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Highly stable low temperature alcohol sensor

Cite this: RSC Adv., 2015, 5, 82159
Received 22nd July 2015
Accepted 21st September 2015
DOI: 10.1039/c5ra14518j
www.rsc.org/advances
based on hydrothermally grown tetragonal titania
nanorods
B. Bhowmik and P. Bhattacharyya*


Highly stable, low temperature (27–175 C) alcohol (ethanol, methanol and 2-propanol) sensing
performance of a hydrothermally grown tetragonal TiO2 nanorod array, targeting the detection level of
1–100 ppm, is reported in this paper. Synthesized titania nanorods were characterized by X-ray
diffraction, energy dispersive spectroscopy (EDS) and field emission scanning electron microscopy
(FESEM) to investigate the crystallinity, chemical compositions and surface morphology, respectively.
Photoluminescence spectroscopy (PL spectra) was employed to find out the surface oxygen vacancies
and band gap of the material. An alcohol sensing study, in resistive mode, was carried out and the
optimum temperature for alcohol sensing was found to be 75
C with the corresponding maximum
response magnitude of 69%, 75% and 80% towards 100 ppm ethanol, methanol and 2-propanol,
with corresponding response time/recovery time of 13 s/24 s, 11/21 s and 9/18 s, respectively. The
sensor also offered efficient detection (response magnitude of 29%, 37% and 40%) of 1 ppm alcohol(s)
with fast response time and recovery time of 12–14 s and 4–5 s, respectively. The minimal cross
sensitivity, with other interfering species like acetone, benzene, xylene and 2-butanone, and appreciable
long term stability showed the potential of the developed sensor for commercial applications.

desorption kinetics, but non-uniformity in the nanoforms (lack

1. Introduction
One dimensional (1-D) oxide nanoforms with tuneable struc-
tural, morphological and electronic properties have recently
attracted the attention of gas/vapor sensor researchers.1–5 The
manipulation of one dimensional (1-D) nanostructures viz.,
nanobelts,2 nanotubes,3 nanowires4 and nanorods5 is
immensely favourable for gas adsorption owing to their high
surface to volume ratio, possible quantum connement and
one dimensional electron transport eventually resulting in
improved speed of the device. Various nanoforms of the semi-
conducting metal oxides like ZnO, SnO2 and TiO2 were inves-
tigated.2–5,7,8 Among them, nanoforms of TiO2 (nanotubes,
nanowires and nanorods) received serious attention in recent
years owing to its high chemical and physical stability.3,12,13 In
this category, nanotubes offer easy diffusion (and subsequent
adsorption) of the gas molecules into the core of the nano-
structure (as both the inner and outer surfaces are available for
gas interaction), but, the complete desorption from such
nanostructure takes longer time eventually leading to sluggish
recovery characteristics of the device.3 On the other hand,
though, nanowire and nanobelts attribute relatively faster
Nano Thin Film and Solid State Gas Sensor Devices Laboratory, Department of
Electronics and Telecommunication Engineering, Indian Institute of Engineering
Science and Technology, Shibpur-711103, Howrah, India. E-mail: pb_etc_besu@
yahoo.com; Fax: +91 3326682916; Tel: +91 3326684561 ext. 544
of repeatability in the nanoforms limits the regular array
formation probability) severely constraints the repeatability and
reliability of the sensors.2,4 However, fairly good as well as high
surface to volume ratio of the nanorods makes them nearest
competitor to the nanotubes towards gas/vapor sensing.6–8
However, literature review reveals that gas/vapor sensors based
on TiO2 nanorods have not been extensively investigated.
Moreover, these sensors offered appreciable response magni-
tude ([(Ra  Rg)/Ra]  100 > 90%), but usually at the cost of
higher operating temperature (180–500
C).5–10 For example,
highly crystalline TiO2 nanorods, doped with 3 wt% Nb offered
the maximum response magnitude of 64%, 94% and 91%
towards 400 ppm H2, 4000 ppm C2H5OH and 4000 ppm LPG at
500
C.10 At the same temperature (500
C), response magnitude
of 95% towards acetone, employing electrospun TiO2/PVP
hybrid nanorods structure, were evident in the work of Bian
et al.9 Matrix assisted pulse laser evaporated (MAPLE) TiO2
nanorods showed trace level NO2 (30 ppb to 50 ppm) detection
capability with corresponding response magnitude of 95% at
300
C temperature.8 However, the sluggish response time and
recovery time of 120 s and 780 s was the primary disadvantage of
this sensor.8 At similar temperature (300
C), use of Pt doping
on TiO2 nanorods was found to be benecial in making the
ethanol response time and recovery time faster (9–12 s and 10–
15 s, respectively with response magnitude of 95%).7 In the work
of Chen et al.,6 it was found that, a-MoO3/TiO2 core/shell

