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Abstract
Titanium dioxide nanotubes, made by anodization, are highly sensitive to hydrogen; for example, cycling between nitrogen atmosphere and
1000 ppm hydrogen a variation in measured resistance of 103 is seen for 46 nm diameter nanotubes at 290 8C. The hydrogen sensors are
completely reversible and have response times of approximately 150 s. Field emission scanning electron microscopy and Glancing angle X-
ray diffraction (GAXRD) are used to study the surface morphology and crystal structure of the nanotubes.
# 2003 Elsevier Science B.V. All rights reserved.
0925-4005/03/$ – see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0925-4005(03)00222-3
O.K. Varghese et al. / Sensors and Actuators B 93 (2003) 338–344 339
Fig. 1. Schematic representation of (a) the electrode geometry, and (b) the experimental apparatus.
metal foil with a nanotube array grown on the top. An under test was heated to the desired temperature. The test
insulating barrier layer separates the nanotubes from the gases examined, oxygen, carbon dioxide, ammonia, carbon
conducting titanium foil. Preliminary studies using evapo- monoxide or hydrogen, were mixed in appropriate ratios
rated gold films as well as silver paste as interdigital with nitrogen to create the necessary test gas ambient.
electrodes showed that these materials diffuse into the titania
nanotubes at elevated temperatures resulting in sensor con-
tamination. Hence a pressure contact was used to electrically 3. Results and discussion
contact the nanotubes, with two spring-loaded parallel
10 mm by 2 mm platinum contact pads (100 mm thickness). The surface morphology of nanotube arrays prepared
A schematic diagram of the experimental set up used for using an anodization potential of 20 V and annealed at
the gas sensing studies is shown in Fig. 1b. The test chamber 500 8C for 6 h in a pure oxygen ambient is shown in
consists of a 1.3 l quartz tube, with stainless steel end caps, Fig. 2a and b. It can be seen from these images that the
placed inside a furnace (Thermolyne, USA model 21100 nanotubes are uniform over the surface. The nanotubes are
tubular furnace). The electrical contact was formed by approximately 400 nm in length and have a barrier layer [1]
attaching the platinum pads to the ends of a spring-loaded thickness of 50 nm. For the nanotubes fabricated using
‘U’ shaped quartz rod. Gas flow through the test chamber 20 V anodization the average pore diameter, as determined
was controlled via a computer-controlled mass flow con- from FESEM images, is 76 nm (standard deviation 15 nm),
troller (MKS instruments, Austin, TX, USA). The electrical with a wall thickness of 27 nm (standard deviation 6 nm).
resistance of the titania sensors were measured using a The sample anodized at 12 V was found to have an average
computer-controlled digital multimeter (Keithley, USA pore diameter of 46 nm (standard deviation 8 nm) with a
model 2000). Prior to data collection the test chamber wall thickness 17 nm (standard deviation 2 nm). The por-
was initially evacuated using a mechanical pump, where- osities of the 20 and 12 V samples were calculated as 45 and
upon nitrogen (99.999% pure) was passed while the sensor 61%, respectively.
340 O.K. Varghese et al. / Sensors and Actuators B 93 (2003) 338–344
Fig. 3. Glancing angle X-ray diffraction pattern of a 20 V sample (glancing angle ¼ 28) annealed at 500 8C in oxygen ambient. A, R and T represent the
reflections from anatase crystallites, rutile crystallites, and the titanium substrate, respectively.
O.K. Varghese et al. / Sensors and Actuators B 93 (2003) 338–344 341
Fig. 4. Variation of resistance Rg, normalized with respect to baseline resistance R0, of a 20 V sample with time on exposure to 1000 ppm hydrogen at
different temperatures. It may be noted that the inverse of Rg/R0 was used in the plot for representing data in positive y-direction.
the measurement chamber, estimated to be 30 s). The of the 20 V prepared nanotube sensors, kept at 290 8C, is
response time reduces exponentially with temperature. shown in Fig. 7. The behavior of the sensor is consistent,
To check the behavior of the sensor on repeated hydrogen recovering its original resistance after repeated exposure to
exposure, the hydrogen concentration was varied in discrete varying hydrogen gas concentrations. The sensitivity of the
steps of 100 ppm from 0 to 500 ppm while keeping the sensor in this concentration range is plotted in Fig. 8a; there
temperature constant at 290 8C; the chamber was flushed is a linear increase in sensitivity at low concentrations. The
with nitrogen after each exposure to hydrogen. The response sensitivity of the hydrogen sensor over 100 ppm to 4% (the
explosive limit in the presence of oxygen) is shown in
Fig. 8b.
Fig. 9 shows the hydrogen sensitivities, at 290 8C, of
nanotube sensors having a pore diameter of 76 nm, and a
pore diameter of 46 nm. While smaller diameter nanotubes
had greater sensitivity to hydrogen the samples made at
lower anodizing voltages tended to be more brittle, and
harder to mechanically handle without breaking.
