Microelectronics

Journal

Microelectronics Journal 31 (2000) 561–567

www.elsevier.com/locate/mejo

Microfabrication and reliability study of sapphire based Ti/Pt-electrodes

for thin-film gas sensor applications
W. Qu*, W. Wlodarski, M. Austin
Department of Communication and Electronic Engineering, RMIT University, Melbourne, Vic. 3001, Australia
Received 30 November 1999; accepted 30 December 1999

Abstract
The paper describes the design, fabrication and characterisation of a Ti/Pt-electrode system (an interdigital electrode with an aligned
heater) on a sapphire substrate. It serves as substrates for subsequent deposition of gas sensitive films. The fabrication has been accomplished
on both sides of a sapphire wafer. Wet chemical etching and the lift-off method have, respectively, been used for structuring the electrode and
the heater patterns. The mechanical stability and the electrical conductivity of the resultant Ti/Pt-films are greatly affected by the subsequent
heat treatment procedures. The diffusion of titanium ions into platinum has been examined using SIMS depth profiles. After annealing at
600⬚C for 5 h, the temperature coefficient of the Ti/Pt-film stabilised at the value of 0.0033 K ⫺1, which approaches the pure platinum bulk
value of 0.0039 K ⫺1. With a good mechanical and thermodynamical stability at high temperatures and under oxidising and reducing
conditions, the sapphire based Ti/Pt-electrode system is well suited for gas sensor fabrication. As an example of its application, we report
a highly sensitive O3 gas sensor developed by evaporating a WO3 thin-film onto this electrode. 䉷 2000 Elsevier Science Ltd. All rights
reserved.
Keywords: Ti/Pt-electrode; Sapphire; Thin-film; Diffusion; Thermodynamic stability; Harsh environment; Ozone sensor

1. Introduction ceramic surface. Ceramic processing methods were first

Gas sensors usually have to work at high temperatures
and in aggressive oxidising or reducing gas media. For
example, gas sensors applied in automotive and aerospace
industry must tolerate with temperatures of up to 850⬚C and
resist strong oxygen aggressions. Although silicon tech-
nology has had tremendous success in the microelectronics
area, its components could rarely be applied to harsh envir-
onments such as high temperature, aggressive media and
radiation exposure. The main limitations of using silicon
components at high temperatures are junction leakage,
metallisation degradation as well as packaging failure at
elevated temperatures. Nowadays, the III–V semiconduct-
ing oxides are still the dominating materials for gas sensing,
mainly due to their excellent tolerance with high tempera-
tures and aggressive media.
Gas sensing is a surface- and interaction-related process.
It makes use of molecular adsorption and reaction at a
* Corresponding author. Address: Institut für Halbleiter- und Mikro-
systemtechnik, Technische Universität Dresden, 01062 Dresden, Germany.
Tel.: ⫹ 49-351-463-6450; fax: ⫹ 49-351-463-7021.
E-mail address: qu@ihm.et.tu-dresden.de (W. Qu).
used for gas sensor fabrication [1]. Powders of the sensing
material were pressed into tablets and subsequently sintered.
After being evaporated with the electrodes, the tablet was
mounted inside a coil that was used to heat the sensor to its
high working temperature. The drawbacks of the ceramic
device are the large size and high power consumption. At
the beginning of the 1980s, the Japanese company FIGARO
advanced gas sensor fabrication by screen printing the elec-
trode and sensing film onto a ceramic substrate. 1 The sensor
size and the power consumption were hence reduced to a
certain extent. Since the 1990s, thin-film technologies have
been increasingly used for gas sensor fabrication. Compared
with the ceramic tablets and thick-films, thin-films have
great advantages of being excellently reproducible and
eligible for cost-effective mass production. For the systema-
tic investigation of thin-film gas sensors, we developed a Ti/
Pt-electrode system on the sapphire substrates. It has an
overall dimension of 4 × 6 × 0:25 mm3 : Various gas sensi-
tive films can be subsequently deposited onto this basic
structure using different coating technologies, such as
1
Technical data sheet of FIGARO company (1984–1998).

