Available online at SciVerse ScienceDirect

J. Mater. Sci. Technol., 2013, 29(5), 411e414

Comparative Analysis of Ti, Ni, and Au Electrodes on Characteristics of TiO2

Nanofibers for Humidity Sensor Application
S.S. Batool1,2)*, Z. Imran1,2), M. Israr Qadir2), M. Usman1), H. Jamil1), M.A. Rafiq1)*, M.M. Hassan1),
M. Willander2)
1) Micro and Nano Devices Group, Department of Metallurgy and Materials Engineering, Pakistan Institute of Engineering and
Applied Sciences, PO Nilore, Islamabad 45650, Pakistan
2) Department of Science and Technology, Campus Norrköping, Linköping University, SE-60174 Norrköping, Sweden
[Manuscript received June 13, 2012, in revised form October 26, 2012, Available online 1 March 2013]

The effect of metal (Ti, Ni, and Au) electrodes on humidity sensing properties of electrospun TiO2 nanofibers was
investigated in this work. The devices were fabricated by evaporating metal contacts on SiO2 layer thermally
grown on silicon substrate. The separation between the electrodes was 90 mm for all sensors. The sensors
were tested from 40% to 90% relative humidity (RH) by AC electrical characterization at room temperature.
When sensors are switched between 40% and 90% RH, the corresponding response and recovery time are
3 s and 5 s for Ti-electrode sensor, 4 s and 7 s for Ni-electrode sensor, and 7 s and 13 s for Au-electrode
sensor. The hysteresis was 3%, 5% and 15% for Ti-, Ni-, and Au-electrode sensor, respectively. The
sensitivity of Ti, Ni, and Au-electrode sensors are 7.53 MU/%RH, 5.29 MU/%RH and 4.01 MU/%RH
respectively at 100 Hz. Therefore Ti-electrode sensor is found to have linear response, fast response and
recovery time and higher sensitivity as compared with those of Ni- and Au-electrode sensors. Comparison of
humidity sensing properties of sensors with different electrode material may propose a compelling route for
designing and optimizing humidity sensors.