The 20 V sample was exposed to oxygen, carbon mon-
oxide, ammonia and carbon dioxide at 290 8C. The sensor
was found to have no detectable variation in resistance on
exposure to carbon dioxide. The sensitivities of the titania
will not immediately occur hence the sensor requires several [6] S. Hasegawa, Y. Sasaki, S. Matsuhara, Oxygen-sensing factor of
hours to regain its original conductivity. TiO2 doped with metal ions, Sens. Actuators B 13-14 (1993) 509.
[7] A. Rothschild, F. Edelman, Y. Komem, F. Cosandey, Sensing
It should be noted that the conducting titanium foil behavior of TiO2 thing films exposed to air at low temperatures, Sens.
beneath the nanotubes ultimately limits the sensitivity by Actuators B 67 (2000) 282.
reducing the baseline resistance of the sensor. [8] G. Sakai, N.S. Baik, N. Miura, N. Yamazoe, Gas sensing properties
of tin oxide thin films fabricated from hydrothermally treated
nanoparticles dependence of CO and H2 response on film thickness,
Sens. Actuators B 77 (2001) 116.
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Actuators B 21 (1991) 209.
Titania nanotubes prepared using anodization and [10] O.K. Varghese, L.K. Malhotra, G.L. Sharma, High ethanol sensiti-
annealed in an oxygen atmosphere at a temperature of vity in sol–gel derived SnO2 thin films, Sens. Actuators B 55 (1999)
500 8C were found highly sensitive to hydrogen. The nano- 161.
[11] V.A. Chaudhary, I.S. Mulla, K. Vijayamohanan, Comparative studies
tube sensors contain both anatase and rutile phases of titania, of doped and surface modified tin oxide towards hydrogen sensing:
and showed appreciable sensitivity towards hydrogen at synergistic effects of Pd and Ru, Sens. Actuators B 50 (1998) 45.
temperatures as low as 180 8C. The sensitivity increased [12] H. Tang, K. Prasad, R. Sanjines, F. Levy, TiO2 anatase thin films as
drastically with temperature showing a variation of three gas sensors, Sens. Actuators B 26-27 (1995) 71.
orders in magnitude of resistance to 1000 ppm of hydrogen [13] S.A. Akbar, L.B. Younkman, Sensing mechanism of a carbon
monoxide sensor based on anatase titania, J. Electrochem. Soc. 144
at 400 8C. The response time decreased with increasing (1997) 1750.
temperature; at 290 8C full switching of the sensor took [14] Y. Shimizu, N. Kuwano, T. Hyodo, M. Egashira, High H2 sensing
approximately 3 min. Results were highly reproducible with performance of anodically oxidized TiO2 film contacted with Pd,
no indication of hysteresis. Our results showed these sensors Sens. Actuators B 83 (2002) 195.
are capable of monitoring hydrogen levels from 100 ppm to [15] M.C. Carotta, M. Ferroni, D. Gnani, V. Guidi, M. Merli, G.
Martinelli, M.C. Casale, M. Notaro, Nanostructured pure and Nb
4%. At 290 8C nanotubes with smaller pore diameter doped TiO2 as thick film gas sensors for environmental monitoring,
(46 nm) showed higher sensitivity to hydrogen compared Sens. Actuators B 58 (1999) 310.
to larger pore diameter samples (76 nm). The sensors [16] N.O. Savage, S.A. Akbar, P.K. Dutta, Titanium dioxide based high
showed high selectivity to hydrogen compared to carbon temperature carbon monoxide selective sensor, Sens. Actuators B 72
monoxide, ammonia and carbon dioxide. Although the (2001) 239.
[17] E. Comini, G. Faglia, G. Sberveglieri, Y.X. Li, W. Wlodarski, M.K.
sensor was sensitive to high concentrations of oxygen, the Ghantasala, Sensitivity enhancement towards ethanol and methanol
response time was high and the sensor did not completely of TiO2 films doped with Pt and Nb, Sens. Actuators B 64 (2000)
regain the original condition. We believe that the hydrogen 169.
sensitivity of the nanotubes is due to hydrogen chemisorp- [18] I. Hayakawa, Y. Iwamoto, K. Kikuta, S. Hirano, Gas sensing
tion onto the titania surface where they act as electron properties of platinum dispersed-TiO2 thin film derived from
percursor, Sens. Actuators B 62 (2000) 55.
donors. In summary, it was demonstrated that sensors com- [19] N. Savage, B. Chwieroth, A. Ginwalla, B.R. Patton, S.A. Akbar, P.K.
prised of titania nanotubes prepared using anodization can Dutta, Composite n–p semiconducting titanium oxides as gas sensors,
successfully be used as hydrogen sensors. Sens. Actuators B 79 (2002) 17.
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[21] H.-M. Lin, C.-H. Keng, C.-Y. Tung, Gas sensing properties of
Acknowledgements nanotcrystalline TiO2, Nanostructured Mater. 9 (1997) 747.
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Partial support of this work by the National Science the interface of palladium–titanium dioxide schottky diodes as
Foundation through grant ECS-9875104 is gratefully hydrogen sensors studied by work function and electrical character-
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