Thin Solid Films 518 (2009) 1294–1298

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Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / t s f

Nanoporous TiO2 thin film based conductometric H2 sensor

A.Z. Sadek a,⁎, J.G. Partridge b, D.G. McCulloch b, Y.X. Li c, X.F. Yu c, W. Wlodarski a, K. Kalantar-zadeh a
a
School of Electrical and Computer Engineering, RMIT University, Melbourne, VIC 3001, Australia
b
Applied Physics, School of Applied Sciences, RMIT University, Melbourne, VIC 3001, Australia
c
Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, China

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

Available online 9 April 2009 Nanoporous titanium dioxide (TiO2) based conductometric sensors have been fabricated and their sensitivity
to hydrogen (H2) gas has been investigated. A filtered cathodic vacuum arc (FCVA) system was used to
Keywords: deposit ultra-smooth Ti thin films on a transducer having patterned inter-digital gold electrodes (IDTs).
Nanoporous TiO2 Nanoporous TiO2 films were obtained by anodization of the titanium (Ti) thin films using a neutral 0.5% (wt)
Anodization NH4F in ethylene glycol solution at 5 V for 1 h. After anodization, the films were annealed at 600 °C for 8 h to
FCVA
convert the remaining Ti into TiO2. The scanning electron microscopy (SEM) images revealed that the average
H2 sensor
diameters of the nanopores are in the range of 20 to 25 nm. The sensor was exposed to different
concentrations of H2 in synthetic air at operating temperatures between 100 °C and 300 °C. The sensor
responded with a highest sensitivity of 1.24 to 1% of H2 gas at 225 °C.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction foils, preventing their application in the standard mass production of

Gas sensors are increasingly required for ensuring industrial health
and safety, environmental monitoring, automotive applications and
manufacturing process control. Recently, much attention has been
given to gas sensitive materials in nanostructured forms as they often
exhibit novel and enhanced properties compared to their bulk
counterparts [1,2]. It is well known that the performance of a gas
sensor is directly related to the granularity, porosity and surface to
volume ratio of the sensing materials [3,4]. Additionally, gas-sensing
performances of nanostructured metal oxide films can improve
remarkably when the size of the nanomaterials becomes comparable
to Debye length [5,6]. Low dimensional nanostructured materials
having increased surface to volume ratio facilitate rapid diffusion of
gases into and out of the materials' nanoporosities. This rapid
diffusion increases the reaction rate, resulting in faster sensor
response and recovery [7,8].
Titanium dioxide (TiO2) is one of the most widely used functional
materials with applications in gas sensors [4,9], dye-sensitized solar
cells [10,11], electro-chromic devices [12] and photocatalysis [5,13].
TiO2 films have been investigated as sensors for H2 [3,9], CO and NO2
[4,14], O2 [15], and hydrocarbons [16]. The gas-sensing capability of
TiO2 is due to changes in the film conductivity in the presence of
oxidizing or reducing gases. Recent successes in synthesizing TiO2 in
nanotubular and nanoporous forms have prompted explorations into
gas-sensing applications. However, most of the nanotubular and
nanoporous TiO2 forms produced to date have been synthesized in
⁎ Corresponding author.
E-mail addresses: sadek@ieee.org (A.Z. Sadek), Kourosh.kalantar@rmit.edu.au
(K. Kalantar-zadeh).
thin film based sensors.
Many research groups [17–24] have reported formation of
nanoporous and nanotubular surfaces of titanium oxide since Zwilling
et al. [25,26] first reported on self-organized nanotubular surfaces by
anodic oxidation of Ti foil. Anodization of Ti foils/films were
conducted in diluted fluoride ion containing electrolytes at a fixed
[23,27] or variable voltage [22,28] for a given time. Recently, it has
been reported that nanotubes can be formed in Ti using chloride and
bromide containing electrolytes as well [29,30]. A variety of electro-
lytes have been used to prepare TiO2 nanostructures such as acidic
[18], neutral [23,31], aqueous or non-aqueous electrolytes
[19,23,32,33]. Typically, the pore/tube diameter is controlled by the
applied anodization voltage, and the length can be varied by using
different anodization time and electrolytes [34]. The nanoporous/
nanotubular layers can be grown with tube or pore dimensions
varying from a few hundreds of nanometers to 1 mm in length, and
with diameters varying from 10 to 200 nm [17,23,32–35]. It has been
reported that the nanopore/tube growth mechanism involves initial
oxidation of Ti to form an oxide layer and the subsequent localized
dissolution of this layer by fluoride ions [22]. Details of the suggested
mechanisms for the formation of nanotubes/pores during the
anodization process can be found elsewhere [22,36,37].
The self-organized nanoporous/tubular structures of TiO2 have
already been tailored for various applications with improved
performance, such as dye-sensitized solar cells [38–41], sensors
[3,42–48], photocatalysts [49,50], electro-chromic displays [51–53]
and wettability applications [54,55]. Recently, Grimes et al. [3,42–44]
have reported TiO2 nanotube based conductometric H2 sensors where
nanotubes were anodized on Ti foil using acidic electrolyte solution. To
obtain experimental gas-sensing responses, they placed platinum