KEY WORDS: Titanium dioxide; Nanofibers; Metal electrodes; Humidity sensor

1. Introduction evaluating the current voltage measurements[8]. In spite of all

Tremendous attention has been paid to the development of
ever more sensitive humidity device has been paid due to its
applications in environmental monitoring in living space,
manufacturing space, industrial processing control, inspection
and medical diagnostics[1e3]. Hitherto, many efforts have been
exercised to increase the sensitivity and achieve the rapid
response and recovery time. However, most of them have
focused on investigating the effect of metal doping on electro-
spun nanofibers. Doping of nanofibers increases the number of
target molecules that interact with the semiconductor[4e7]. At the
same time, contact resistance between metal electrode and
sensing material can also affect the efficiency of the sensing
film[8]. Therefore the change in sensitivity of direct current hu-
midity sensor with different electrodes was investigated by
* Corresponding authors. Mrs.; Tel.: þ92 51 2207381; Fax: þ92 51
2208070; E-mail addresses: sitwat_naqvi@yahoo.com (S. S. Batool),
fac221@pieas.edu.pk (M. A. Rafiq).
1005-0302/$ e see front matter Copyright Ó 2013, The editorial office of
Journal of Materials Science & Technology. Published by Elsevier
Limited. All rights reserved.
http://dx.doi.org/10.1016/j.jmst.2013.02.017
these improvement in sensitivity of humidity sensor, it is
impossible to ignore the size and surface of sensing material. The
nanomaterials significantly enhance the humidity sensing prop-
erties as compared with the traditional porous ceramic structure
due to high surface-to-volume ratio[1,9e11]. Porous ceramic
nanomaterials have been extensively investigated as humidity
sensitive materials in recent years. These materials exhibit better
sensing properties, such as shorter response time, smaller hys-
teresis, higher sensitivity and improved stability. Among all
these ceramic semiconductors, titanium dioxide (TiO2) and its
nano devices are of remarkable importance due to its porous
structure and wide band gap (w3.00) with their increasing ap-
plications in the sensing and photocatalytic activities[7,12e14].
Humidity sensor based on TiO2 nanomaterials have been widely
reported[15
17], however the effect of electrode material on
sensing properties is rarely investigated.
Previously, our group has applied TiO2 nanofibers in DC
humidity sensors[18]. The present study aims at describing the
alternating current (AC) humidity sensing properties of these
nanofibers, and the effect of three different electrode materials on
sensors properties are also reported. The present results offer an
effective approach to understand and design TiO2 based hu-
midity sensing material.
412 S.S. Batool et al.: J. Mater. Sci. Technol., 2013, 29(5), 411e414
Fig. 1 (a) Schematic of the final device for the RH sensors, (b) TiO2 nanofibers annealed at 600  C, (c) TEM image of TiO2 nanofibers.
2. Experimental
TiO2 nanofibers were prepared through electrospinning and
calcination techniques. In a typical procedure, 1.5 ml of titanium
tetraisopropoxide was mixed with 3 ml of ethanol and 3 ml of
acetic acid in a glove box under vigorous stirring for 10 min. The
prepared solution was added to 7.5 ml of ethanol containing
0.45 g of Polyvinylpyrrolidone (PVP, Mw ¼ 1,300,000) one drop
at a time under continuous stirring for 1 h and the resulting
mixture was loaded into plastic syringe. Positive terminal of high
voltage power supply was connected to syringe needle tip, while
the collector covered with aluminum foil was grounded. The
voltage of 10 kV was applied between needle and collector. The
distance between the needle tip and collector plate was 10 cm.
The obtained product was dried at room temperature for 24 h and
then calcined at 600  C for 3 h in open air to form TiO2
nanofibers.
To fabricate relative humidity (RH) sensors, the TiO2 nano-
fibers were mixed with isopropanol in a weight ratio of 100:5
and mixed to form a suspension. The prepared solution was spin
coated onto three different silicon substrates having top SiO2
layer at 2000 r/min before the deposition of Ti, Ni and Au
electrodes, which acts as sensing region between the electrodes.
The 80 nm thick metal electrodes (Ti, Ni, and Au) were evap-
orated using a shadow mask. 20 nm thick Cr was evaporated
before the evaporation of metal electrodes (Ti, Ni, and Au) to
improve adhesion with substrate. The distance between the
