Materials Science in Semiconductor Processing 86 (2018) 79–84

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Materials Science in Semiconductor Processing

journal homepage: www.elsevier.com/locate/mssp

Synthesis of WO3 nanorods by thermal oxidation technique for NO2 gas T

sensing application
⁎
Bhagaban Beheraa, , Sudhir Chandrab
a
Centre for Applied Research in Electronics, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India
b
Electronics and Communication Department, Bennett University, Plot No. 8-11, Tech Zone-II, Greater Noida 201310, UP, India

A R T I C LE I N FO A B S T R A C T S

Keywords: In this work, WO3 nanorods were successfully synthesized by thermal oxidation method and further investigated
WO3 Nanorods for gas sensing application. For WO3 nanorods synthesis, tungsten film was deposited on oxidized Si substrate by
NO2 sputtering method and subsequently subjected to thermal oxidation process at 500 °C in atmospheric environ-
Gas sensor ment. The synthesized nanorods were analyzed using SEM, XRD, Raman, and XPS. A chemiresistive type MEMS-
Selective detection
based sensing device was fabricated incorporating these nanorods. The sensor was tested for different gases and
VOCs over operating temperatures ranging from 75 to 300°C. It showed high selectivity towards NO2 gas over
H2S, NH3, acetone, methanol, and ethanol. The excellent sensing performance and sophisticated method of
synthesis make this a promising candidate for gas sensing applications.

1. Introduction for synthesis of these WO3 nanostructures [10–13,16–22]. All these

methods have certain limitations such as (i) high thermal budget (ii)
High-performance gas sensors have gained increasing attention due complicated processing technique (iii) use of catalyst (iv) long proces-
to their diverse applications such as pollutant detection, medical di- sing time (v) high cost (vi) adaptability for mass production, (vii) un-
agnosis, chemical monitoring, food processing etc. Day by day, the wanted byproducts (vii) not being environment-friendly. Among these
amount of air pollutants such as NH3, CO, SO2, H2S NO2, and volatile methods, sol-gel and chemical bath depositions are economical, low
organic compounds (VOCs) exhaust from combustible engines, auto- temperature, and mass production worthy process. However, the sol-gel
mobiles are increasing [1]. NO2 is one of the major pollutants found in films create uncontrolled porosity, weak adhesion to substrate and
the atmosphere which causes acid rain, ozone layer thinning and re- unwanted cracks. On the other hand, chemical bath deposition and
spiratory related diseases. Thus, an efficient NO2 sensor needs to be hydrothermal methods produce unwanted byproducts after each de-
developed for environmental monitoring and protection of humans position.
from over-exposure. In the field of sensor technology, intensive research is in progress for
Over the last decade, research has been devoted considerable efforts optimal sensing performances by controlling grain sizes, shapes, por-
for development of sensitive and reliable gas sensor. Various semi- osities and/or active surface areas and makes it compatible with post-
conducting metal oxides such as SnO2, ZnO, CuO, WO3, In2O3, and TiO2 CMOS processing [23]. Nanostructures synthesis by thermal oxidation
have been used as sensing material [2–7]. Among these, tungsten oxide technique is simple, cost-effective, and production worthy method.
(WOx) has received considerable attention as a promising sensing ma- Nanostructures of ZnO, CuO and F2O3 have been successfully synthe-
terial due to its high sensitivity and stability, specifically towards NO2 sized by thermal oxidation technique [3,24,25]. There are only few
gas [5,8–11]. Various WO3 nanostructures such as nanoparticles, na- reports on synthesis of tungsten nanostructures by thermal oxidation
nowhisker, nanorods, and nanowires have shown enhanced sensing technique and thus more studies are needed on this method for different
properties towards different gases [12–15]. The prime reason for such applications [5,26].
enhancement is due to improvement in surface area to volume ratio In this work, WO3 nanorods are synthesized by thermal oxidation
which propels the chemical interaction between analytes and sensing technique in atmospheric environment from sputter deposited tungsten
element. Till date, several methods such as thermal evaporation, che- film. Post-oxidized sample was analyzed using various techniques such
mical vapor deposition, electro-spinning, sol-gel, chemical bath de- as scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman
position, hydrothermal and template-directed synthesis have been used Spectroscopy and X-ray photoelectron spectroscopy (XPS) to study its