0026-2692/00/$ - see front matter 䉷 2000 Elsevier Science Ltd. All rights reserved.
PII: S0026-269 2(00)00030-6
562 W. Qu et al. / Microelectronics Journal 31 (2000) 561–567

Fig. 1. Schematic drawing of the thin-film electrode system: (a) interdigital-electrode on the front side; (b) heater on the backside.

sputtering, evaporation and sol–gel. The electrode system
possesses a new electrode and heater configuration. The
heater serves simultaneously as a thermometer whose
resistance provides the working temperatures of the sensor.
The electrode system showed a good mechanical and ther-
modynamic stability even at high temperatures with the
presence of aggressive gases. The following sections
describe the design, fabrication and process optimisation
of the Ti/Pt-electrode system on a sapphire substrate,
emphasising on the film stability and its electrical proper-
ties. Then, as an example of its application, a thin-film WO3
ozone sensor is reported.
2. Sapphire based Ti/Pt-electrode system
2.1. Configuration and fabrication
A new design of the electrode and heater configuration
has been applied to the electrode system, as shown in Fig. 1.
In particular, the unique configuration of the heater is able to

Fig. 2. Flow chart of the fabrication steps of the sapphire based Ti/Pt-thin-film electrode.
 W. Qu et al. / Microelectronics Journal 31 (2000) 561–567
Fig. 3. Photograph of the sapphire based Ti/Pt-thin-film electrode.
provide a homogeneous temperature distribution across the
entire sensing area. In addition, unlike the previous elec-
trode systems based on a sapphire substrate [2], this new
design enables the sensor to be vertically mounted on a TO-
8 base, providing a very effective packaging for sensor
elements working at high temperatures.
Because of the required thermodynamic stability and
the need for temperature measurement, platinum was
used as the raw material for the electrode and the
heater. Sapphire was selected as substrate due to its
excellent mechanical, thermal and chemical stability in
harsh environments as well as a good surface finish for
thin-film deposition.
To enhance the adhesive strength between the electrode
material (Pt) and the sapphire (Al2O3), the surface of
double-side polished sapphire wafers has been pre-treated
to be a physically clean, but rough mechanical interface
zone with following three main steps:
1. Pre-cleaning the sapphire surface outside a vacuum
employing ultrasonic and chemical means, like CxHy,
NH4F, Cr2(SO4)3, etc.
2. Slight wet-etching the sapphire surface chemically using
NaOH.
3. Plasma cleaning the substrate in vacuum, with the
substrate being heated to a high temperature of about
500⬚C. This step is aimed at removing the chemically
adsorbed water film on the substrate surface.
The electrode system is then fabricated in a batch process
onto the pre-treated sapphire. Fig. 2 illustrates the essential
fabrication steps:
1. A titanium layer of approximately 30 nm in thickness
and a platinum layer of approximately 120 nm in thick-
ness were thermally evaporated successively onto the
sapphire substrate.
2. An AZ1512 resist layer of approximately 1.8 mm in
563
thickness was spun onto the Pt-film and patterned photo-
lithographically using the mask for interdigital electrode.
3. The Ti/Pt-film system was wet-chemically structured
using two etching solutions for Pt and Ti.
4. The resist was risen away using acetone.
5. An AZ1512 resist layer of approximately 1.8 mm in
thickness was spun onto the other side of the substrate.
6. The resist was patterned in a precise alignment to the
electrode patterns using the mask for the heater.
7. A titanium layer of approximately 30 nm in thickness
and a platinum layer of approximately 170 nm in thick-
ness were thermally evaporated successively onto the
patterned resist.
8. The Ti/Pt-film system was structured in a lift-off process.
The electrode units on the wafer were separated from
each other using a diamond saw. Then, platinum wires
with a diameter of 100 mm were thermally pressed onto
the electrode pads. Fig. 3 is a photograph of the finished
sapphire based Ti/Pt-electrode system. The system has to be
treated thermally at medium high temperatures in air before
the sensing films were coated.
In this fabrication, titanium is deposited as an intermedi-
ate layer prior to the functional material, platinum. The film
deposition rate for titanium at a chamber vacuum of 1:0 ×
10⫺7 bar is 0.1 nm/s. While the deposition rate for platinum
at a chamber vacuum of 8:6 × 10⫺8 bar is 0.05 nm/s. Tita-
nium is a very reactive metal, it reacts chemically or
diffuses onto the substrate and alloys itself with the plati-
num film. In this way, it promotes the adhesive strength
between the functional metal film and the substrate. The
titanium layer has also an influence on the electrical prop-
erties of the Ti/Pt-electrode system, as will be discussed
in Section 2.2.
Our available mask aligner could not perform double-
sided lithographic operation. Hence, to align the structures
on both sides of the wafer, wet-chemical etching and lift-off
564 W. Qu et al. / Microelectronics Journal 31 (2000) 561–567

Fig. 4. SIMBAD simulated profiles of thin-films growing on patterned photoresists with an opening ratio of 4:3 and resist thickness of: (a) 3 mm; (b) 5 mm; and
(c) 10 mm.

