow rates (sensors #1 and #3).

those NO molecules trapped on the chamber wall. The
trapped NO molecules would escape slowly from the cham-
ber wall leading to a gradual increase of NO concentration
in the chamber. The frequency-changing rate was fluctuated
for different measurements, which may be related to the
amount and the release process of trapped NO gas. The
possible corrosion of the ITO electrode may not be the cause
of the diverse frequency-shift rate, as it could not explain
that only the second run showed a different behavior in this
case.
Fig. 5 shows the frequency responses of sensors #1 and #3
working at a NO gas concentration of 1770 ppm. The
frequency shift for sensor #3 was 3990 Hz, however, it
was 2514 Hz for sensor #1. This implies that sensor #3,
made with a higher conductive ITO of 3000 S, exhibits
higher sensitivity to NO than sensor #1 with ITO of
2000 S. Fig. 6 shows the frequency shift of sensors #1
and #3 working under different gas concentrations within
the same time interval of 600 s. The results show that
sample #3 made with ITO, prepared at a hydrogen flow rate
of 1.5 sccm, showed a large frequency response. In a pre-
vious work, we have shown that the presence of hydrogen
during the film deposition increases film conductivity and
reduces the ITO surface roughness [18,20]. As such, sensor
#3 had a smoother surface than sensor #1. We know that the
higher sensitivity (sensor #3) can be related to either the
electrical or the surface morphologic properties of the ITO
films. If the surface roughness plays a crucial role in the
sensor response, in principle, sensor #1 should have bigger
frequency shifts than sensor #3. However, this was not found
in our experiment. Therefore, the different sensor sensitiv-
ities of these two samples may be mainly due to the
difference in electric properties of the ITO electrodes. We
know that the use of hydrogen in the film deposition creates
addition number of oxygen vacancies leading to an enhance-
ment in the ITO conductivity. In the NO detection, these
oxygen vacancies could be involved in the processes of
physical or/and chemical adsorptions of NO. An increase in

Fig. 6. Frequency shift of QCM gas sensors (#1 and #3) as a function of the NO concentration.
 J. Hu et al. / Sensors and Actuators B 93 (2003) 175–180
Fig. 7. XPS spectra of (a) O 1s peak of ITO surface before and after NO
adsorption and (b) N 1s peaks before and after the Arþ sputtering of NO-
exposed ITO surface.
oxygen vacancies may provide more adsorption/reaction
sites, resulting in higher NO mass loading [19], or higher
frequency shift.
XPS has been used to examine the chemical binding
energies of O 1s and N 1s for ITO films before and after
NO exposure. Fig. 7(a) shows the O 1s peaks of ITO-film
surface before and after NO exposure, and Fig. 7(b) shows
the N 1s spectra of NO-exposed ITO surface, before and
after the surface removal with argon ion sputtering. In
Fig. 7(a), an extra shoulder was found in the O 1s profile
from a NO-exposed ITO surface. This peak can be decon-
voluted into two components with the binding energies
located at 530.8 and 532.3 eV, respectively. The observed
O 1s peak at 530.8–531.2 eV can be assigned to the lattice
oxygen in In2O3 [21]. The peak at a binding energy of
532.3 eV can be attributed to a different oxidation state [22].
Fig. 7(b) suggest that the ITO surface may contain two
different nitrogen species corresponding to the N 1s peaks at
the binding energies of 407 and 400.5 eV, respectively.
The weak peak at 400.5 eV may be attributed to the
adsorbed NO. The strong peak at 407 eV may come from
the NO3 species [23]. This suggests that new chemical
species were formed on the ITO surface. After removing the
surface layer, both of the two nitrogen peaks disappeared,
179
suggesting that the gas adsorption/reaction occurred on the
ITO surface.
The existence of new NO3 species on the NO-exposed
ITO surface indicates the reaction between NO and ITO,
which causes the mass increase. The formation of new
species may also change the mechanical and electronic
properties of the ITO electrode. The possible ITO/quartz
interfacial stress changes may also affect in the resonant
frequency of the device. However, the precise verification of
this interfacial effect is difficult to determine directly using
XPS measurement. Behavior of ITO-QCM sensor is quite
complicated. Apart from NO, some others, like water vapor
and oxygen, may also influence the sensor response. For
example, when the sensor is exposed to oxygen, negatively
charged oxygen species could accumulate on ITO surface by
grabbing electrons from the conduction band [24]. This
causes the formation of an electron-depleted region near
the ITO surface region and makes the ITO surface easier to
absorb the target gases [24]. In order to avoid the inter-
ference, the use of dual sensors or operation of the sensors at
two different temperatures [25] could be an alternative
approach. The corresponding experiments are currently in
progress.
4. Conclusions
Gas sensors based on the ITO-coated quartz crystal
microbalance have been fabricated. Such sensors are sensi-
tive to NO gas with good repeatability at room temperature.
The resonant frequency-changing rates of 0.2, 0.4, 0.7 and
2.0 Hz/s has been found when the sensor is exposed to NO
gas at different concentrations of 60, 295, 590 and 1180 ppm
in air, respectively. XPS analyses reveal that NO also reacts
with ITO leading to the formation of NO3 species on its
surface.
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