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RSC Advances
nanorods hybrid structure showed 93% response to ethanol at
only 180
C with response time/recovery time of 40 s/40 s. On
the other hand, TiO2/ZnO nanorod hybrid structure offered
appreciably high response magnitude of 99% towards ethanol
at only 150
C at the expense of sluggish response time (70 s).5
As reected from the earlier reports, on the TiO2 nanorod
based gas/vapor sensors, extensive efforts have been exerted to
maximize the sensor response magnitude (summarized in
Table 2).5–10 To the contrary, other crucial sensor parameters
like selectivity, stability, operating temperature and response
time/recovery time were relatively less explored arena.5–10 It is
evident that, existing TiO2 nanorod based sensors, either suffer
mostly from higher operating temperature (150–550
C) or their
response time is relatively sluggish (>60 s) making them inap-
propriate for real life applications.5–10 Moreover, such higher
operating temperatures of the device not only increase the
overall power consumption but also become the prime obstacle
to integrate it in a monolithic gas sensor system.11 Therefore
further reduction of operating temperature with appreciable
stability and selectivity, without jeopardizing the response/
recovery kinetics, is a timely demand.
In present study, one dimensional TiO2 nanorod array (due
to their numerous benecial features) was employed to develop
resistive device for alcohol sensing with an aim to enhance the
sensing features compared to present state of art with key focus
on operating temperature, selectivity and stability improve-
ment. In the present endeavour, we report on dramatic
improvement in the alcohol sensing characteristics, primarily
the parameters mentioned above, employing tetragonal nano-
rod array of TiO2 as the sensing layer. 1-D tetragonal titania
nanorods, on FTO glass substrate, were prepared by a low
temperature (120
C) hydrothermal process. Resistive congu-
ration of the TiO2 nanorod array offered the maximum response
(69%, 75% and 80%) to alcohol (ethanol, methanol and 2-
propanol) at relatively low temperature (75
C) with appreciably
fast response time and recovery time of (5–30 s) and (4–22 s),
respectively. Moreover, sensor showed the minimum alcohol
detection level of only 1 ppm with corresponding response
magnitude of 29%, 37% and 40% towards ethanol,
methanol and 2-propanol, respectively. The minimal cross
sensitivity against other interfering species (acetone, benzene,
xylene and 2-butanone) and excellent long term stability (reli-
ability) of the device paved the path of a promising alcohol
sensor for real life applications mitigating the constraints of the
existing state of art.
2. Experimental
Fluorine doped FTO glass (F:SnO2, Tec 10, Sigma Aldrich) was
used as the substrate for titania nanorod growth. FTO glass was
thoroughly cleaned with acetone, ethanol and de-ionized (18.2
MU cm) water. Titanium tetra(IV) iso-propoxide (TTIP), HCl,
CH3COOH and water were used for the growth of TiO2 nano-
rods. Initially, 25 ml 37% HCl (Merck) was mixed with 40 ml
H2O. Then 5 ml 98.8% CH3COOH (Merck) was added to that
solution. The solution was then stirred vigorously. Under stir-
ring condition 0.5 ml titanium tetra(IV) iso-propoxide (TTIP)
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(Sigma Aldrich) was mixed drop wise till the solution turned
transparent. FTO substrate was placed in Teon beaker, con-
taining the solution, at an angle of 45
against the wall with
conducting surface facing upward. The complete set up was
then placed in an autoclave (70 ml) and transferred to an oven
with temperature 120
C  2
C for 2 hours. Finally, autoclave
was allowed to cool naturally to room temperature. The oxide
coated FTO glass was then rinsed in de-ionized water. The dried
samples were then annealed at 350
C for 3 hours.
Crystallinity of the sample was analysed using X-ray diffrac-
tometer (Rigaku MiniFlex II, Cu Ka radiation with l ¼ 1.54 Å at
2q angle of 20–75
with the scanning rate of 0.02
). The energy
dispersive spectroscopy (EDS) (EDAX, model: EAG AN461) was
carried out to determine the elemental composition in the
sample. The size, thickness and surface morphology of the
deposited lm was investigated through eld emission scan-
ning electron microscopy (ZEISS SIGMA). Band gap and oxygen
vacancies were obtained by photoluminescence spectroscopy
(PL spectra) using Horiba Jobin Yvon, Fluorolog-3 spectrouo-
rometer (model FL3-22).
The schematic of the two terminal resistive device congu-
ration, employing nanorods as the sensing layer, is shown in
Fig. 1. Two Pd electrodes having dimensions of 2 mm  1 mm
 50 nm were deposited by e-beam evaporation techniques. The
gap between the two electrodes was maintained at 3 mm. A
barrier layer of TiO2 having thickness of 90–110 nm was
formed between FTO substrate and TiO2 nanorods. Such barrier
layer was the initial formation of oxide layer on FTO substrate by
precipitation of the intense TiO2 gel.6,7,10
A dynamic gas ow measurement system was used to
measure the gas sensing properties of the TiO2 nanorod based
sensor devices. The details of the gas sensor measurement
system were already described in our earlier publications.12,13
The measurement system consists of a sensing chamber,
temperature controller, mass ow controllers, Keithley 6487
picoammeter/programmable voltage source with computer
interfacing. Two mass ow controllers (MFC) (MKS USA) were
used; one to control the ow of carrier gas (air in the present
case) through the liquid volatile organic compounds (VOCs)
and other one to control the ow of diluent gas (air in the
Fig. 1 Schematic of the tetragonal TiO2 nanorod array based two
terminal resistive device configurations with requisite dimensions (not
in scale).
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Paper
present case) to achieve the desired concentrations of VOCs in
the test chamber. The diluted gas/vapor was then allowed to
ow in the sensing chamber. The temperature of the sensing
chamber was maintained by a proportional-integral-derivative
(PID) temperature controller with temperature accuracy of
1
C. Before starting the measurement, sensor device was pre-
heated at 100
C for 1 hour to remove the unwanted adsorbed
molecules. Response magnitude was calculated following the
eqn (1).


