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Unprecedented ultra-high hydrogen gas sensitivity in undoped titania nanotubes

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2006 Nanotechnology 17 398

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INSTITUTE OF PHYSICS PUBLISHING NANOTECHNOLOGY
Nanotechnology 17 (2006) 398–402 doi:10.1088/0957-4484/17/2/009

Unprecedented ultra-high hydrogen gas

sensitivity in undoped titania nanotubes
Maggie Paulose1 , Oomman K Varghese2 ,
Gopal K Mor2 , Craig A Grimes2 and Keat G Ong1
1
SentechBiomed Corporation, 200 Innovation Boulevard, State College, PA 16803, USA
2
Department of Electrical Engineering, Department of Materials Science and Engineering,
The Pennsylvania State University, University Park, PA 16802, USA

E-mail: kgong@sentechbiomed.com

Received 9 September 2005, in final form 10 November 2005

Published 14 December 2005
Online at stacks.iop.org/Nano/17/398
Abstract
A highly ordered array of micron-length undoped titania nanotubes exhibits
an unprecedented variation in electrical resistance of about 8.7 orders of
magnitude (50 000 000 000%), at room temperature, when exposed to
alternating atmospheres of nitrogen containing 1000 ppm hydrogen and air.
This represents the largest known change in electrical properties of any
material, to any gas, at any temperature. The nanotube arrays were
fabricated using anodic oxidation of titanium foil in a pH 4.0 electrolyte
containing potassium fluoride, sodium hydrogen sulfate monohydrate and
sodium citrate tribasic dihydrate. The dramatic change in resistance is
believed to be due to the highly active surface states on the nanoscale walls
of the tubes, high surface area of the nanotube architecture, and the
well-ordered geometry allowing for hydrogen-sensitive tube-to-tube
electrical connections.
(Some figures in this article are in colour only in the electronic version)

1. Introduction titania nanotube array fabricated by anodization of titanium

Metal oxide semiconductors are known to vary their electrical
resistance with respect to the gas ambient and hence are
widely used for chemical sensing [1, 2]. However, elevated
temperatures, typically several hundred degrees Celsius, are
needed for these materials to obtain any notable gas responses.
Furthermore, in pure form these materials do not have the
ability to selectively respond to a particular gas from a
mixture and hence chemical modification, such as doping
or surface functionalization, must be used [2–5]. For
example, to improve the sensitivity and selectivity of metal
oxides to hydrogen at room temperature it is common to use
palladium as a dopant or thin surface coating [6, 7]. With
the advent of nanotechnology, nanostructures of functional
metal oxides such as SnO2 , ZnO, TiO2 , WO3 , Ga2 O3 and
In2 O3 have been developed for environmental sensing, and
it has become evident that nanoscale architectural features
have the ability to yield superior and often unexpected
gas-dependent electrical behaviour [8–17]. With a unique
architecture comprising a highly ordered, high aspect ratio
we have observed an unprecedented, phenomenal change in
electrical resistance in response to low levels of hydrogen
at room temperature. Carbon monoxide and methane,
both strong reducing gases, do not significantly impact
the resistance of the nanotubes. Our results demonstrate
the ability of the nanodimensional structures to possess
extraordinary properties that micro/macroscale structures have
never exhibited.
Earlier we reported on the fabrication of titania nanotube
arrays having lengths up to 400 nm and pore diameters
from 22 to 90 nm using anodic oxidation of titanium thick-
film foils and thin films in hydrofluoric acid containing
electrolytes [18, 19]. The structure consisted of adjacently
located parallel nanotubes separated from the un-anodized
titanium foil by a thin oxide layer (barrier layer). Nanotube
arrays of length 200 nm and pore diameter 22 nm coated with
a thin palladium layer showed a resistance variation of about
five orders in magnitude on exposure to 1000 ppm (parts per
million) hydrogen at room temperature [20]. However, device
performance was limited, and made problematic, by the very