⁎
Corresponding author.
E-mail address: bhagaban7044@gmail.com (B. Behera).

https://doi.org/10.1016/j.mssp.2018.06.022
Received 16 May 2018; Received in revised form 14 June 2018; Accepted 23 June 2018
Available online 30 June 2018
1369-8001/ © 2018 Elsevier Ltd. All rights reserved.
B. Behera, S. Chandra Materials Science in Semiconductor Processing 86 (2018) 79–84

morphology, crystalline nature, and chemical composition. A micro- different VOCs (ethanol, acetone, and methanol) and toxic gases (NH3,
electromechanical systems (MEMS) based sensing device was fabricated H2S and NO2) of concentration 2–50 ppm at different operating tem-
incorporating nanorods and their performances towards different VOCs perature. The sensor sensitivity also known as response magnitude is
(ethanol, acetone, and methanol) and toxic gases (NH3, H2S and NO2) defined as [30]:
were evaluated. The sensor's response over different operating tem-
Ra − Rg
perature and concentrations was evaluated for optimal sensing perfor- S= × 100% (for reducing gas)
mances. Rg
Rg − Ra
S= × 100% (for oxidizing gas)
Ra (1)
2. Experimental works
Where Rg and Ra are the resistance of nanorods in presence and absence
Tungsten metal film of thickness 100 nm was deposited on SiO2 of target gas respectively. The sensing was evaluated to find out para-
coated Si substrate using RF sputtering technique. The deposited film meters for optimal sensing performance.
was oxidized in a horizontal tube furnace at 500 °C for 4 h in atmo-
spheric ambient. Post-oxidized sample's morphology was observed 3. Results and discussion
using SEM (Model: Zeiss, EVO 18) and its crystallography was analyzed
using XRD (Model: Phillips X’pert, Cu Kα X-ray source with a wave- Fig. 2(a) shows SEM image of as-deposited 100 nm thick tungsten
length of 1.54 Å) and Raman Spectroscopy (Model: HORIBA, LabRAM film. Subsequently, the sample is oxidized at 500 °C for 4 h in atmo-
HR Evolution, laser source: 514 nm). The chemical composition of na- spheric environment and its SEM is presented in Fig. 2(b). It is observed
norods was studied using XPS (Model: SPECS, Phoibos 100). After WO3 that uniformly distributed nanorods having diameter ~ 80 nm and
nanorods growth, a sensor was fabricated using planar MEMS tech- length and ~ 400 nm are formed.
nology as mentioned in our previous publication [4]. The device con- Post-oxidized sample's XRD pattern is shown in Fig. 3(a). The pat-
sists of a micro-heater and surrounding IDE (Inter Digited Electrode) tern is indexed as (002), (020), (211), (022), (222), 132) and (004) of
structure and both of these are placed on solid thermal insulator. A monoclinic-WO3. Also, it confirms that the nanorods are polycrystalline
schematic diagram of micromachined gas sensor and its optical image with monoclinic phase having lattice parameters a = 7.300 Å, b
are shown in Fig. 1. The size of the device was 1.21 mm2 and had = 7.538 Å, c = 7.689 Å and β = 90.892◦ (JCPDS 75–0192). The in-
minimum feature size 40 µm. This device was fabricated by following tensity of (002) diffraction peak is strongest indicating most of the
various microfabrication steps such as oxidation, photolithography, nanorods fabric axis is along the [002] direction. The grain size of
anisotropic etching, deposition, chemical mechanical polishing and lift- nanorod was calculated using Scherrer's formula
off. In this micromachined platform, a solid thermal insulator (6 µm kλ
thick of SiO2) was created by burying it into the silicon substrate. This D=
βcosθ
platform reduces heat spreading from localized area and thus power
consumption is reduced [4]. The temperature is generated by a joule Where k represents Scherrer's constant, λ is 1.54 Å and β is FWHM of
heating when a voltage is applied across the terminals of the micro- XRD peak. The nanorods average grain size is 26 nm.
heater. For calibration purpose, a dc voltage was applied through Fig. 3(b) shows Raman spectra of synthesized nanorods. It can be
source pads and simultaneously, the current was measured between the observed that peaks are sharp indicating nanorods are crystalline in
two pads i.e. resistance was measured at different voltage. In a separate nature. In general tungsten oxides show two characteristics peaks cor-
experiment, microheater resistance was measured at different tem- responding to stretching range (200–400 cm−1) and bending range
peratures by keeping it on a stabilized hot plate. Resistance measured (600–900 cm−1). The recorded spectrums are compared with pre-
by both these techniques were compared and calibrated to find out viously published results, which indicate that nanorods are in mono-
temperature of the heater when a voltage was applied during actual clinic phase [31]. The peak at 273.3 and 326.6 cm−1 represents
operation of the sensor [27–29]. Thus, the temperature of the micro- bending vibration of W–O–W. The peaks 690.4 and 807.1 cm−1 re-
heater was not measured directly but estimated by characterizing the presents asymmetric and symmetric vibration of W6+–O bonds in
current-voltage and resistance-temperature curves of the microheater. stretching mode [31,32].
The nanorods resistance was measured using a resistance meter (Kei- Chemical states of nanorods were studied using XPS technique.
thely 2400) connected across IDE structure. The sensor was tested for Fig. 4 shows XPS core level spectra of W 4f and O 1s. All these peaks