Ra  Rg
RM ¼  100 (1)
Ra
where Ra represents the sensor resistance in air and Rg repre-
sents the same in test gas/vapor.12
3. Results and discussions
3.1. Structural characterizations
XRD pattern of the annealed TiO2 thin lm containing tetrag-
onal nanorod array is shown in Fig. 2(a). The diffraction peaks
at 30.02
, 39.4
, 43.89
are indexed as (116), (305) and (400)
planes of TiO2 anatase phase. On the other hand, peaks at
64.09
and 72.46
correspond to (310) and (311) plane of TiO2
rutile phase. All the planes in both anatase and in rutile phases
are in agreement with the standard JCPDS le no. 21-1272 (ref.
14) and 86-0148.15 The crystalline size of the TiO2, from the
Scherrer's formula, was found to be 35–37 nm.
Fig. 2 (a) XRD pattern of the hydrothermally grown TiO2 nanorod array (b) EDS spectra of the hydrothermally grown TiO2 nanorod array (c)
FESEM image of the hydrothermally grown TiO2 nanorods (inset shows the magnified view). (d) Room temperature PL spectra of the grown TiO2
nanorods.
This journal is © The Royal Society of Chemistry 2015
RSC Advances
Fig. 2(b) shows the EDS spectra of the TiO2 sample. The
major elemental composition was found to be Ti and O. The
obtained Ti and O weight percentage in the sample were
calculated to be 46.06% and 47.80%, respectively. The presence
of Sn was found due to the FTO substrate. Non existence of
other peaks in the EDS spectra authenticates the purity of the
TiO2 thin lms. Fig. 2(c) shows the FESEM image (top view) of
the grown TiO2 nanorod array. FESEM image conrms the
formation of densely packed tetragonal nanorod array with
square top facet (magnied view shown in the inset). The
lengths of the nanorods were found to be 710–750 nm.
Lengths of the side arm(s) and diagonal of the tetragonal
nanorod were 90–94 nm and 120–126 nm, respectively. Such
unique structure offer high specic surface area and higher
concentrations of interaction sites for gas/vapor sensing.
Nanorod growth was started by hydrolysis of titanium tetra(IV)
iso-propoxide (TTIP) in the aqueous media of HCl and CH3-
COOH. A ligand exchange reaction between TTIP and CH3-
COOH occurred where titanium tetra was replaced by acetoxyl
group.16,17 The hydrolysis of TTIP in acidic medium produces a
complex polymeric Ti(IV) alkoxides which are saturated in
solution and make a network of –Ti–O– bond together. Such
reactions produce a seed layer of TiO2 with a large number of
heterogeneous nucleation centres on FTO substrate.7,10,16,17 At
elevated temperature, the dissolution of seed layer (by concen-
trated HCl) followed by the deposition produces uniform
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nanorod, situated vertically, on FTO substrate. The role of HCl
is to grow the crystal TiO2 into one direction by controlling the
dehydration of Ti alkoxides. Further, the minimum lattice
mismatch between FTO substrate and anatase/rutile TiO2 plays
a vital role for uniform nucleation as well as growth of TiO2
nanorods.17
Room temperature PL spectra of the grown sample were
carried out for the excitation wavelength of 300 nm and the
results are shown in Fig. 2(d). The corresponding PL intensity
were recorded in the wavelength range of 350–550 nm. Mainly
three peaks were observed at 399 nm, 428 nm and 461 nm. The
peak at 399 nm is related to band to band emission i.e. direct
transition of electron from valence band to conduction band.
From the direct transition, the calculated band gap was found
to be 3.1 eV. The peaks at 428 nm reveals the band to band
indirect transition of electron which further proves the states
are intrinsic rather than surface state.18 The peak at 461 nm
corresponds to the presence of surface oxygen vacancies (OVs).19
Higher peak intensity at 461 nm than that of the band edge
emission peak at 399 nm conrms the existence of higher
amount of OVs than that of Ti vacancies.19
3.2. Sensor study
Alcohol sensing performance of the TiO2 nanorod array was
tested in the temperature range of 27–175
C. The experiment
started at room temperature (27
C) then in the range of
50–175
C, the temperature was increased at a step of 25
C.
Baseline resistance of the sensor device as a function of oper-
ating temperature were investigated in air, 1 ppm and 100 ppm
of alcohols (ethanol, methanol and 2-propanol) and the results
are shown in Fig. 3. In exposure of air, baseline resistance of the
sensor was 6.75 MU and 0.34 MU at room temperature
(27
C) and at 175
C, respectively. On the other hand, with
exposure to 1 ppm/100 ppm alcohols, the baseline resistance
variations were found to be 6.2/5.5 MU (at 27
C) and 0.2/0.05
MU (175
C), respectively. Such a relatively lower baseline
resistance value (<100 MU) of the present sensor is an
Fig. 3 Sensor resistance as a function of operating temperatures in air,
ethanol, methanol and 2-propanol; inset shows the magnified view of
the selected portions.
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additional advantage and offer opportunity to integrate the
same with a monolithic gas sensor system.11
Sensor response towards different alcohols for different
temperatures was investigated and the results are shown in the
Fig. 4(a). It was found that the response magnitude increased up
to 75
C and then decreased with increase in temperature. Such
nonlinear variation in response with temperatures is possibly
attributed to the dissimilar adsorption–desorption kinetics at
different temperatures.12 At room temperature (27
C), sensor
showed the response magnitude of 0.8/12%, 1.02/14% and 1.36/
15% towards 1/100 ppm of ethanol, methanol and 2-propanol,
respectively. The optimum operating temperature was found to
be only 75
C which is signicantly lower compared to the
earlier reported TiO2 nanorod based gas/vapor (180–500
C)
sensors.5–10 Such high operating temperatures of those sensors
was the prime obstacle to integrate them into the monolithic
gas sensor system.11 At optimum temperature (75
C), the