electrodes was 90 mm for all sensors. The metal contacts sit on
the top of the TiO2. The schematic picture of final device is
depicted in Fig. 1(a).
Field-emission scanning electron microscopy (FE-SEM) and
transmission electron microscopy (TEM) images were recorded
using a JSM-6490LA and Jeol 2010 (200 kV) Japan, respec-
tively. Thermogravimetric analysis and differential scanning
Fig. 2 TGA/DSC curve of TiO2/PVP nanofibers.
calorimetry (TGA & DSC) data (TiO2/PVP) were obtained by
using TGA Q500 and DSC Q100 under nitrogen flow (10 ml/
min) with sample weight of 1.950 mg and heating rate of 10  C/
min.
The characteristic curves of RH sensors were measured by
using a dielectric spectrometer (broad band dielectric spec-
trometer, Novo Control Germany) at ambient temperature. The
fixed value of 1 V AC signals is used in our studies while the
frequency was varied from 10
1 Hz to 106 Hz. The RH envi-
ronment in the range of 40e90% was achieved by the well-
controlled climate chamber (Blue M electric, Japan). The
WINDATA software was used for output data, which is fully
automated by interfacing the dielectric spectrometer with a
computer. The complete experimental work was done in a clean
room at a controlled temperature of 25  C.
3. Results and Discussion
The morphology of the as calcined nanofibers was charac-
terized by FE-SEM and TEM. The FE-SEM image in Fig. 1(b)
indicates that the nanofibers interlace each other. The typical
length of nanofibers ranges from 100 mm to 200 mm while the
diameter of nanofibers ranges from 100 nm to 150 nm. The
length and diameter were estimated from SEM images. TEM
image confirms the porous nature of nanofibers (Fig. 1(c)).
Fig. 2 shows the TGA and DSC curves of as prepared TiO2/
PVP nanofibers. From room temperature to 49  C and then to
about 100  C, weight loss is attributed to the release of
remaining solvents and physically absorbed water on the fibers
surface, respectively. Weight loss between 100  C and 400  C
corresponds to the decomposition of PVP. Between 420 and
490  C, PVP completely burns out and abrupt change in weight
was obtained. In DSC curve the endothermic peak at 98  C
corresponds to the removal of absorbed water in the pores of the
Fig. 3 Dependence of sensors impedance on RH at 1 V and 100 Hz.
 S.S. Batool et al.: J. Mater. Sci. Technol., 2013, 29(5), 411e414
surface of TiO2/PVP nanofibers. The pores with small radius
make it difficult for the desorption of water molecules from the
surface of nanofibers and so the strong endothermic peak ap-
pears[15]. Again an endothermic peak at 420  C may confirm the
decomposition of residual organic moieties in the nanofibers.
Above 490  C, sample weight only slightly decreased, indicating
most of the organic moieties decomposed below 490  C.
In order to explore the effect of electrode on humidity sensing
characteristics of TiO2 nanofibers sensor, the Ti-electrode, Ni-
electrode, and Au-electrode sensors were tested from 40% to
90% RH at room temperature. Fig. 3 shows the impedance of Ni-
electrode, Ti-electrode and Au-electrode sensors vs RH at
100 Hz. The impedance of three sensors becomes smaller as the
RH increases. But the decrease rate is quite different, i.e.
impedance changes from 300 MU to 38 MU for Ni-electrode
sensor, 381 MU to 4.7 MU for Ti-electrode sensor and from
199 MU to 0.03 MU for Au-electrode sensor, as the humidity
changes from 40% to 90% RH. In other words, the sensors with
different metal electrodes exhibit different sensitivities to the
change of RH. Ti-electrode and Ni-electrode sensor shows quite
linear behavior in this range but the Au-electrode sensor offers
low impedance as compared with Ti-electrode and Ni-electrode
sensor with poor linearity. From Fig. 3, sensitivity of the TiO2
nanofibers sensors can be calculated by using the formula[19].
Sensitivity ¼ DðimpedanceÞ=D%RH
From Eq. (1) sensitivity of Ti-electrode, Ni-electrode, and Au-
electrode sensors are 7.53 MU/%RH, 5.29 MU/%RH and
4.01 MU/%RH respectively at 100 Hz.
The response time and recovery time are key parameters for
evaluating the performance of a humidity sensor. The response
and recovery characteristics of the TiO2 nanofibers sensors were
measured when RH was switched from 40% to 90% and then
Fig. 4 Response and recovery curve of RH sensors: (a) Ti-electrode sensor; (b) Ni-electrode sensor; (c) Au-electrode sensor.
Fig. 5 Hysteresis effect of RH sensors: (a) Ti-electrode; (b) Ni-electrode sensor; (c) Au-electrode sensor.
413
Table 1 Comparison of RH sensors with using different electrodes