0957-4484/06/020398+05$30.00 © 2006 IOP Publishing Ltd Printed in the UK 398

 Unprecedented ultra-high hydrogen gas sensitivity in undoped titania nanotubes
a voltage and pH conditions and their maximum resistance variation
b to 630 ◦ C in oxygen for 6 h at a heating/cooling rate of
Figure 1. FESEM images of illustrative nanotube-array samples:
(a) cross-sectional view of nanotubes grown in an electrolyte pH 3
using 25 V, and (b) top view of a sample fabricated in a pH 1.1
electrolyte using 25 V.
low thickness of the array structure, which provided a low
resistance path for the current to flow between the platinum-
film electrodes on the nanotube surface and the underlying
titanium metal layer.
Recently we have improved the anodization process to
fabricate nanotube-array architectures with lengths up to
6.5 µm, pore diameters from 22 to 110 nm, and wall
thicknesses from 9 to 34 nm [21, 22]. Our ability to control
the nanotube-array dimensions has enabled our ability to
meaningfully test the gas-sensing properties of the nanotube
arrays. More importantly, our studies on these highly
stable nanostructures have revealed their unusual behaviour
to hydrogen gas, which can open new avenues in nanoscience
and nanotechnology.
2. Experimental details
Nanotube arrays were prepared by anodization of 250 µm thick
titanium foil (99.7% Aldrich, Milwaukee, WI) in an electrolyte
containing 1 M sodium hydrogen sulfate monohydrate, 0.1 M
potassium fluoride (ACS reagent 99% Alfa Aesar, Ward Hill,
MA) and 0.2 M sodium citrate tribasic dihydrate (ACS reagent
99% Aldrich). Electrolyte pH was adjusted by the addition
of sodium hydroxide (97% Aldrich). Nanotube lengths varied
from 380 nm to 6 µm and pore diameters from 30 to 110 nm as
dependent on the electrolyte pH (1.11–5) and the anodization
potential (10–25 V); the anodization was conducted for 17 h
for all samples. The as-prepared amorphous samples were
crystallized by annealing at temperatures ranging from 370
Table 1. Summary of the nanotube dimensions under different
to 1000 ppm H2 at room temperature.
10 V (30 nm pore size)
Length Log(S) Log(S)
pH (nm) no Pd with Pd
1.1 350 7.2 7.3
3.0 730 8.0 8.7
4.0 990 8.7 8.3
4.5 1400 8.0 8.3
5.0 2000 – –
1 ◦ C min−1 .
For the electrical measurements platinum circular
electrodes (500 µm diameter, 100 nm thick, 1 mm edge to
edge spacing) were sputter coated onto the nanotube-array
samples; increasing the electrode separation increases the
baseline resistance, but does not affect sensitivity. After
fixing the samples to TO-8 steel headers (Electrovac GesmbH,
Klosterneuberg, Austria), gold wire (1 mil) was bonded on
the platinum pads with a Mech-El-907 ultrasonic wire bonder
(Mech-El Industries, Woburn, MA). The behaviour of the
nanotube samples in the presence of different gases was tested
in a sealed Plexiglas chamber of 110 cm 3 volume. Electrical
resistance was measured using an electrometer (Keithley,
Model 6517A). MKS mass flow controllers were used for
regulating the chamber gas (ultra-high purity) flow. Data
collection and instrument control were managed by a personal
computer. Titania, an n-type semiconductor, decreases its
resistance in the presence of reducing gases and hence the gas
sensitivity S is defined as
G gas − G air G gas
S= ≈ when G air  G gas
G air G air
where G air and G gas are, respectively, the conductance of the
nanotubes in air and the test gas.
3. Results and discussion
FESEM images (JEOL, Japan, model 6700F) of illustrative
nanotube-array samples are shown in figure 1. The pore
diameter depends on the anodization voltage, whereas the
nanotube length is a function of both pH and the anodization
voltage. With the increase in voltage at a particular pH value
the pore size as well as length of the tube increases. For
example, a 10 V anodization in pH 1.1 results in a nanotube
array of 350 nm length and 30 nm pore diameter. A 25 V
anodization in pH 5.0 results in a nanotube array of 6.5 µm
length, the longest nanotube array we have achieved, with a
110 nm pore diameter. The greatest hydrogen sensitivities are
achieved with the 30 nm pore diameter samples fabricated at
10 V; consequently, the majority of our discussion is focused
on these samples. Table 1 summarizes the maximum room
temperature hydrogen sensitivity, log(S), of the 30 nm pore
diameter nanotube arrays in response to 1000 ppm hydrogen, as
a function of length which in turn is determined by electrolyte
pH. We note that in crystallizing the initially amorphous
nanotube array samples maximum hydrogen sensitivity was
399
K G Ong et al
Figure 2. Variation in hydrogen sensitivity S of 30 nm pore
diameter nanotube-array samples as a function of electrolyte pH.
achieved with a 480 ◦ C annealing. It can be seen from