maximum response of the present sensor was found to be 29/
69%, 37/75% and 40/80% towards 1/100 ppm ethanol,
methanol and 2-propanol, respectively. Sensor response
magnitude variations as a function of alcohol concentrations
was also plotted for the temperature of 27
C and 75
C and
shown in Fig. 4(b). As revealed from this gure, at 75
C,
response magnitude increased almost linearly with a steep
nature up to 10 ppm and aer that increased in a linear fashion
Fig. 4 (a) Sensor response magnitude as a function of operating
temperatures for the alcohol concentrations of 1 ppm and 100 ppm.
(b) Sensor response magnitude as a function of alcohol concentrations
at 75
C operating temperature; inset shows response magnitude as a
function of concentrations at room temperature.
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Paper
Fig. 5 Transient characteristics of the TiO2 nanorod based resistive
device towards ethanol, methanol and 2-propanol at 75
C for the
concentrations of 1, 5, 10, 50 and 100 ppm.
with relatively lower slope. On the other hand, at room
temperature also, sensor showed similar increasing trends in
response magnitude but the overall response magnitude was
found to be lower than that of the response magnitude at 75
C
(shown as inset of Fig. 4(b)). At very lower concentrations (#10
ppm at present study), the surface coverage's (q) as well as
diffusion of alcohol molecules is very fast which manifest itself
as a rapid increase in response magnitude. However, with
increasing concentrations as the adsorption sites are gradually
occupied the slope of the curve decreases. Following the Wol-
kenstein adsorption–desorption isotherm, both adsorption and
desorption of vapor molecules concomitantly occur on the TiO2
sensing surface when the vapor pulse is ‘ON’.20 To the contrary,
when the vapor pulse is ‘OFF’, only desorption process remain
active. In the present study, the phenomenon (lower slope of
response magnitude aer 10 ppm) suggests that, upon reaching
the maximum surface coverage, the adsorption rate is no longer
able to compete with the desorption rate. In principle, the
decrease of response rate at high gas concentration could be
mainly due to the two reasons. On one hand, the adsorption
sites become less and less as well as the sticking probability of
the incoming gas molecule decreases due to the decreased
adsorption energy at higher adsorption density/coverage. On
the other hand, the adsorbed gas molecules become important
scattering centres to the carrier in the sensing materials that
lead to the degradation of carrier mobility.21,22
Fig. 5 shows the transient response characteristics of the
sensor with exposure to ethanol, methanol and 2-propanol at
Table 1 Sensor response magnitude (RM%) with exposure to 1 ppm and 100 ppm alcohols (ethanol methanol and 2-propanol) in dry air and
different relative humidity (% RH) background at 75
C
Concentration VOCs RM (%) in dry air
1 ppm Ethanol 29
Methanol 37
Propanol 40
100 ppm Ethanol 69
Methanol 75
Propanol 80
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RSC Advances
75
C. Sensor showed appreciable recovery characteristics
within <40 s aer cutting off the alcohol pulse. The baseline
resistance of the sensor was found to remain almost constant
with a deviation of only 0.5–1.7% for the all the cases (ethanol,
methanol and 2-propanol, for all the concentrations). Moreover,
at even 1 ppm ethanol, methanol and 2-propanol, sensor
offered acceptable response magnitude of 29%, 37% and
40%, respectively. Such appreciable response magnitude of
TiO2 nanorods towards trace level of alcohol (1 ppm) at such a
lower temperature (75
C) is a signicant improvement with
reference to the existing state of art.5–10
The effect of relative humidity (% RH) on the sensing
performance of the device was carried out at 75
C with expo-
sure to 1 ppm and 100 ppm alcohols (ethanol, methanol and 2-
propanol) for humid air background (8% RH, 52% RH and 75%
RH). The maximum base line resistance variation was found to
be 1.56%, 2.26% and 2.74% for 1 ppm concentration and
2.33%, 3.63% and 3.75% for 100 ppm alcohols (ethanol,
methanol and 2-propanol) in 8% RH, 52% RH and 75% RH,
respectively. Sensor response magnitude was found to be
decreased with increase in relative humidity (% RH). The sensor
response magnitude (RM%) towards alcohols at dry air and
different relative levels of humidity is shown in Table 1.
Fig. 6(a) and (b) shows the response time and recovery time
of the sensor device as a function of operating temperatures. As
demonstrated in the Fig. 6(a) and (b), in such temperature range
(27–175
C), both response time/recovery time were faster than
the earlier reported ones.5,6 However, such, faster response/
recovery characteristics with increase in operating tempera-
ture is attributed to fast adsorption/desorption and diffusion
kinetics.12,13 Moreover, it is evident from Fig. 6(a) and (b) that
response time became faster at higher concentrations whereas
recovery became slower. Following the Wolkenstein adsorp-
tion–desorption isotherm, alcohol surface coverage (q) (occu-
pancy of the adsorption sites on TiO2 nanorods) at higher
partial pressure (higher ppm level) is faster compared to its low
pressure counterpart (low ppm level).20 Fast response time of 8
s, 6 s and 5 s were obtained in 100 ppm concentrations of
ethanol, methanol and 2-propanol, respectively. On the other
hand, fast recovery time of 5 s, 6 s and 4 s was found in 1 ppm
concentrations of ethanol, methanol and 2-propanol, respec-
tively. Such fast recovery at lower concentrations possibly
attributed to the lower scattering phenomena. In general,
adsorbed molecules act as scattering centres for the carriers in
RM (%) at 8% RH RM (%) at 52% RH RM (%) at 75% RH
28.5 26.38 26.2
36.42 36.16 35.98
39.37 39.09 38.9
67.39 67.39 66.9
73.25 72.75 72.21
78.16 78.4 77.52
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by low temperature hydrolysis method was investigated for H2,