were, respectively, used for patterning the electrode and the
heater structures.
Lift-off was not used to pattern the electrode structure
mainly because the microstructure of a thin-film is a result
of self-shadowing in the depositing film, nucleation
phenomena and surface diffusion. Hence, film growth is
under highly non-linear conditions and is strongly depen-
dent on the angular distribution of the incoming atomic flux.
In addition, the UV patterned photoresists do not have an
absolute vertical edge [3]. Column growth in the patterned
area is therefore unavoidable. Fig. 4 illustrates the simulated
film profiles growing on patterned photoresists. The simula-
tion was done by using the SIMBAD simulation tool at the
Institute for Semiconductor and Microsystems Technology,
Dresden University of Technology. The simulation was
based on the STS cluster-tool in this Institute, the target
material was copper and the distance between the target
and the substrate was 200 mm. Evidently, the lift-off of
such structures will result in bad edge cuttings, as shown
in a SEM photograph in Fig. 5. It is not very bad if the
subsequent films are deposited by PVD or CVD means.
However, if the films have to be formed from a coated
solution, such as in the case of the sol–gel technique,
these rough edges on the electrodes will prevent a homo-
genous distribution of the solution in the whole substrate.
On the other hand, we used lift-off for patterning the
heater structure. This is mainly due to the need for aligning
the relevant structures on both sides of the wafer. Where
metal films are deposited first, alignment of the structures
with the other side could not be achieved, as the mask
aligner cannot be used for double-sided lithographic opera-
tion. The lift-off process, however, enables us to align the