Sensors Response/recovery Hysteresis Sensitivity
time (s) (%) (MU)/%RH
Ti-electrode 3/5 3 7.53
Ni-electrode 4/7 5 5.29
Au-electrode 7/13 15 4.01
back to 40% at room temperature. Fig. 4(a)e(c) shows the
response and recovery curves for the Ti-electrode, Ni-electrode
and Au-electrode sensor, respectively. The response time is the
time to reach 90% of the final impedance (for humidification
from 40% to 90% RH)[19]. The response time for the Ti-
electrode, Ni-electrode and Au-electrode sensors are 3 s, 4 s
and 7 s, respectively. The recovery time is the time required to
attain 90% of total impedance change in case of desorption (90e
40% RH)[19]. The recovery time is 5 s, 7 s and 13 s for Ti-
electrode, Ni-electrode and Au-electrode sensor, respectively.
Therefore, it can be concluded that Ti-electrode sensor has better
response time and recovery time as compared with Ni-electrode
and Au-electrode sensors.
To check the calibration accuracy of our TiO2 nanofibers
sensors we measured the hysteresis by running the sensors in full
humid loop (40e90% RH) with dwell time of half an hour at
(1) each point. For the calibration accuracy at a certain RH value the
mean of the measured value of ascending and descending path
can be calculated and then the difference of these mean values
determine the hysteresis value. Hysteresis values of our sensors
are 3%, 5% and 15% for Ti-electrode, Ni-electrode and Au-
electrode sensors, respectively, as shown in Fig. 5. It is evident
that Ti-electrode sensor has low hysteresis values as compared
with those for the Ni-electrode and Au-electrode sensors.
Table 1 shows the comparison of the characteristics of three
sensors. It can clearly be seen that Ti-electrode sensor exhibits
414 S.S. Batool et al.: J. Mater. Sci. Technol., 2013, 29(5), 411e414
Fig. 6 Micrographs of the Ti-electrode (a), Ni-electrode (b) and Au-electrode (c).
relatively shorter response time and recovery time with small
hysteresis and higher sensitivity as compared to Ni-electrode and
Au-electrode sensors. Moreover Ti-electrode sensor has good
linearity. This suggests that Ti electrodes are beneficial in
improving the TiO2 nanofibers humidity sensor.
Complex impedance is the best way to explain the sensing
mechanism. At low RH the chemisorptions of hydroxyl ions take
place on the surface of sensing material, and these hydroxyl ions
trapped and dissociate upon the application of electric field. This
dissociation provides charge and ions (Hþ) as a charge carrier of
hopping transport but the chemisorbed layer cannot cover the
sensing material continuously, so the ion transport rarely
happened and high impedance was observed[6]. The phys-
isorption phenomenon occurs at higher RH causing water mol-
ecules to attach with the neighboring hydroxyl groups through
hydrogen double bond, and a proton may be transferred from a
hydroxyl group to the water molecule to form hydroxyl (H3Oþ)
ions. So, the concentration of Hþ and H3Oþ ions increases with
increasing RH and transportation of ions is more easy as
compared to low RH[1]. Thus, the impedance continuously de-
creases by some order compared to the initial values.
The sensors fabricated with Ti-electrode exhibit improved
sensing properties compared to the sensors with Ni-electrode and
Au-electrode. This may be attributed to the porous structure of
metal electrode. By comparing the microstructure of three
different electrodes (Fig. 6) it can be confirmed that Ti-electrode
exhibits the porous structure which causes the water vapor
diffusion through pores to reach the sensing material layer[20].
The Au-electrode forms dense layer than Ni and Ti which
adversely affect the water vapor diffusion. This might be one of
the reasons for nanofibers humidity sensor with Ti-electrode to
exhibit better characteristic than Ni- and Au-electrode.
4. Conclusion
In this research, TiO2 nanofibers have been synthesized via
electrospinning and calcinations techniques. An interesting cor-
relation between sensing properties and different metal contacts
has been observed by fabricating three humidity sensing devices.
Ti-electrode sensor shows higher sensitivity and faster response
and recovery time with good linearity as compared to Ni- and
Au-electrode sensors. The results may propose a compelling
route for designing and optimizing RH sensors.
Acknowledgment
We acknowledge the financial support of the Higher Edu-
cation Commission (HEC), Pakistan.
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