Fig. 6 Sensor (a) response time as a function of temperatures (b)
recovery time as a function of temperatures; for the alcohol
concentrations of 1 ppm and 100 ppm.
the sensing channel materials that lead to the degradation of
carrier mobility and hence sluggish recovery characteristics at
higher concentrations level.21
A comparative study of the present work with the sensor
parameters (operating temperature, response magnitude, and
response time/recovery time) in the earlier reported TiO2 based
gas/vapor sensors are summarized in Table 2. As evident from
Table 1, hydrothermal is the most used technique for TiO2
nanorod array synthesis. Apart from hydrothermal, electrospun,
hydrolysis and MAPLE technique were also used for nanorod
synthesis. However, it is envisaged that, gas/vapor sensing
properties of TiO2 nanorod array synthesized by other than
hydrothermal technique usually offered high temperature
sensing.8–10 For example, Nb doped TiO2 nanorod synthesized
C2H5OH and LPG sensing.10 For all the cases (H2, C2H5OH and
LPG), an optimum temperature of 500
C was found with cor-
responding response magnitude of 64.28%, 94.11% and
91.66%, respectively. Fast response time of 3–5 s and sluggish
recovery time of 49–79 s were achieved at 500
C for the H2,
C2H5OH and LPG concentrations of 400–4000 ppm. Similar
high operating temperature (500
C) was also evident in the
work of Bian et al.9 Electrospun TiO2/PVP hybrids nanorods
based sensor showed high response of 95% with fast
response/recovery of 11 s/4 s towards acetone.9 Authors claimed
that the surface catalytic effect of nanostructured TiO2 nanorod
possibly be the reason of such high response magnitude and
fast response time towards acetone. However, high operating
temperature was the main disadvantage of their work.9 The
trace amount of NO2 detection (30 ppb) employing TiO2 nano-
rods synthesized by matrix assisted pulsed laser evaporation
(MAPLE) technique was reported by Caricato et al.8 Their sensor
showed as high as 96.15% response magnitude in exposure of 1
ppm NO2 at an optimum temperature of 300
C. But the slug-
gish response/recovery prole (120 s/780 s) and relatively high
operating temperature are the major constraints the work.8 At
same temperature (300
C), ethanol sensing performance of Pt
doped hydrothermally grown TiO2 nanorod based resistive
devices was demonstrated by Epifani and his co-workers.7 The
resistive conguration of their TiO2 nanorod array showed the
maximum response of 96% with fast response time of 9–12 s
and recovery time of 10–15 s but at the cost of high operating
temperature (300
C). Relatively lower operating temperature
ethanol sensing performance was reported in the work of Chen
et al.6 and Park et al.5 Crystalline a-MoO3/TiO2 core/shell
nanorods synthesized by hydrothermal method showed
maximum response of 93.37% at 180
C.6 Authors claim that
such high response was due to the effect of formation of het-
erojunctions at the interfaces between MoO3 nanoparticles and
TiO2 nanorods.6 They found that the optimum temperature for
bare a-MoO3 sample was 270
C, whereas bare TiO2 nanorod did
not show any response below 180
C. Further, they found that,
compared to bare MoO3, the inclusion of TiO2 core/shell
nanorod with smaller thickness exhibited enhanced response