0040-6090/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2009.02.151
 A.Z. Sadek et al. / Thin Solid Films 518 (2009) 1294–1298
Fig. 1. SEM image of the FCVA deposited Ti film supported on a LiTaO3 substrate and
planar Au contacts (as indicated).
electrodes on the same side of the nanotube foil and found that the
device is highly sensitive towards H2. The electrical resistance of the
TiO2 nanotubes changes by almost four-orders of magnitude upon
exposure to 100 ppm H2 in N2 against air base line at room
temperature [44]. Grime et al. [48] also developed thin film gas
sensors based on TiO2 nanotube arrays and reported a four-order
magnitude drop in resistance on exposure to 1000 ppm H2 gas in N2
and negligible sensitivity to other reducing gases like methane, carbon
monoxide and ammonia. Zhang et al. [56] developed TiO2 nanotube
based humidity sensors using anodization of Ti foil. They observed
nearly two orders of magnitude change in resistance during the
relative humidity variation from 11 to 95%.
In this paper, we report a conductometric H2 sensor based on
nanoporous TiO2 thin films. Ultra-smooth Ti thin films were deposited
by filtered cathodic vacuum arc (FCVA) onto inter-digital transducers
(IDTs) supported on LiTaO3 substrates. The Ti films were then
anodized using a neutral NH4F/ethylene glycol electrolyte solution.
The completed nanoporous TiO2 films exhibited high surface to
volume ratio, homogenous pore growth and good adherence to the
substrate/contacts. Measurements were conducted for various gas
concentrations of H2 mixed in synthetic air.
2. Experimental
The sensor was designed and fabricated to operate as a resistive
element. The device comprises a sensitive TiO2 nanoporous layer
anodized over gold (Au) sputtered inter-digital electrodes on a
12 × 12 mm2 LiTaO3 substrate. The IDTs were formed by patterning
an 80 nm layer of gold (Au) and a 20 nm titanium layer. The titanium
layer is added as an under-layer to improve adhesion of the gold layer.
After formation of the contacts, the thin film Ti was deposited onto
the substrate using a FCVA system operated with a 70 mm diameter
cathode of 99.99% purity Ti. The cathode is struck by a grounded
mechanical striker to initiate the plasma. An arc current of 120 A (and
average arc power 3 kW) was found to be sufficient to produce a stable
plasma for the deposition experiments. A double-bend magnetic filter
was incorporated into the system and this prevented deposition of
macro-particles onto the sample, thereby minimizing surface rough-
ness. The samples themselves were mounted on a metallic holder
which slides onto an electrically isolated arm inside the chamber. A
1295
negative bias voltage can be applied to the holder via a high-voltage
feed-through. This bias causes the incident ions to be accelerated
towards the sample and this energetic deposition process assists in
the production of dense flat films. For these experiments the sample
bias was −100 V. The Ti films (with a thickness ranging from 250 nm
to 300 nm) prepared by FCVA were dense, smooth and highly
adherent to the substrates.
Anodization of the Ti films was carried out using a neutral
electrolyte medium of 0.5% (wt) NH4F in ethylene glycol solution at
5 V for 1 h. A platinum foil was used as a counter electrode for the
anodization at room temperature. Anodized samples were washed
with DI water before blow drying with dry nitrogen (N2) gas. After
anodization, the film was annealed at 600 °C for 8 h for conversion to
TiO2.
The sensor was mounted inside an enclosed environmental
chamber. Four mass flow controllers (MFCs) were connected to
form a single output that supplies gas to the cell. The gas delivery
system has the ability to accurately control and vary concentrations
for four different gases simultaneously. In this work, the authors have
employed two channels of MFCs at a time, one for synthetic air and
one for the target analyte (H2). The concentration of the gas was
varied by changing the synthetic air to analyte gas ratio while