Fig. 1. (a) Schematic diagram of micromachined gas sensor (b) Optical image of the sensing device.

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B. Behera, S. Chandra Materials Science in Semiconductor Processing 86 (2018) 79–84

Fig. 2. SEM image of 100 nm tungsten film (a) as-deposited (b) oxidized at 500 °C for 4 h.

Fig. 3. (a) XRD pattern and (b) Raman spectra of nanorods synthesized from 100 nm tungsten film oxidized at 500 °C.

were calibrated with standard C 1s peak (284.8 eV). Two major peaks 3.1. Gas sensing measurement
centered at 35.7 and 37.8 eV are identified as W4f7/2 and W4f5/2
respectively. This spin-orbit splitting of W4f is 2.1 eV, which agrees WO3 nanorods are promising gas sensing material due to their en-
with previously published literature for W6+ ions [33,34]. The peak at hanced surface related activities. A sensing device was fabricated using
530.1 eV is attributed to O2- ions of WO3. The XRD, Raman and XPS planar MEMS technology incorporating WO3 nanorods as shown in
study strongly supports the formation of WO3 nanorods. Fig. 1. The resistance of nanorods was measured using IDE structure at
different temperatures. The baseline resistance of nanorods at 225 °C

Fig. 4. (a) XPS survey scan of WO3 nanorods (b) core level doublet spectra of W4f (c) core level spectra of O1s.

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B. Behera, S. Chandra Materials Science in Semiconductor Processing 86 (2018) 79–84

Fig. 5. (a) The sensor's change in resistance during exposure of 10 ppm NO2 gas at 225 °C operating temperature (b) The sensitivity comparison for different gases of
10 ppm concentration at 225 °C operating temperature.