Table 2 A comparative study of the sensing parameters with earlier reported TiO2 nanorods based gas/vapor sensors with the present work

Material Method Gases/vapors Opt tempb (
C) Detection range (ppm) RMc (%) Res timed (s) Rec timee (s) Ref.

TiO2aNR Hydrothermal Ethanol 75 1–100 69 8 5 This work

Methanol 75 1–100 75 6 6
2-propanol 75 1–100 80 5 4
TiO2/ZnO NR Hydrothermal C2H5OH 150 5–25 99.58 70 30 5
MoO3/TiO2 NR Hydrothermal C2H5OH 180 10–500 93.37 40 40 6
Pt/TiO2 NR Hydrothermal C2H5OH 300 10–1000 96 9–12 10–15 7
TiO2 NR MAPLEf NO2 300 30 ppb to 50 ppm 96.15 120 780 8
TiO2 NR Electrospun CH3COCH3 500 1–1000 95 11 4 9
Nb/TiO2 NR Hydrolysis H2 500 4000 64.28 4 70 10
C2H5OH 500 400 94.11 3 79
LPG 500 4000 91.66 3 45
a
NR ¼ nanorod. b Opt temp ¼ optimum temperature. c
RM ¼ response magnitude. d
Res time ¼ response time. e
Rec time ¼ recovery time.
f
MAPLE ¼ matrix assistance pulse laser evaporation.

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Paper
at relatively lower temperature. Moderately high response time/
recovery time prole was the only disadvantage of their sensor
devices. A ve times increase in ethanol response was achieved
by TiO2 nanorods functionalized with ZnO nanoparticles.7 Such
high response was possibly due to ZnO functionalization which
offer hetero-interfaces (TiO2 nanorod/ZnO nanoparticle) to the
sensor system. However, their sensor offered sluggish response/
recovery of 70 s/30 s. As revealed from the literature survey,
earlier researchers achieved >90% response magnitude at the
cost of either higher operating temperature or sluggish
response/recovery prole. As far as the present work is con-
cerned, the developed titania tetragonal nanorods based sensor
offered the most promising result at only 75
C which is the
lowest one ever reported for TiO2 nanorod based gas/vapor
sensors. The minimum alcohol detection was as low as 1 ppm
with response magnitude of 29%, 37% and 40% towards
ethanol, methanol and 2-propanol. Fast response/recovery
characteristics with appreciably high response magnitude at
relatively low temperature (75
C) makes the present an
improved alternative compared to the existing ones.
The cross sensitivity of the developed alcohol sensor device
was investigated with the other interfering species like acetone,
2-butanone, benzene and xylene and the results are shown in
Fig. 7. The response magnitudes of the sensor towards these
interfering species were found to be 15.1/32.52%, 12.4/30.5%,
10.2/21.2% and 8.7/20.12% for 1/100 ppm of respective species
(acetone, butanone, benzene and xylene, respectively). Acetone
was revealed to the nearest interfering neighbour followed by
butanone, benzene and xylene. A response magnitude differ-
ence of 14%, 21.88% and 24.74% in 1 ppm and 36%,
43.27% and 46.77% in 100 ppm were observed for ethanol–
acetone, methanol–acetone and 2-propanol–acetone,
respectively.
Long term stability (dri in the base line resistance as well as
resistance variation in alcohol exposure) of the MOX based
Fig. 7 Cross sensitivity study of the TiO2 nanorod array based alcohol
sensor towards different interfering species like acetone, butanone,
benzene and xylene. The response magnitude difference between
alcohols (ethanol, methanol and 2-propanol) with respect to acetone
(nearest interfering neighbour) is shown pictorially for both 1 ppm and
100 ppm concentrations.
This journal is © The Royal Society of Chemistry 2015
RSC Advances
chemical sensor is still a burning issue.5,13 The proper annealing
of the sample and judicious control of stoichiometry were
reported to be the effective measures to improve the
stability.13,19 In the present study, the stability study was carried
out over a span of four weeks, in air, ethanol, methanol and 2-
propanol background and the results are shown in Fig. 8.
Clearly, TiO2 nanorods offered fairly promising stability over
such a long duration. The resistance dri of 1%, 1.75%,
1.93%, and 1.25% were observed in air, 10 ppm of ethanol,
methanol and 2-propanol, respectively. Such a small dri in
baseline resistance in turn ensures the improved repeatability
of the device also.
3.3. Alcohol sensing mechanism
Alcohol sensing mechanism of TiO2 tetragonal nanorod array
has been illustrated with the help a Wolkenstein adsorption–
desorption isotherm by considering (i) electron exchange
between adsorbed species and TiO2 nanorod surfaces (Fig. 9(a))
and (ii) band bending in the corresponding energy band
diagram (Fig. 9(b)). A single tetragonal TiO2 nanorod with
surface depletion by chemisorbed oxygen ion was considered
and shown as Fig. 9(a). Initially, oxygen from ambient at
elevated temperature gets adsorbed on the TiO2 surfaces in the
form of O2, O and O2.12,13 The chemisorbed species (O) act
as the electron trap centres on the semiconductor surfaces and
cause electron depleted regions on the TiO2 surfaces as depicted
in Fig. 9(a) and (b). Such accumulation of trapped electrons on
the sensing surface forces the band to bend upward (as shown
in Fig. 9(b)). The details of the oxygen chemisorptions and
corresponding band diagram have already been discussed in
ref. 12 and 13. Due to the sufficient separations among the
nanorods, alcohol molecules can diffuse along the nanorod
length and as a result chemisorptions can extend almost up to
the bottom of the rods (vertically along Z axis in the Fig. 9(a)).
Due to unavailability of free electrons conductivity of the sensor
device reduces. With exposure to alcohols, the replacement of
oxygen species by alcohols molecules decrease the
Fig. 8 Long term stability study of the TiO2 nanorod array based
alcohol sensor device at 75
C in air and in 10 ppm of ethanol,
methanol and 2-propanol, respectively.
RSC Adv., 2015, 5, 82159–82168 | 82165
RSC Advances Paper