maintaining a constant flow rate of 200 sccm.
Highly pure low concentration H2 (1%) gas balanced in synthetic
air in a cylinder was employed for this work. A high precision Keithley
2001 multimeter was used for measuring the variation of sensor
resistance. Custom LabVIEW-based software was utilized to control
the experimental setup and take measurement data from the sensor.
The sensor responses were displayed in real-time and saved for off-
line processing and analysis. The gas exposure time was fixed for each
pulse of analyte gas and the cell was purged with synthetic air for
fixed periods of time between each pulse to allow full recovery of the
sensor.
A planar micro-heater with dimensions of 25 × 25 mm2 was placed
beneath the sensor. The micro-heater was fabricated on a sapphire
substrate with a patterned platinum resistive element. A regulated DC
power supply was connected to the heater to control the operating
temperature of the sensor between the range of 100 and 300 °C in
increments of approximately 30 °C. A thermocouple was employed to
Fig. 2. SEM image of the anodized TiO2 film deposited around the boundary of an Au
electrode and the LiTaO3 substrate.
1296 A.Z. Sadek et al. / Thin Solid Films 518 (2009) 1294–1298
Fig. 3. SEM image of the anodized TiO2 film supported on LiTaO3.
obtain a real-time reading of the sensor surface temperature with an
accuracy of 1 °C.
3. Results
An SEM image of the FCVA deposited Ti film supported on the
conductometric transducer is shown in Fig. 1. Since the FCVA
deposited films are ultra smooth, the SEM image reveals little detail.
SEM images of the nanoporous TiO2 film are shown in Fig. 2 (over
film-contact interface), Fig. 3 (over LiTaO3 surface), and Fig. 4 (over
gold electrode surface). The SEM images revealed that the morphol-
ogy of the anodized Ti film is very similar, irrespective of whether the
film is over the Au or the LiTaO3. The average diameter of the
nanopores is 23 nm ± 3 nm. An XRD pattern of a FCVA deposited Ti
film supported on a LiTaO3 substrate is given in Fig. 5. The XRD pattern
shows that for the FCVA deposited Ti thin film, only the (002)
reflection was produced. It has been previously reported that after the
anodization of Ti films which were sputtered at elevated tempera-
Fig. 4. SEM image of the anodized TiO2 film supported on Au.
Fig. 5. XRD patterns of an FCVA deposited Ti film on a LiTaO3 substrate (bottom); and of
an anodized film annealed at 600 °C (top).
tures, nanotubes are obtained [48,57]. These films exhibit XRD
reflections corresponding to (101) and (002). The anodization of
FCVA deposited films only resulted in nanopores. It is therefore
possible that the initial (002) orientation of Ti films promotes the
formation of nanopores. A (101) reflection peak was observed in the
XRD spectra after annealing the anodized films at 600 °C for 8 h,
indicating the formation of rutile TiO2 (Fig. 5).
The dynamic response of a TiO2 sensor to a sequence of different H2
concentrations in synthetic air is shown in Fig. 6. The sensor response
for a reducing gas, defined as the ratio of the baseline resistance to the
sensor resistance after exposure to gas (Rair/Rgas), is 1.24 for 1% of H2 in
synthetic air at 225 °C. The highest sensitivity with the fastest
response and recovery were measured at 225 °C for 1% H2. The sensor
response as a function of the operating temperature in the presence of
1% H2 is shown in Fig. 7.
The repeatability of the sensor's response towards H2 was
observed with two 0.12% H2 pulses on the sequence shown in Fig. 6.
It was observed that magnitude of the second pulse decreased slightly
(~2%) with a downward baseline drift due to slower desorption rate.
The chemisorption of hydrogen ions (H2f2H+) onto the TiO2
nanopores is the basic mechanism for the sensor response. The
efficient interaction area between the gas molecules and the sensitive
nanoporous TiO2 surface determines the performance of the gas
sensor. Thus, increasing the surface to volume ratio of the TiO2 films