table 1 that the highest resistance variation, 8.7 orders of
magnitude (50 000 000 000%), was obtained for nanotube
samples prepared using electrolyte pH 4.0 (length ∼1 µm,
pore diameter ∼30 nm and wall thickness ∼13 nm). To the
best of our knowledge, this is the largest change in electrical
resistance of any material, to any gas, at any temperature.
Assuming a 10
measurement resolution, linear extrapolation
of the sensitivity indicates the ability of the nanotube array
to detect hydrogen at 20 ppt (parts per trillion). We make
note that a test chamber capable of accurately flowing less
than, approximately, 10 ppm of any gas is a difficult challenge
requiring considerable resources. Consequently, we are not
able to directly measure the low-level sensitivity of the sensor.
The lower limit of our test chamber is approximately 20 ppm,
at which we see 7.2 orders of magnitude variation in electrical
resistance to 20 ppm hydrogen. The response of the sensor
is linear to, approximately, 1000 ppm, when it begins to
demonstrate a nonlinear response.
Figure 2 shows the variation in hydrogen sensitivity of
the 10 V samples as a function of electrolyte pH; note that
the pH 5.0 sample was not tested, as nanotube array formation
occurs on only ≈25% of the film. The typical response of a
pH 4.0 sample on switching the ambient atmosphere between
air and 1000 ppm hydrogen in nitrogen is shown in figure 3.
On exposure to hydrogen a rapid reduction in resistance
from several hundred giga-ohms to a few hundred ohms is
observed; there is no indication of measurement hysteresis.
The sensitivity S is not greatly influenced by nanotube length;
for the 10 V samples a sensitivity shift of 7 orders to 8.7 orders
is found with an increase in length from 380 nm to 1 µm. It
was found that 6 µm long samples (25 V, pH 5.0) showed less
sensitivity, with significantly longer response/recovery times
due to the time required for hydrogen to diffuse inside the
long pores. The sensitivity of the nanotube arrays is in stark
contrast to the hydrogen sensitivity of a crystalline TiO2 film
made by thermal oxidation of a Ti film which demonstrates,
to 1000 ppm hydrogen at room temperature, a resistance
variation of approximately 400%. As palladium is known
400
Figure 3. Room-temperature resistance variation of a
nanotube-array sample prepared in a pH 4.0 electrolyte using 10 V
(30 nm pore diameter), annealed at 480 ◦ C, alternately exposed to
air and 1000 ppm hydrogen in nitrogen.
to help hydrogen detection in metal oxide materials, some
nanotube array samples were coated with a 10 nm Pd layer
and their response to hydrogen tested. The Pd layer degraded
the sensitivity of the highly sensitive samples due to a drop in
the base resistance; samples of relatively lower performance
typically saw a modest sensitivity increase (table 1).
It behooves us to consider how hydrogen interacts with the
titania nanotube architecture, a material which is essentially
all surface and no bulk, to achieve such remarkable changes
in electrical resistance. At room temperature there is little
reduction of the surface or bulk oxide [23, 24], while the
fast response and recovery without hysteresis (figure 3) rules
out a significant contribution from diffusion of hydrogen into
the titania lattice [25]. Oxygen in air may be chemisorbed
in the form of O− 2 on the nanotube surface by trapping
electrons from its conduction band leading to an enhanced
base resistance [3, 4]. Hydrogen can remove this chemisorbed
oxygen thus reducing the resistance [26]. To understand the
role of chemisorbed oxygen, we initially passed air through
the test chamber, then nitrogen, then a hydrogen–nitrogen
mixture, and finally nitrogen. It was observed that nitrogen
reduced the 1000 ppm hydrogen sensitivity to approximately
six orders of magnitude while only slightly reducing the base
resistance, and greatly extended the needed recovery time.
The high sensitivity in the absence of oxygen indicates that
direct chemisorption of hydrogen on the nanotubes is the
dominant mechanism leading to the tremendous reduction
in resistance of the titania nanotubes, while the presence
of oxygen facilitates removal of the chemisorbed hydrogen.
Platinum is known to be a catalyst that activates hydrogen
by adsorbing and dissociating hydrogen molecules which
are then spilled over to the semiconducting material for
chemisorption [27, 28]. Replacing the platinum electrodes
with gold reduced the 1000 ppm sensitivity of the pH 4.0
10 V nanotube sample to ≈5 orders of magnitude with a
considerably slower response time. While it is evident that the
platinum electrodes facilitate the high sensitivity by providing
 Unprecedented ultra-high hydrogen gas sensitivity in undoped titania nanotubes