2CH3CH3CHO(ads) + 12O(ads) /
5CO + CO2 + 7H2O + 12e for 2-propanol (11)

A generalized formula for response magnitude of the TiO2

nanorod array can be theoretically represented and correlated
with the present study following the above discussions. A single
TiO2 nanorod is considered here for the sake of simplicity.
Assuming that, initial chemisorptions of oxygen molecules
produce a depletion region of width W and carrier concentra-
tions in nanorod in air and in alcohol are na and ng, (respec-
tively) the rate equation (dn/dt) for the eqn (8) following the
Wolkenstein adsorption–desorption isotherm, can be repre-
sented as;22

Fig. 9 Schematic illustration of the ethanol molecule adsorption and ng ¼ kalcohol(T)[O]m[A0 –O]mt + na (12)
desorption on a single nanorod surfaces (along with horizontal and
vertical diffusion) assuming depletion region (W) formed in air (b) where kalcohol(T) ¼ reaction rate constant at temperature T, T ¼
corresponding energy band diagram of the nanorod in air and in
absolute temperature, t ¼ reaction time, m ¼ 1 for O ion and
alcohol.
1/2 for O2. The eqn (12) reveals that concentrations of electron
are dynamic and strongly depend on rate constant (k) and
reaction time (t). If we consider that the vapor pulse is ‘ON’ at
concentrations of O ions and releases the electrons back to the time t1 and reach steady state under exposure of alcohols at
TiO2 surface (conduction band). Subsequently, the band time t2, then, a time constant s ¼ (t2  t1) must be considered to
bending is reduced (Fig. 9(b)) and hence higher conductivity of calculate approximate electron concentrations (ng) under steady
the sensor devices is evidenced. The dissociative oxidation of state condition. By putting time constant (s) in eqn (12) we get
alcohols (ethanol, methanol and 2-propanol) on the nanorod
ng ¼ kalcohol(T)[O]m[A0 –O]ms + na (13)
surfaces in presence of O ions can be explained as follows; the
adsorbed alcohols dissociate to form A–O(ads) radicals and
As, resistance (R) is inversely proportional to carrier
adsorbed H+ ions (eqn (2)), where A ¼ CH3CH2O for ethanol,
concentrations (n), the response magnitude (RM) of the present
CH3O for methanol and CH3CH3CH2O for 2-propanol, respec-
nanorod array based sensor in terms of carrier concentrations
tively. Further, A–O(ads) dissociates to form A0 –O (eqn (3)), where
(n) and rate coefficient (kalcohol) can be written as;
A0 ¼ CH3CHO (for ethanol), CH2O (methanol) and CH3CH3CHO
(2-propanol). Finally, A0 –O reacts with O and produces CO, Ra  Rg skalcohol ðTÞ½Om ½Am
RM ¼ ¼ (14)
CO2, H2 and n number of electrons, where n ¼ 4, 4 and 12 for Ra ng
ethanol, methanol and 2-propanol, respectively.6,10,19 The details
of the ethanol, methanol and 2-propanol oxidation on the It is assumed that, negative surface charge on the semi-
nanorod surfaces are described in eqn (2)–(11). conductor surface is due to the chemisorbed oxygen ions only
and every oxygen ion generate one electron on the surface.
A–OH(gas) ¼ A–O(ads) + H(ads) (2)
Therefore, one can nd the number of available O ions by
A–O(ads) ¼ A0 –O + H(ads) (3) calculating number of trapped electrons on the sensing surface.
In chemisorption process, the number of trapped electron
H(ads) + H(ads) / 2H(ads)+ + 2e (4) concentration depends on the degree of surface coverage (q),
distribution of density of surface state (fa) and allowed surface
2H(ads)+ + 2O(ads) / 2OH(ads) (5) states i.e. number of adsorption sites (Nf) and they are related as
per eqn (15);20
2OH(ads) / H2O(ads) + O(ads) (6)
N ¼ O ¼ faqNf (15)
 
O(ads) + e / O(ads) (7)
1
fa ¼     (16)
0 
A –O + 4O(ads) / CO + CO2 + 2H2 + ne 
(8) Ec  Ess eVs
1 þ ga exp  exp 
KB T KB T
CH3CHO(ads) + 4O(ads) / where fa ¼ Fermi Dirac distribution function, ga ¼ degeneracy
CO + CO2 + 2H2O + 4e for ethanol (9) factor, EC ¼ conduction band energy, ESS ¼ surface state energy,
KB ¼ Boltzmann constant, T ¼ absolute temperature, q ¼
2CH3O(ads) + 4O(ads) /
surface coverage ¼ [bP/(1 + bP)], Nf ¼ total surface sites on the
CO + CO2 + 3H2O + 4e for methanol (10)