introducing nanoporosity improves the sensitivity as well as the
dynamic performance of the sensor. Although the interaction of a gas
with a sensing material is primarily a surface phenomenon, the gas-
sensing responses of the TiO2 nanopores/tubes cannot be explained
on the basis of surface interaction alone [43,44,47]. The nanoporous/
tubular forms of TiO2 have greatly reduced diameters and wall
thickness whose dimensions are comparable to the depletion layer
depth. The space charge layers are thus strongly modulated by the
dimensional features. Accordingly, oxygen adsorption to the nano-
pore/tubes' wall can lead to a complete depletion of conduction-band
electrons with a large variation in resistance.
Fig. 6. Dynamic response of the sensor to different H2 gas concentrations at 225 °C.
 A.Z. Sadek et al. / Thin Solid Films 518 (2009) 1294–1298
Fig. 7. Sensor sensitivity to 1% H2 gas versus the operating temperature.
In order to clarify the performances of the developed nanoporous
TiO2 based devices for H2 sensing, a brief comparative study of
previous works on TiO2 and other metal oxide based H2 sensors is
given here. The authors previously reported [8] a conductometric H2,
NO2 and hydrocarbon gas sensor based on single-crystalline zinc
oxide (ZnO) nanobelts deposited using a radio frequency (RF)
magnetron sputterer. The sensitivity of the developed sensor to 1%
H2 was calculated to be 14.3 at 385 °C. Although the sensitivity of the
ZnO nanobelt based sensor towards H2 is higher than the reported
nanoporous based TiO2 sensor, the optimum operating temperature
for the latter is much lower (225 °C). The author also recently reported
[7] hydro-thermally grown ZnO nanorod based surface acoustic wave
(SAW) sensors and found that the optimal operating temperature of
the devices for H2 sensing was 265 °C with a response of 274 kHz
towards 0.15% of H2. Wang et al. [58] developed self-assembled SnO2
nanowire sensors for H2 sensing and the device response was
measured to be 3.25 towards 1000 ppm H2 at 300 °C.
Grimes' group reported room temperature hydrogen sensors based
on anodic TiO2 nanotube arrays in foil [44] and in thin films [48].
These TiO2 nanotube array sensors showed a change in electrical
resistance upon exposure to 100 ppm hydrogen in N2 of four orders of
magnitude against the air base line at 25 °C. In this study, the
sensitivity seems to be lower than the sensitivity of the devices
previously fabricated by Grimes group. However, we tested the
nanoporous TiO2 against target H2 gas in synthetic air ambient and not
N2 which is the simulation of a real field application. The presence of
ambient oxygen (21%) affects the performance of the sensor and thus,
results are not comparable with the results obtained by Grimes group.
In the future work, we intend to enhance the performance of these
nanoporous sensors by modifying the pore diameters, layer thickness
and doping with noble catalytic metals (Pt, Pd or Au).
4. Conclusion
Conductometric hydrogen sensors based on nanoporous titanium
dioxide (TiO2) thin films have been developed and studied. Nano-
porosity on the films was obtained by the anodization of Ti thin films
deposited onto conductometric transducer substrates using a FCVA
system. Anodization of the Ti films was performed using a neutral 0.5%
(wt) NH4F in ethylene glycol solution at 5 V for 1 h. The films were
annealed at 600 °C for 8 h for conversion to the rutile form of TiO2. The
SEM images showed that the average diameter of the nanopores was
23 nm ± 3 nm. The XRD patterns suggest that the presence of (002)
preferred orientation on the FCVA deposited films may be the reason
behind the nanopores (instead of nanotubes) formation during
anodization. The sensor was exposed to different concentrations of
H2 in synthetic air at operating temperatures in a range of 100 °C to
300 °C and the sensor response of 1.24 towards 1% of H2 at 225 °C was
measured. The developed sensors are worthy of further investigation
for commercial applications.
1297
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