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Tin dioxide nano-wire device for sensing kinetics of acetone and ethanol
towards diabetes monitoring

Article  in  IEEE Sensors Journal · November 2013

DOI: 10.1109/ICSENS.2013.6688338

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 Tin dioxide nano-wire device for sensing kinetics of
acetone and ethanol towards diabetes monitoring
Bonex Wakufwa Mwakikunga
DST/CSIR National Centre for Nano-Structured Materials
Council for Scientific and Industrial Research, Pretoria, South
Africa,
Department of Physics and Biochemical Sciences, University
of Malawi-The Polytechnic, Private Bag 303, Chichiri,
Blantyre 0003, Malawi.
Email: bmwakikunga@csir.co.za
Suprakas Sihna Ray
DST/CSIR National Centre for Nano-Structured Materials
Council for Scientific and Industrial Research, Pretoria, South
Africa
Abstract—We demonstrate how to establish reliable contacts to
SnO2 nano-wires by growing these nano-wire on-chip on gold
contacts deposited on alumina. The sensor device is used to sense
the concentrations of acetone and ethanol in air and their
reaction kinetics. Acetone molecules have higher adsorption and
desorption rates on SnO2 nanowires than ethanol molecules
which leads to a lower critical acetone concentration at which
the SnO2 sensor saturates than is the case for ethanol. These
differences suggest a new way of introducing selectivity to the
notoriously non-selective SnO2 and other oxide-based nano-scale
sensors.
Keywords: tin dioxide sensor, human breath, acetone, ethanol
Introduction
Tin dioxide structures have been known to sense various
gases [1-8]. Due to this high sensitivity especially as these
structures are reduced to the nano-scale, tin dioxide like other
oxides lose their ability to distinguish between these various
stimuli. In this brief paper, we show the possibility of
calibrating a sensor based on tin dioxide nanowires to acetone
and ethanol which are ingredients found in human breath,
especially in diabetes patients.
Exposing such nano-scale sensors to human breath, while
it leads to rapid response, may culminate in very slow
recovery. In order to increase the recovery rate, many studies
describe the operation of gas sensors at elevated temperature
[2,7,8].
978-1-4673-4642-9/13/$31.00 ©2013 IEEE
Malose Mokwena, John Dewar
Department of Life and Consumer Sciences, University
of South Africa (UNISA), Florida Campus,
Johannesburg, South Africa
Irina Geibelhaus, Trilok Singh, Thomas Fischer,
Sanjay Mathur
Chair, Inorganic and Materials Chemistry, Department of
Chemistry, University of Cologne, Germany
Operating such sensors at high temperatures comes at a
high cost of operating them unless the sensors are
miniaturized. Single to few nanowires based sensors may
solve this challenge as room-temperature sensing becomes
possible. As materials are reduced to the nano-scale, the cost
of making electrical contacts to them also becomes high as
advanced vacuum techniques, nano-manipulation and focused
ion beam technologies have to be employed to accomplish
these tasks. We show how the nanowire device is cheaply
fabricated with good electrical contacts and then tested to
show the response and recovery profiles to acetone and
ethanol individually as well as acetone and ethanol in
combination.
I. METHODOLOGY
A. How the SnO2 nanowire bridge device is fabricated
Square-shaped 2 cm by 2 cm alumina substrates were cut
out of the alumina wafer. A thin gold film was evaporated
onto the alumina substrate to a typical thickness of 100 nm by
plasma-enhanced chemical vapour deposition (CVD).
Thereafter, a 30-micron diamond tip was used to scribe (etch?)
a chasm into this film. Nanowires of SnO2 are grown on-chip
by CVD of precursor solution contain Sn with a substrate
temperature of 700oC.
(a) (b)
Nanowire(s) (c)
Cathode Anode Cathode Anode
Au
Alumina
Alumina
Alumina
Figure 1. The process for growing SnO2 nanowire bridges between two Au
contacts. (a) The alumina substrate is sputtered with Au, (b) a 30-micrometer
tip diamond scriber is used to cut the Au film until electrical insulation is
established between the electrodes and (c) nanowire bridges are grown on-
chip by CVD of two types of SnO2 precursors at 500oC

