Article

Journal of
Copyright © 2016 American Scientific Publishers
Nanoscience and Nanotechnology
All rights reserved Vol. 16, 11580–11585, 2016
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Growth of Networked TiO2 Nanowires for

Gas-Sensing Applications
Jun-Seong Lee, Akash Katoch, Jae-Hun Kim, and Sang Sub Kim∗
Department of Materials Science and Engineering, Inha University, Incheon 402-751, Republic of Korea

For the first time, we report on the synthesis of networked TiO2 nanowires using the vapor-phase
growth technique. The gas-sensing properties of prepared samples were tested. The networked
TiO2 nanowires were grown over patterned interdigital electrodes with width of 20
m and spacing
of 10
m. The use of a catalytic Ti layer with Ti vapor being supplied was the essential condition
for growth of networked TiO2 nanowires. The accumulation of Ti vapor on the Ti catalytic layer and
subsequent oxidation of Ti to TiO2 are the source of the growth of TiO2 nanowires. The average
diameter of the synthesized TiO2 nanowires was 90 nm and were single crystalline with pure TiO2
rutile phase. According to the results of the sensing measurements, the networked TiO2 nanowires
showed the comparable sensor response to other forms of TiO2 and have potential for use as a
sensor platform to detect reducing or oxidizing gases.
Keywords: TiO2 , Nanowire, Vapor-Phase Growth, Oxide, Gas Sensor.
IP: 5.62.159.212 On: Sun, 21 Oct 2018 08:14:00
1. INTRODUCTION Copyright: American Scientific Publishers oxide nanowires have been used
Multiply-networked
In recent years, the detection of chemical gases Delivered
is a bytoIngenta
circumvent the drawbacks of single-nanowire sensors.
primary concern for the safety of mankind and the They have been known to be effective in the actual
environment. Oxide semiconductor-based chemiresistive- implementation of nanowire-based gas sensors with good
type gas sensors have been used for the detection of reproducibility, easier device fabrication and lower cost.
chemical species whose concentration is of the order of In previous works,12–14 we have succeeded in making net-
part per million (ppm). 1
2
Importantly, one-dimensional worked SnO2 nanowires and thoroughly investigated the
oxide nanostructures including nanowires,3 nanofibers4 most suitable design and geometry of these SnO2 nanowires
and nanorods5
6 have shown superior gas-sensing charac- for enhanced sensing properties. It has been confirmed that
teristics in comparison to their thin-film7 or bulk counter- such networked-type nanowires can form a good sensing
parts due to their peculiar materials characteristics, such as platform. In addition, ZnO nanowires were grown in a
large surface-to-volume ratios, high crystalline quality, and network arrangement using the vapor-phase growth tech-
Debye-length dimension, which are promising properties nique and their sensing properties were thoroughly inves-
for ensuring outstanding gas-sensing capabilities.8 tigated in earlier reports.15
16 Thermal oxidation is another
Single oxide nanowire sensors have been found to be method which has been used to grow crystalline p-type
highly sensitive regarding the detection of very low con- CuO nanowires with higher aspect ratio for fabrication of
centrations of certain gaseous species.9 In spite of their crabwise CuO interconnect structures.17
18 Very recently,
superior sensing characteristics, the practical application p-type networked CuO nanowires were also synthesized in
of single-nanowire sensors has been limited by some a network arrangement on a deliberately designed patterned
serious disadvantages including tedious device fabrica- interdigital electrode (PIE) by thermal heating a metallic
10
tion, poor reliability, and high cost. Moreover, retain- Cu layer.19 In Ref. [19], it has been shown that networked
ing reproducible sensing characteristics is hard to ensure CuO nanowires are promising candidates to be applied in
and highly precise instruments are required for the detec- form of a sensor platform particularly for the detection of
tion of extremely small resistance modulations induced by reducing gases.
the adsorption and desorption of a small number of gas Except for the above mentioned SnO2 , ZnO, and CuO
molecules. 11 nanowires, as far as the authors know, there is no report
on sensors based on networked nanowires of other poten-
∗
Author to whom correspondence should be addressed. tial sensor materials, such as TiO2 , In2 O3 etc. Previously,