82166 | RSC Adv., 2015, 5, 82159–82168 This journal is © The Royal Society of Chemistry 2015
Paper
sensing surface. b ¼ adsorption co-efficient, P ¼ gas/vapor
pressure, eVs ¼ barrier height.
Therefore, eqn (14) can be written as;
Ra  Rg skalcohol ðTÞ½Am fa qNf
RM ¼ ¼ (17)
Ra ng
From eqn (17), it can be seen that the response magnitude is
proportional to reaction rate coefficient (kalcohol(T)) and
inversely proportional to carrier concentrations. Response
magnitude is principally governed by the surface coverage (q)
and the sticking co-efficient (S) of the target molecules. At a
particular temperature, for homogeneous and at surface,
sticking co-efficient (S) is a function of alcohol surface coverage
(q) as per eqn (18):23
S ¼ S0(1  q)r (18)
where S0 ¼ sticking coefficient at clean surface and r is a curve
tting constant with a value between 1 and 2.23 The sticking
coefficient decreases with increase in temperature.23 The
amount/number of target molecules stick to the sensing surface
is proportional to the sticking coefficient (S) which is also
proportional to the ux (F). Therefore, response magnitude in
terms of sticking coefficient can be written as (putting eqn (18)
into eqn (17));
"  r #
S response of 69%, 75% and 80% towards 100 ppm ethanol,
skalcohol ðTÞ½Am fa 1  Nf
Ra  Rg S0
RM ¼ ¼ (19)
Ra ng
To understand the sensor response characteristics, one
needs to thoroughly analyze the parameters like carrier
concentration (n), carrier mobility (m) and sticking coefficient
(S) including the effect of temperature variations as well as
variations in gas/vapor exposure. Initially, the effect of gas
exposure on these parameters (n, m and S) and subsequently the
effect of temperature (T) will be considered in this discussion.
Conductivity (s) of the sensing layer decreases in air due to the
decrease of effective carrier concentrations (n). Upon gas/vapor
exposure, conductivity increases as carrier concentrations (n) in
the semiconductor increases and mobility (m) of the carrier
remains almost unaffected (because of negligible carrier–carrier
scattering). In such situation (when temperature (T) is xed),
sticking coefficient (S) is the function of surface coverage (q)
only, as per eqn (18). Now, with increase in temperature, the
sticking coefficient decreases gradually but aer a certain
temperature (75
C in the present study), the rate of such
decrease is more prominent.23 At higher temperatures, due to
thermal vibration, gaseous molecules and TiO2 surface atoms
act as the scattering centres for the new incoming target
molecules and hence the sticking coefficient is decreased.
Further, carrier concentration (n) is found to increase with
increase in temperature whereas carrier mobility (m) decreases
with increase in temperature (due to dominant lattice scat-
tering). Therefore, it can be envisaged that, at low temperature
This journal is © The Royal Society of Chemistry 2015
RSC Advances
range (27–75
C), mobility (m) decreases, carrier concentration
(n) increases but sticking coefficient (S) decreases but at a very
slow rate. The resistance Ra and Rg both reduces but the rate of
decrease of Rg is much higher (as sticking coefficient is higher at
low temperature) than that of Ra. So, response magnitude
[RM% ¼ ((Ra  Rg)/Ra)  100] in the temperature range 27–75
C
is expected to be increased which is in conrmation with the
experimental results [Fig. 4(a)]. On the other hand, at relatively
higher temperature range (75–175
C), both the rate of increase
of carrier concentration (n) and the rate of decrease of mobility
(m) is much higher than that in the lower temperature range
(27–75
C). Consequently, overall base line resistance (Ra) vari-
ation is not so signicant in that temperature range (Fig. 3). In
addition, Rg value is found to decrease insignicantly in the
temperature range (75–175
C) due to the decrease of sticking
co-efficient (S) at much higher rate (compared to low tempera-
ture zone). Possibly that is why the response magnitude
decreases gradually in that temperature range (75–175
C).
4. Conclusions
Low temperature (75
C), low ppm (1–100 ppm) alcohol detec-
tion employing one dimensional tetragonal nanorod array of
TiO2 has been demonstrated in the present paper. Hydrother-
mally grown nanorod array showed both anatase and rutile
crystallinity with grain size of 35–37 nm. The maximum
methanol and 2-propanol was achieved at an operating
temperature of only 75
C which reasonably lower than that of
the earlier reported works. Further, sensor offered the
minimum alcohol detection level of 1 ppm with appreciable
response magnitude (29%, 37% and 40% towards ethanol,
methanol and 2-propanol) with fast response time and recovery
time of 12–14 s and 4–5 s, respectively. The sensor also
offered very promising stability over a span of four weeks. The
sensing mechanism of TiO2 nanorod array has also been illus-
trated with the help of Wolkenstein adsorption–desorption
isotherm and corresponding energy band diagram. Measure-
ment of the specic surface area of TiO2 nanorod, using BET
method, has been considered as a future work for better
quantitative understanding of the related sensing mechanism.
Acknowledgements
This work was supported by Indian National Science Academy
(INSA) (No. SP/YSP/81/2013/735). B. Bhowmik thankfully
acknowledges COE, TEQIP-II, IIEST, Shibpur for his PhD
fellowship.
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