B. How acetone and ethanol concentrations are determined

Sensing experiments were conducted in a chamber of
known volume (7040 cm3) in which a box having air-tight
terminals connect the sensor placed inside the box to the
measurement system outside the box. The measurement
system is a PC having the Keithley Semiconductor
Characterization System (SCS) 4200 run by the KITE
(Keithley Interactive) software.
A drop of analyte of known radius (about 1 mm) was
released into the chamber where it was allowed to evaporate
and thereby diffuse into the air in the chamber. During this
time the sensor resistance was monitored until the droplet fully Drain
evaporated. This droplet fully evaporated to a typical
concentration of 92 ppm in accordance with the following
equation [9]:

Vdroplet 4pr 3
c f ( ppm) = · 106 = · 106 (1)
Vbox 3Vbox

II. RESULTS
The morphology of the SnO2 nano-wire device is illustrated
in Fig. 2. The figure clearly shows nano-wires that are
growing from one gold contact to another. During the actual
sensing experiments, the gold contacts are designated as drain
Source
(where the positive terminal is connected) and source (where
the negative terminal is connected).

The resistance-time profiles for acetone and ethanol are

depicted in Fig. 3. It can be noted that the initial resistances
of the sensor R0 are different – high during the ethanol
sensing session (about 40 MW) and low (about 20 MW)
during the acetone sensing session. This difference may affect
the final performance of the sensor in that sensing session.
However, this difference becomes irrelevant as response, S,
of the sensor is defined as the fractional change (Rgas-R0) of
the resistance as follows:
Rgas - R0
S=
R0
Figure 2. Morphology of the SnO2 nanowire bridge device showing
nanowires growing from one gold electrode (Drain) to another (Source)
From Fig. 3, the period of time between ON and OFF of the
stimulus (acetone or ethanol) was kept constant. The fact that
the traces generally rise over time shows that in both sessions,
the sensors have a longer recovery time than response time.
This is a typical characteristic of nano-structures i.e. as the
(2)
sensor structures get smaller and smaller, the adsorption of
the analyte molecules which leads to the response increases
while analyte desorption and sensor recovery is reduced.
 100 of available sites for further adsorption and relates this sum to
12 the response rates. The final equation for response against
90 10
11
concentration can be derived from this relation as [10-16]
9
8
80
[ ( )]
7
6 S = S 0 1 - exp - ac f (3)
Resistance (MW)

70
5
4
60 3
2 acetone where S0 is the response without stimulus at t = 0 or cf = 0
50 1 ethanol and a determines the rate of adsorption and desorption per
40 5 8 9 10 unit concentration of the analyte molecules.
4 6 7
3
30 2
1
bk a c f
20 S0 = ;a = kac f + kd (4)
ka c f + kd
0 4000 8000 12000 16000
Time (seconds)
where ka and kd are adsorption and desorption rates,
respectively, and b is the factor that transforms the number of
Figure 3. Resistance-time curves for the sensor response to varying number
of droplets of acetone and ethanol in a chamber of known volume
adsorbed sites and the available (unabsorbed) sites to the
observed response.
When data from Figure 3 were transformed according to
Equation 2 and then plotted against analyte concentration in From fitting Equation 3 to the data sets in Figure 4, one
ppm as calculated from Equation 1 one obtains a plot given in obtains for the acetone S0 = 0.84–0.02 and a = (9.39
Figure 4. –0.84)· 10-3 ppm-1. Correspondingly, for ethanol, S0 =
4.91–1.76 and a = (5.30 –0.22)· 10-4 ppm-1.
1.4
Assuming that the proportionality constant b between the
1.2 number of adsorbed/available sites and the observed
resistance is unity then ka and kd values for both 1 ppm of
1.0 acetone and ethanol can be estimated as: ethanol (ka = 2.6 ·
Response (R-R0)/R0