Fig. 5. SEM photograph showing lift-off structured thin-films with bad edge cutting.
 W. Qu et al. / Microelectronics Journal 31 (2000) 561–567
Table 1
Average intensities of 48Ti ⫹ as determined by SIMS analysis of the plati-
num layer and the resultant film resistances after 30 min of heat treatment at
various temperatures
Treating temperature (⬚C) Intensity of 48Ti ⫹ in Film resistance (V)
Pt-layer (cps)
As-deposited Below detection limit 372
500 87 202
600 320 232
800 1100 162
negative pattern of the heater structure in the form of a
photoresist with the electrode structures on the other side.
After metallisation and photoresist stripping, the structured
positive metallic patterns are precisely aligned with the rele-
vant structure on the other side. The unsmooth edges on the
heater structure caused by the lift-off operation have in fact
no effects on the sensing film distribution on the other side
of the wafer.
2.2. Electrical properties and stability of the sapphire based
electrode system
The stability of the Pt/Ti-electrode–sapphire–Pt/Ti-
heater system is a necessity for the reproducible function-
ality of the thin-film gas sensor as a whole. The mechanical
stability of the deposited Ti/Pt-film could only be achieved
through subsequent heat treatment. During heat treatment,
titanium ions diffuse into the polycrystalline platinum layer.
The SIMS depth profile investigation on the platinum layer
confirmed the titanium diffusion at elevated temperatures. A
remarkable increase in the concentrations of titanium in the
platinum layer was observed at higher treating temperatures,
as given in Table 1.
Titanium diffusion promotes the adhesive strength
between platinum and sapphire. On the other hand, the
diffusion of titanium into the platinum layer changes both
the bulk conductivity and the surface conductivity due to the
Fig. 6. The resistance of the Ti/Pt-film heater versus time at an annealing
temperature of 600⬚C.
565
influence of titanium on the electro-mobility in platinum.
We found that the electrical resistance of the thermally trea-
ted Ti/Pt-film becomes considerably smaller than the resis-
tance of the as-deposited film. In the temperature range of
400–800⬚C, the higher the treating temperature, the smaller
the resultant resistance. However, temperatures higher than
850⬚C could result in a very large film resistance due to
titanium oxidation underneath the platinum layer.
Our experiments indicated that the optimal treating
temperature is about 600⬚C. Fig. 6 records the resistance
of Ti/Pt-film versus time at an annealing temperature of
600⬚C. After 5 h, the temperature coefficient of the Ti/Pt-
film stabilised at the value of 0.0033 K ⫺1, which approaches
the pure platinum bulk value of 0.0039 K ⫺1. In fact, the film
resistance could reach 98% of its end value within 20 min of
heat treatment, as illustrated in Fig. 6.
As a heater, the Ti/Pt-film is able to heat the sensor device
to a temperature of up to 800⬚C. As a thermometer, the
resistance of the thermometer has an almost linear relation-
ship with the temperature variations, as shown in Fig. 7. The
relationship between the Ti/Pt-film resistance R (V) and the
temperature T (K) can be approximately described by
R ˆ 5:5622T ⫹ 180:51: 1†
The annealed Ti/Pt-film electrode system exhibits an
excellent stability even in harsh environments, i.e. at high
temperatures of up to 800⬚C and under oxidising and redu-
cing conditions. The ambient temperature or the working
temperature of the sensor for gas sensing can be therefore
directly deduced from the resistance value of the Ti/Pt-film
thermometer. The response time of the film resistance to
temperature changes is less than 5 s.
3. A WO3 thin-film ozone sensor
3.1. Sensor fabrication
Ozone is a strong oxidising agent. In this work, an O3
sensor is taken as an example to illustrate the ability of
the electrodes to operate in a harsh environment application.
WO3 is selected as the sensing material. Although WO3 is a
relatively inert material showing only a little sensitivity to
organic vapours (CxHy) and some reducing gases, its elec-
trical conductivity varies greatly under the influence of
oxidising gases. The reaction of oxidising gases on the
surface of WO3 attracts electrons from the semiconducting
films, resulting in a decrease in conductivity [4]. Thin-films
are best suited for O3 detection, as a large part of the O3 is
thermally decomposed on the fine particle surface and
cannot reach the sensing film inner bulk parts [5].
Commercial WO3 powders with 99.9% purity were then
evaporated onto the substrate. The film deposition rate at
5 × 10 ⫺4 Pa was about 6 nm/min. The evaporated amor-
phous film was subsequently crystallised in an annealing
process carried out in air. Our examination revealed that
566 W. Qu et al. / Microelectronics Journal 31 (2000) 561–567
Fig. 7. The temperature-dependence of the Ti/Pt-heater as a thermometer.
the as-deposited WO3 films were amorphous. However,
after annealing at 400–800⬚C, the films crystallised to
homogeneous porous structures with nano-grains of 20–
100 nm, depending on the annealing temperature and
time. The morphology of the WO3 sensing film annealed
at 550⬚C is given as a SEM photograph in Fig. 8. The thick-
ness of the WO3 sensing film was determined to be about
150 nm.
3.2. Sensor characteristics
At high temperature, O3 seems to decompose on the WO3
sensing film surface as:
O 3 ! O2 ⫹ O⫺
The atomic oxygen can be then easily adsorbed on the
sensing grain surface as O ⫺. The negative oxygen ion on the
sensing grain surface raises the existing electrical barrier
between adjacent grains. As a result, the electrical conduc-
tivity of the film decreases.
The reaction of the O3 gas with the WO3 sensing film is
Fig. 8. SEM picture of the WO3 layer annealed at 550⬚C for 60 min.
Fig. 9. Sensor response to ozone gas at a working temperature of 300⬚C.
affected greatly by the sensor working temperatures. At
temperatures around 300⬚C, the sensor yields a reasonable
value of ozone sensitivity with a recovery time of 2 min [4].
Fig. 9 shows a chart recording the sensor response to ozone
gas at a working temperature of 300⬚C. The recording time
for each ozone concentration (50, 100, 150 and 175 ppb) is
10 min. The measured O3 gas was generated by a gas cali-
bration establishment which pumps ambient air at a flow
rate of 1.8 l/min through a pen-ray UV lamp to a quartz
chamber where the sensors are housed. The intensity of the
UV radiation is continuously adjustable by means of shifting
the metal shutter around the lamp. Flowing through the pen-
ray lamp, the oxygen molecules in air can be oxidised under
the UV radiation to ozone molecules with a concentration in
2† the range of 0–175 ppb, according to the UV-radiation inten-
sity. The gas response of the sensor was recorded by a
computerised multimeter system (HP 34401A).
4. Conclusions
A Ti/Pt-thin-film electrode with associated heating
element has been fabricated on both sides of a sapphire
substrate. The fabrication procedure has been discussed
and the manufacturing parameters have been subsequently
optimised. The electrode system has shown a good mechan-
ical, chemical and thermodynamical stability at harsh envir-
onments, i.e. at high temperatures and in an oxidising or
reducing gas media. Hence, it is suitable for gas sensor
fabrication. In addition, the Ti/Pt-film heater at the backside
of the substrate works also as a thermometer, measuring
directly the ambient temperature or the working temperature
of the gas sensor.
A thin-film WO3 ozone sensor has been described as an
example of the electrode’s application for gas sensor fabri-
cations. Films of WO3 with a thickness of 150 nm have been
thermally evaporated onto the sapphire based Ti/Pt-
electrode. At high temperatures, the electrical conduction
of the WO3 thin-films decreases upon the adsorption of
ozone gases.
 W. Qu et al. / Microelectronics Journal 31 (2000) 561–567
Acknowledgements
Wenmin Qu wishes to thank Dr.rer.nat. Christian Wenzel
and Dr.-Ing. Norbert Urbansky, Institute for Semiconductor
and Microsystems Technology (IHM), Dresden University
of Technology, Dresden, Germany, for their continuos
encouragement and support in the film characterisation.
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