Figure 4. Hydrogen sensitivity (1000 ppm) of a 10 V
nanotube-array sample prepared in a pH 4.0 electrolyte as a function
of relative humidity. The sensitivity of the sample to carbon
monoxide and methane in dry ambient is also shown.
spilt-over hydrogen for chemisorption, it is not the only cause
of observed nanotube response.
Hydrogen activation appears to occur on the walls of the
undoped nanotubes at highly active surface states provided by
nanoscale surface defects. The dissociated hydrogen species
form OH groups with the surface oxygen accompanied by
electron transfer to the titania conduction band and formation
of an electron-rich region within the nanotube walls. To ensure
that the nanotube samples were undoped, samples annealed at
480 ◦ C were studied using XPS (Kratos Analytical Axis Ultra).
In addition to the Ti and O peaks the XPS spectra showed a
weak carbon (C 1s) peak. Depth profiling showed that carbon
was present inside the sample at low concentrations. The
carbon peak is believed to come from adventitious carbon or
hydroxyl and carboxyl groups. Our studies do not show any
effect of C on the hydrogen sensitivity. Figure 4 shows the
response of the nanotubes of 1 µm length and 30 nm pore
diameter to 1000 ppm hydrogen in humid ambients. In humid
conditions physisorption of water molecules takes place on
a layer of initially chemisorbed OH radicals at the nanotube
surface which reduces the base resistance of the nanotubes
in air [29]. The adsorbed water molecules block the active
sites where hydrogen chemisorption occurs, thus reducing the
sensitivity. Figure 4 also shows the response of the nanotube
sample to 1000 ppm carbon monoxide and 1000 ppm methane;
although both gases are strongly reducing, the sensitivity to
these gases is negligible.
We believe that the crystallized nanoscale walls and inter-
tubular connecting points play critical roles in determining
the remarkable hydrogen sensitivities of the titania nanotube
arrays. The adsorption of oxygen in air takes place on either
side of the nanotube walls, creating an electron depletion
region. The width of the space charge layer L is given by
L = L D (2eV /kT )1/2 , where L D = (ε0 εkT /2e2 ND )1/2
is the Debye length, eV is the barrier height, kT is the
thermal energy and ND the ionized donor density. In metal
oxides the space charge layer extends to a few tens of
nanometres [30]. If the nanotube wall half-thickness t/2
Figure 5. The influence of nanotube wall thickness on band bending
due to oxygen chemisorption. (a) When the nanotube wall
half-thickness (t/2) is much greater than the space charge layer, (b)
when the thicknesses are comparable, and (c) when t/2 is less than
the width of the space charge region, (d) schematic illustration of
nanotubes, top view, and the tube-to-tube connecting points
corresponding to the case shown in (a).
is significantly greater than the width of the space charge
region, as shown in figure 5(a), oxygen removal by hydrogen
and subsequent hydrogen chemisorption will have little effect
on device resistance, and hence high sensitivity cannot be
expected. In contrast, when t/2 is comparable to or less than
the space charge region the shift in the electrical resistance
on exposure to hydrogen can be very high (figures 5(b), (c)),
with a flat-band condition existing when the wall thickness is
less than the width of the space charge region. The nanotube
sample showing the highest sensitivity had a wall thickness of
≈13 nm, corresponding to the geometry of figure 5(b). The
inter-wall connecting points also appear to play a significant
role in enabling the ultra-high hydrogen sensitivity. The
oxygen adsorption and its removal by hydrogen atoms as
well as chemisorption of hydrogen at these constricted points,
figure 5(d), regulates the current passing from nanotube to
nanotube.
In summary, our studies on the interaction of titania
nanotube arrays with hydrogen reveal an unprecedented gas-
dependent shift in electrical resistance. The synergetic effect of
platinum electrodes, highly active nanoscale surface states that
activate oxygen and hydrogen for chemisorption, tremendous
surface area, nanosized walls and inter-tubular connecting
points is believed responsible for the remarkable behaviour.
Extension of the material architecture to other metal oxides
should enable dramatically improved broad-spectrum gas-
sensing materials.
Acknowledgments
This work was partially supported by the National Institutes of
Health grant number 5 R43 HD049233-02, and the National
Science Foundation grant number CTS-0518269. The authors
wish to thank the referees for their careful reading of the
manuscript and helpful suggestions.
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