working temperatures was 8.9 × 105 Ω. When NO2 gas was introduced electrons to the surface of nanorods which causes decrease in depletion
into the sensing chamber, the resistance was observed to be rising from width and potential barrier height. This difference in sensing me-
its base value and it decreased after venting the chamber. The sensor's chanism is the possible reason for selective detection of NO2 gas over
change in resistance during exposure and ventilation of 10 ppm of NO2 other gases and VOCs.
gas is presented in Fig. 5(a). Similarly, the device was tested with NH3
O2 (gas)↔O2 (ads) (2.0)
gas, H2S gas, acetone, methanol, and ethanol vapors. The sensitivity of
the sensor for different gases has been calculated using Eq. (1) and O2 (ads) +2e−→2O− (ads)orO2 (ads)+4e− → 2O2 − (ads) (2.1)
results are compared as shown in Fig. 5(b). It is observed that the WO3
nanorods are highly sensitive towards NO2 gas whereas it shows rela- NO2 (gas) → NO2 (ads) (3.0)
tively low sensitivity towards NH3, H2S, ethanol, methanol, and
NO2 (ads) + 2e−→NO−2 (ads) (3.1)
acetone. At 225 °C operating temperature, the sensor showed selective
towards NO2 gas with selectivity coefficients SNO2/SNH3 = 5.4, SNO2/ NO2 (ads) + O− (ads) + 2e−→NO−2 (ads) + O2 − (ads) (3.2)
SH2S = 6, SNO2/SEthanol = 4.8, SNO2/SMethanol = 9 and SNO2/SAcetone
= 22. The response and recovery times (90% and 10% of total change NO−2 (ads) + O− (ads) + 2e−→NO(gas)+2O2 − (ads) (3.3)
in resistance) were calculated at 225 °C operating temperature for
10 ppm of gases. The response time for ethanol, methanol, acetone, 2NH3+3O− (ads) → N2 + 3H2 O +3e− (4)
NO2, NH3, and H2S are 112, 115, 110, 96, 145 and 160 s whereas re-
covery time are 124,126, 140, 81, 155 and 126 s. The sensing perfor-
2CH3OH + 60– (ads) → 2CO2 + 4H2O + 6e– (5)
mance of WO3 nanorods towards NO2 gas indicates that it will be an
ideal detector during competency detection of NO2 gas in various en- 2H2S+ 3O2- (ads) → 2H2O + 2SO2+ 3e– (6)
vironments. – –
CH3COCH3 + 80 (abs) ↔ 3CO2 + 3H2O + 8e (7)
From Fig. 5(a), it is observed that the resistance increases during
– –
exposure to NO2 gas (oxidizing gas) indicating WO3 nanorods are n- 2C2H5OH + 50 (ads) → 4CO2 + 4H2O + 5e (8)
type semiconductors. The baseline resistance was decreasing (not
shown here) during exposure of reducing gases such as ethanol, me- The operating temperature of chemeoresistive gas sensor is one of
thanol, acetone, NH3, and H2S. This change in resistance is due to the critical parameters which decide sensor performance. To determine
physisorption and/or chemisorptions of oxygen and gases on surface of optimal working temperature, the sensor was tested at different tem-
sensing layer. The detail reactions of oxygen and NO2 gas are explained peratures (75–300 °C) by exposing 10 ppm of different gases. From
in Eqs. (2.0)–(3.3) [35]. The overall reactions of rest of the analytes are Fig. 6(a), it is quite evident that the sensitivity improves with tem-
explained in Eqs. (4)–(8). In first step the reactive oxygen species perature up to 225 °C and then decreases steadily as the temperature
available in the atmosphere is converted into its ions by capturing increases up to 300 °C. The rate of reactions, diffusion, ion-sorption and
electrons from surface of sensing layer as expressed in Eq. (3.0), leading ion-desorption rates are enhanced with rise in temperature. Thus, the
an electron depletion width and potential barrier at the surface of na- sensitivity increases with rise in temperature until the ion-sorption/ion-
norods. During baseline resistance measurement, a small voltage is desorption rates are in equilibrium to produce optimal response results.
applied between two electrodes so that high energy thermionic emitted After optimal working temperature, the oxygen molecules absorptions
electrons can jump over these potential barriers. It is well known that on the active sites of sensing material are quite fast. The absorption of
electron mobility strongly depends on potential barrier height i.e. re- analytes on these active sites is less effective [36]. Also, the desorption
sistivity increases exponentially with rise in barrier height. When sensor rate of analytes is increased with rise in operating temperature. In ad-
is exposed to NO2 gas, it will absorb as NO2– ions by capturing electrons dition to that, the reaction mechanisms of analytes and Debye length of
(Eq. (3.1)) from the conduction band of WO3 nanorods. The depletion nanorods are changed after optimal operational temperature [37–39].
width and potential barrier height is increased which causes more All these effects are responsible for decrease in sensitivity at higher
hindrance of electrons movement and thus resistance is increased as working temperature. However, more detailed studies are needed to
shown in Fig. 5(a). When reducing gases like ethanol, methanol, understand which mechanism is dominating.
acetone, NH3 and H2S are introduced, the resistance decreases. In these The response amplitude of gas sensor strongly depends on con-
cases, the reactions require pre-adsorbed oxygen ions to release centration gases. Thus, the sensor's sensitivity for different gases with
varying concentrations at optimal working temperature is presented in