11580 J. Nanosci. Nanotechnol. 2016, Vol. 16, No. 11 1533-4880/2016/16/11580/006 doi:10.1166/jnn.2016.13555

Lee et al.
the methods such as wet chemical approach and lithog-
raphy techniques have been used to synthesize TiO2
nanowires.20–22 However, these methods are not suitable
particularly for fabrication of networked metal oxide nano-
structures. Exploring how to synthesize sensor materials
with affinity to network formation and their corresponding
sensing properties is essential for practical applications of
multiply-networked nanowires. In this work, for the first
time, we have succeeded in synthesizing networked TiO2
nanowires by using a catalytic Ti layer and simultaneously
supplied Ti vapor, and their gas-sensing properties have
been tested.
2. EXPERIMENTAL DETAILS
2.1. Synthesis of TiO2 Nanowires
To grow networked TiO2 nanowires, Ti vapor was sup-
plied to a Ti layer. For the selective growth of TiO2
nanowires, patterned interdigital electrodes (PIEs) with
width of 20 m and spacing of 10 m were used. The PIEs
were composed of a trilayer of Ti (1 m)/Pt (200 nm)/Ti
(50 nm) which were deposited on SiO2 (200 nm)-grown
Si (100) substrate using a conventional photolithographic
process. The bottom Ti and Pt layers were deposited by
sputtering and the Ti top layer was deposited by electron-
beam evaporation. Here, the bottom Ti layer in between Pt
and SiO2 -grown Si wafer was used to improve the adhe-
sion between the two materials. The Ti top layer played
IP: 5.62.159.212
the role of a catalyst for the growth On: Sun,to21grow
of TiO2 nanowires.
Copyright:
American Scientific Publishers
The PIE-prepared Si wafers were placed in a horizontal
Delivered bysurface
tube-type furnace with distance of 4 cm away from the Ti
powder (99.5%, ∼200 mesh). Referring to the paper [23] in
which the vapor pressure of Ti is reported as high as 205 ×
10−9 atm at 1237  C, the furnace was then evacuated by a
rotary pump down to ∼1 × 10−3 Torr, heated to 1050  C,
and maintained at this temperature for 1 h. O2 (99.995%
purity) and Ar (99.999% purity) were flowed through the
tube at rates 10 and 300 standard cubic centimeters per
minute (sccm), which were controlled by mass-flow con-
trollers, respectively. The TiO2 nanowires were selectively
grown on the PIE pad and cross-linked one to the other
between adjacent PIEs, eventually forming a chemiresistive
electrical passage. During our preliminary investigations,
we have confirmed that the growth of TiO2 was not taken
place in the absence of supplying Ti vapour.
2.2. Characterization
The microstructure and phase composition of the syn-
thesized and networked TiO2 nanowires were examined
by field-emission scanning electron microscopy (FE-SEM,
Hitachi, S-4200) and X-ray diffraction (XRD, Philips
X’pert MRD diffractometer) using Cu K radiation with
 = 15418 Å.
2.3. Sensing Measurement
The gas-sensing properties of the networked TiO2
nanowires were tested with respect to various reducing
J. Nanosci. Nanotechnol. 16, 11580–11585, 2016
Growth of Networked TiO2 Nanowires for Gas-Sensing Applications
and oxidizing gases including carbon monoxide (CO), ben-
zene (C6 H6 ), toluene (C7 H8 ), and nitrogen dioxide (NO2 )
using a gas-sensing system. The sensors were placed in a
horizontal-type tube furnace and the measuring tempera-
ture was varied between 300 and 500  C. The gas concen-
tration was controlled by changing the mixing ratio of the
dry air-balanced target gas and the dry air through accurate
mass flow controllers. The more technical details of the
sensing experiments are described in earlier reports.24
25
The sensor response S for a reducing gas was estimated
according to S = Ra − Rg /Ra × 100%, where Ra is the
resistance in the presence of air without any other gas and
Rg is the resistance measured in the presence of the tar-
get gas. For an oxidizing gas, S = Rg − Ra /Ra × 100%,
was used for the sensor response.
3. RESULTS AND DISCUSSION
Figure 1(a) schematically describes the fabrication pro-
cedure of the gas sensors based on networked TiO2
nanowires investigated in this study. The most important
condition for the growth of the networked TiO2 nanowires
is the use of the catalytic Ti layer and the simultaneous
supply of Ti vapor. We have tested other catalytic layers,
such as Au and Pt that are the most widely used cat-
alytic layer types for the growth of oxide nanowires by
means of the vapor-phase growth technique, but we failed
TiO2 08:14:00
Oct 2018 nanowires in these two cases (Fig. 2). It
is most likely that Ti vapor preferentially arrives at the
Ingentaof the Ti layer and forms seed crystals. Subse-
quently, O2 molecules oxidize Ti to TiO2 , thereby simulta-
neously growing nanowire structure over the seed crystal.
The further supply of Ti facilitates the extensive growth
of TiO2 nanowires while reacting with the oxygen of
ambient air, thereby resulting in the cross-linked structure
between two adjacent PIE pads. Figures 1(b–d) show typi-
cal plane, cross-sectional and high-magnification FE-SEM
images of TiO2 nanowires. It is evident that the selec-
tive growth of TiO2 nanowires on PIE pads is realized
and, consequently, cross-linked TiO2 nanowires are cre-
ated. The average diameter of the TiO2 nanowires was
∼100 nm (Fig. 1(c)). In addition, the growth condition
of TiO 2 nanowires was investigated by changing various
parameters including the distance between the Ti source
and the PIE-prepared substrate, the heating temperature,
the growth time, and the amount of gas flow. Among them,
the distance between the Ti source and PIE-prepared sub-
strate was found to be the key parameter influencing the
growth behavior of the TiO2 nanowires. Figure 3 presents
the growth behavior of TiO2 nanowires in relation with the
heating temperature and the distance between the Ti source
and the PIE-prepared substrate. It is evident that the net-
work junction between TiO2 nanowires was accomplished
by maintaining the distance 4 cm.
The phase of the synthesized TiO2 nanowires was exam-
ined by XRD. Figure 1(e) shows a typical XRD pattern
11581
Growth of Networked TiO2 Nanowires for Gas-Sensing Applications Lee et al.