0.8
0.6
0.4
0.2
0.0
0 100 200
Concentration (ppm)
Figure 4. Response of the sensor to either acetone (black square) or ethanol
(red circle) against their respective concentrations
From Fig. 4, one can note that the sensor has greater tolerance
to ethanol when compared to acetone as the response
saturates at an acetone concentration of about 200 – 300 ppm
whereas the sensor does not saturate to ethanol even at
concentrations as high as 600 ppm.
In order to analyse the data further, the Langmuir isothermal
equation was employed to describe the kinetics of analyte
species at the surface of the sensor material. This equation
describes the number of adsorbed sites and also the number
10-3 ppm-1 and kd = -2.07 · 10-3 ) and acetone (ka = 7.89 · 10-3
ppm-1 and kd = 1.5 · 10-3).
acetone This analysis shows a higher saturation concentration for
ethanol ethanol than for acetone. Furthermore, ethanol has a lower
adsorption and desorption rate when compared to acetone – in
other words, acetone molecules interact more with the sensor
surface than do ethanol molecules.
300 400 500 600 The differences in the interaction characteristics can be
extended to other gas types. These properties can be used to
add selectivity to the notoriously non-selective SnO2 which is
a weakness that plagues so many metal oxide nano-scale
sensors [10-21].
III. CONCLUSION, ON-GOING STUDIES AND OUTLOOK
We have employed a tin dioxide nano-wire sensor to study
the kinetics of acetone and ethanol sensing. It was found that
acetone shows higher adsorption and desorption rates than
ethanol. However, due to these high kinetic properties, the
sensor saturates at lower acetone concentrations than is the
case for ethanol. There exists no change in response to acetone
above 200-300 ppm. As for ethanol, saturation happens well
above 600 ppm.
 ACKNOWLEDGMENT
This work was supported by the Department of Science
and Technology, Council for Scientific and Industrial
Research (HGER27S) and WIROX Project (PIRSES-GA-
2011-295216), a Marie Curie International Research Staff
Exchange Scheme Fellowship within the 7th European
Community Framework Programme. Additional financial
support was also obtained from the Southern Education and
Research Alliance (SERA) and the National Research
Foundation (NRF).
REFERENCES
[1] E. Comini, G. Faglia, G. Sberveglieri, Z. Pan, Z. Wang, “Stable and
highly sensitive gas sensors based on semiconducting oxide nanobelts,”
Appl Phys Lett 2002;81:1869–71.
[2] G. Sberveglieri, C. Baratto, E. Comini, G. Faglia, M. Ferroni, A.
Ponzoni, “Synthesis and characterization of semiconducting nanowires
for gas sensing,” Sensors Actuat B 2007;121:208–13.
[3] Z. Ying, Q. Wan, Z. T. Song, S L Feng, “SnO2 nanowhiskers and their
ethanol sensing characteristics,” Nanotechnology 2004;15:1682–4.
[4] F. Hernandez-Ramirez, S. Barth, A. Tarancon, O. Casals, E. Pellicer, J.
Rodriguez, “Water vapor detection with individual tin oxide
nanowires,” Nanotechnology 2007;18:424016.
[5] D. C. Meier, S. Semancik, B. Button, E. Strelcov, A. Kolmakov,
“Coupling nanowire chemiresistors with MEMS microhotplate gas
sensing platforms,” Appl Phys Lett 2007;91:063118.
[6] J. Carrey, M. L. Kahn, L. Sanchez, B. Chaudret, M. Respaud,
“Synthesis and transport properties of ZnO nanorods and nanoparticles
assemblies” Eur Phys J Appl Phys 2007;40:71–5.