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B. Behera, S. Chandra Materials Science in Semiconductor Processing 86 (2018) 79–84

Fig. 6. (a) The sensitivity of sensor towards 10 ppm gases at various operating temperatures (b) transient sensitivity of sensor in 2–50 ppm concentration range, insert
image shows sensitivity of sensor for different concentrations of target gases at 225 °C operating temperature.

Table 1
Comparison of sensing performances of our WO3 based NO2 gas sensor with other published work on WO3 based NO2 gas sensor.
Sl No Sensing material Synthesis method Sensing performances References
(magnitude-conc. at temp)

1 WO3 thin film Reactive sputtering a

1.12-10 ppm at 200 °C [41]
a
2 WO3 nanowire Sputtering 1.46-10 ppm at 150 °C [42]
b
3 WO3 nanorods Thermal evaporation 65%-10 ppm at 300 °C [18]
4 WO3 thin film spray pyrolysis b
80%-5 ppm at 125 °C [19]
b
5 WO3 nanoparticles Sol-gel 16%-5 ppm at 200 °C [20]
b
6 Porous WO3 Anodization 67%-10 ppm at 150 °C [21]
a
7 WO3 nanocolumn Hydrothermal 20.5-10 ppm at 110 °C [22]
a
8 WO3 nanorods Hydrothermal 209-10 ppm at 200 °C [23]
a
9 WO3 nanorods Sputtering 27-2 ppm at 250 °C [24]
a
10 WO3 nanorods Thermal oxidation 2.02-10 ppm at 225 °C This work
or
b
116%-10 ppm at 225 °C

a
Response formula: Rg/Ra.
b
Response formula: (Rg-Ra)× 100/Ra.

Fig. 6(b). It is observed that the response is almost linear with the in- techniques to grow dense nanorods of WO3 on SiO2 coated Si substrate
creasing the concentration gases by following general equation “S” = K which can be further integrated with MEMS technology for gas sensing
× Cm, where K is a constant which depends on sensing material type application. WO3 nanorods are formed when 100 nm tungsten films
and structure and “m” stands for coefficient of power-law dependence. oxidized at 500 °C in atmospheric ambient. From SEM, XRD, Raman
C is the concentration of gas [40]. These results indicate that the re- and XPS analysis, it was confirmed that ~ 80 nm diameter and 400 nm
sponse can be extrapolated over wide range for better calibration. It can length WO3 nanorods were formed. It showed high response of 116.3%
be concluded that the WO3 nanorods based sensor can detect very low towards 10 ppm of NO2 gas at a moderate optimal operating tempera-
concentration (2 ppm) of NO2 gas and a potential candidate for high- ture of 225 °C. The WO3 nanorods based sensor has shown a highly
efficiency gas detector. The sensing performance of sensor has been sensitive and selective response towards NO2 gas as compared to other
compared with some previously published literature as presented in analytes. At optimal working temperature, the sensor was able to detect
Table 1. It is evident that our fabricated sensor performance is nearly small concentration of NO2 gas (2 ppm). This work demonstrates that it
similar or better for selective detection of NO2 gas. Also, sensor per- is a novel method for development of high-performance gas sensors.
formance in some of the published literature on NO2 gas sensing is
better than our results. However, in this case, we have used thermal Acknowledgments
oxidation technique to synthesize WO3 nanorods. Though, only few
publications are available on synthesis of WO3 nanostructures by We would like to thank Nanoscale Research Facility (NRF) at IIT
thermal oxidation technique, they have not used these for gas sensing Delhi for providing help in Raman and XRD measurement.
application. Further studies (like varying oxidation parameters, using
catalyst or composite) can be carried out to improve NO2 sensing per- References
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