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Figure 1. (a) Schematic illustrations of the fabrication process of networked TiO2 nanowire sensors. FE-SEM images of TiO2 nanowires; (b) plane,
(c) cross-sectional view and (d) high-magnification images. (e) Representative XRD pattern of networked TiO2 nanowires.

of networked TiO2 nanowires. The peaks well matched
with the tetragonal rutile structure of TiO2 (JCPDS
89-4920), thereby indicating the successful growth of
TiO2 nanowires in a network having the pure TiO2
phase.
The sensing properties of the networked TiO2 nanowires
were tested for various reducing (CO, C6 H6 , and C7 H8 
and oxidizing (NO2 ) gases. First, the operating tempera-
ture was optimized by measuring the dynamic resistance
curves with respect to CO in the range from 300 to
500  C. Some typical response curves of the networked
TiO2 nanowires measured at concentrations of 1, 5, and
50 ppm of CO are included in Figure 4(a). As is evi-
dent, the resistance tracks the supply and stoppage of
CO, following a typical n-type semiconductor chemire-
sistive behavior. The corresponding sensor responses as a
function of temperature are summarized in Figure 4(b).
For the purpose of showing more clearly the correla-
tion between sensor response and operating temperature,
the sensor response of the networked TiO2 nanowires
at 1 ppm of CO is replotted as a function of temper-
ature in Figure 4(c). As is evident, the maximal sen-
sor response is obtained at 400  C. The volcano-shape
gas sensor response with the operating temperature is
quite common in semiconductor-based chmiresistive-type
sensors.26–28 The sensor response is generally improved
and reaches its maximum at a certain elevated operating
temperature, and then deteriorates with further raising
temperature. The competition between adsorption and
desorption of both oxygen molecules and analyte gas
with respect to the operating temperature is likely to
be responsible for the volcano-shaped sensor response in

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Lee et al. Growth of Networked TiO2 Nanowires for Gas-Sensing Applications

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Copyright: American Scientific Publishers
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Figure 2. FE-SEM images of PIE-prepared substrates with Au and Pt
catalytic layers used for growth of TiO2 nanowires with growth time:
(a) 1 h, (b) 3 h and (c) 5 h for Au; (d) 1 h, (e) 3 h and (f) 5 h for Pt.

dependence of temperature. On the basis of this result, all

sensing measurements were performed at 400  C, although
it is likely that there may be a small difference in the
maximal operating temperature with regard to the kind
of gas.
Figure 5(a) shows the resistance curves of networked
TiO2 nanowires. They were measured at 400  C at con-
centrations of 1, 5, and 50 ppm CO, C6 H6 , C7 H8 , and
NO2 . The obtained sensor responses are summarized in
Figure 5(b), and the sensor responses for the tested gases at
50 ppm are compared in Figure 5(c). The sensor response
Figure 3. The growth of TiO2 nanowires: Temperature (a) 900 (b) 950,
against CO is highest among the tested gases. The sen- (c) 1000 and (d) 1050  C at constant distance between the Ti source and
sor response of networked TiO2 nanowires against CO gas PIE-prepared substrate of 1 cm and growth time of 1 h; distance between
is compared to that of gas sensors using other forms of the Ti source and the PIE-prepared substrate (e) (i) 1, (f) (j) 2.5, (g) (k)
TiO2 including nanofibers, hollow fibers, thin films etc., 4 and (h) (l) 5.5 cm, with growth time of 1 and 3 h at 1050  C. The
as is summarized in Table I.29–31 Considering the sensor insets show a top view of networked TiO2 nanowires selectively grown
on a PIE-prepared substrate.
response, the networked TiO2 nanowires synthesized in
this study are promising candidates for the use as sensor
materials to detect trace concentrations of various gaseous response needs to be investigated for a wider gas concen-
species. Note that the sensor response of the networked tration range in a future study.
TiO2 nanowires measured at concentrations of 1, 5 and The sensing mechanism operating in the networked
50 ppm of CO have no significant difference. The sensor TiO2 nanowires is based on the joint effect of the

J. Nanosci. Nanotechnol. 16, 11580–11585, 2016 11583

Growth of Networked TiO2 Nanowires for Gas-Sensing Applications Lee et al.