[7] Q. Wan, T. H. Wang, “Single-crystalline Sb-doped SnO2 nanowires:
synthesis and gas sensor application,” Chem Commun 2005:3841–3.
[8] F. Hernández-Ram´ırez, A. Tarancón, A. Romano-Rodr´ıguez, O.
Casals, J. Arbiol, J. R. Morante, “High response and stability in CO and
humidity measures using a single SnO2 nanowire,” Sensors Actuat B
2007;121:3–17.
[9] B. W. Mwakikunga (Council for Scientific and Industrial Research,
CSIR) S. Afr.PA158013/P, 2013.
[10] P. M. Parthangal, R. E. Cavicchi, M. R. Zachariah, “A universal
approach to electrically connecting nanowire arrays using
nanoparticles-application to a novel gas sensing architecture,”
Nanotechology 2006;17:3786–90.
View publication stats
[11] B. W. Mwakikunga, S. Motshekga, L. Sikhwivhilu, M. Moodley, G.
Malgas, M. Scriba, S. S. Ray, A classification and ranking system on
the H-2 gas sensing capabilities of nanomaterials based on proposed
coefficients of sensor performance and sensor efficiency equations,
SENSORS AND ACTUATORS B-CHEMICAL 184, 170-178 (2013)
[12] H. T. Wang, B. S. Kang, F. Ren, L. C. Tien, P. W. Sadik, D. P. Norton,
“Hydrogen selective sensing at room temperature with ZnO nanorods,”
Appl Phys Lett 2005;86:243503.
[13] B. W. Mwakikunga, A. Forbes, E. Sideras-Haddad, C. Arendse, Raman
spectroscopy of WO3 nanowires and thermochromism study of VO2
belts produced by ultrasonic spray and laser pyrolysis techniques, Phys.
Stat. Solidi (a) 205, 150 (2008)
[14] B. W. Mwakikunga, E. Sideras-Haddad, M. Witcomb, C. Arendse, A.
Forbes, WO3 nano-spheres into W18O49 one-dimensional nano –
structures through thermal annealing, J. Nanosci. & Nanotechnol 8, 1
(2008)
[15] B. W. Mwakikunga, A. Forbes, E. Sideras-Haddad, C. Arendse,
Optimization,yield studies and morphology of WO3 nanowires
synthesized by laser pyrolysis in C2H2 and O2 ambients – validation of
a new growth mechanism, Nanoscale Res. Lett. 3, 372 (2008)
[16] A. Kolmakov, “The effect of morphology and surface doping on
sensitization of quasi-1D metal oxide nanowire gas sensors,” Proc SPIE
2006;6370:63700X1–X8.
[17] B. W. Mwakikunga, T. Malwela, K. T. Hillie, G Ndlovu, Towards an
electronic nose based on nano-structured transition metal oxides
activated by a tuneable UV light source, IEEE Conference: 10th IEEE
Conference on Sensors Location: Limerick, IRELAND Date: OCT 28-
31, 2011, 2011 IEEE SENSORS 1109-1112 (2011)
[18] L. Liao, H. B. Lu, J. C. Li, C. Liu, D. J. Fu, Y. L. Liu, “The sensitivity
of gas sensor based on single ZnO nanowire modulated by helium ion
radiation,” Appl Phys Lett 2007;91:173110-1–0-3.
[19] C. J. Arendse, G. F. Malgas, T. F. G. Muller, D. Knoesen, C. J.
Oliphant, D. E. Motaung, B. W. Mwakikunga, Thermally Induced
Nano-Structural and Optical Changes of nc-Si:H Deposited by Hot-
Wire CVD, NANOSCALE RESEARCH LETTERS 4, 307-312 (2009)
[20] B. W Mwakikunga, M Maaza, K.T. Hillie, C.J. Arendse, T. Malwela,
E. Sideras-Haddad, From phonon confinement to phonon splitting in
flat single nanostructures: A case of VO2@V2O5 core-shell nano-
ribbons, VIBRATIONAL SPECTROSCOPY 61, 105-111 (2012)
[21] L. M. Sikhwivhilu, S. Mpelane, B. W. Mwakikunga, S. S. Ray,
Photoluminescence and Hydrogen Gas-Sensing Properties of Titanium
Dioxide Nanostructures Synthesized by Hydrothermal Treatments,
ACS APPLIED MATERIALS & INTERFACES 4, 1656-1665 (2012)