Figure 4. (a) Dynamic resistance curves of networked TiO2 nanowires Figure 5. (a) Dynamic resistance curves of networked TiO2 nanowires
measured at various temperatures for CO gas. (b) Summary of the sensor to various gases including CO, C6 H6 , C7 H8 , and NO2 . (b) Summary of
responses of networked TiO2 nanowires with respect to CO gas. (c) Sen- the sensor responses. (c) Sensor response of networked TiO2 nanowires
sor response of networked TiO2 nanowires at 1 ppm CO as a function of to various gases at the concentration of 50 ppm at 400  C.
temperature. IP: 5.62.159.212 On: Sun, 21 Oct 2018 08:14:00
Copyright: American Scientific Publishers
The detection of CO is of importance in diverse areas in
Delivered by Ingenta
radial modulation in the electron-depletion layer along modern industrialized society. For example, the concentra-
the nanowire length 15
32
and changes in the potential bar- tion of CO gas in indoor has been commonly used as an
rier at the nanowire junctions. 33
34
In Figure 6(a), the indicator for level of gas poisoning and smoking condition.
radial modulation is schematically described for oxidiz- The CO gas is known to be a representative toxic molecule
ing and reducing gases. In air, oxygen molecules adsorb that can replace oxygen in the blood of humans, conse-
at the surface of TiO2 nanowires of n-type semiconduc- quently causing hypoxia. In addition, the CO detection
tors, capturing electrons from the conduction band of TiO2 , can be used for an early-fire-monitoring system because
and thereby making the surface region transform into an the CO gas is generated by the incomplete combustion of
electron-depletion layer. The supply of an oxidizing gas C-containing substances so that the presence of CO is a
additionally captures electrons, thickening the electron- signature of fire. Accordingly, the realization of the highly
sensitive CO sensor is strongly required to secure safer
depletion layer underneath the surface of the nanowires
environment, and TiO2 nanowires have the potential to be
and eventually increasing their resistance. In contrast, if
used for detection of CO according to the present work.
a reducing gas is supplied, the gas molecules are likely
to react with pre-adsorbed oxygen, thereby turning into
Table I. Comparison of CO-sensing properties of networked TiO2 -
volatile chemical compounds and releasing the captured nanowire sensors fabricated in this work with those of other forms of
electrons back to the conduction band of TiO2 . This TiO2 reported in the literature.
process eventually thins the electron-depletion layer and
CO gas Sensor
decreases the resistance of the nanowires. The correspond- Material Operating concentration response
ing potential-barrier modulation is depicted in Figure 6(b). type temperature ( C) (ppm) (S) (%) Refs.
At nanowire junctions, the potential barrier is established
Nanowires 400 1 11 This work
similarly to the case of grain boundaries in a bulk sensor Thin film 400 100 9 29
material. In air, the upward band bending takes place due Nanofibers 300 100 10 30
to the adsorption of oxygen species. The additional adsorp- Hollow 25 0.1 12 31
tion of oxidizing gases increases the potential barrier. In nanofibers
Nanofibers 25 10 3 31
contrast, reducing gases reduce the oxygen adsorption and
∗
thereby lower the potential barrier height. Note: Sensor response S = Ra − Rg /Rg × 100(%).

11584 J. Nanosci. Nanotechnol. 16, 11580–11585, 2016

Lee et al.
Figure 6. Schematic illustrations of the sensing mechanism operating in
networked TiO2 nanowires: Potential modulations (a) in radial direction
and (b) across the junctions.
4. CONCLUSION
We have synthesized networked TiO2 nanowires for gas-
IP: 5.62.159.212 On: Sun,20.
sensing applications using the vapor-phase growth
Copyright: tech- Scientific
American
nique. It was essential to apply a Ti layer as catalyst for by21.
Delivered
the growth of TiO2 nanowires. The formation of seed crys-
tals by accumulation of Ti vapors and the subsequent oxi-
dation of Ti to TiO2 were likely to a growth mechanism
of TiO2 nanowires. The continuous supply of Ti vapor
resulted in the selective growth of TiO2 nanowires on the
Ti layer. The synthesized TiO2 nanowires were single crys-
talline and of rutile phase with average diameter of 90 nm.
The gas-sensing properties of the sensors fabricated from
these networked TiO2 nanowires were comparable to those
of alternative sensors using other forms of TiO2 , thereby
demonstrating that networked TiO2 nanowires represent a
potential sensing platform.
Acknowledgment: This work was supported by Inha
University.
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Received: 28 November 2015. Accepted: 5 April 2016.
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