Accepted Manuscript

Title: Structural, morphological, gas sensing and

photocatalytic characterization of MoO3 and WO3 thin films
prepared by the thermal vacuum evaporation technique
Author: A. Arfaoui S. Touihri A. Mhamdi A. Labidi T.
Manoubi
PII:
DOI:
Reference:

S0169-4332(15)02218-7
http://dx.doi.org/doi:10.1016/j.apsusc.2015.09.124
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Structural, morphological, gas sensing and photocatalytic characterization of

MoO3 and WO3 thin films prepared by the thermal vacuum evaporation
technique
A. Arfaouia,*, S. Touihria, A. Mhamdia, A. Labidib, T. Manoubia
Unit de physique des dispositifs a semi-conducteurs, Facult des sciences de Tunis,
Tunis El Manar University, 2092 Tunis, Tunisia

Unit de Recherche de Physique des Semiconducteurs et Capteurs, IPEST, BP 51 La

Marsa 2070, Tunis, Tunisia

author: E-mail: asma17687@gmail.com

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* Corresponding

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Abstract

Thin films of molybdenum trioxide and tungsten trioxide were deposited on glass substrates

using a simplified thermal evaporation under vacuum method monitored by heat treatment in
flowing oxygen at 500 C for 1 h. The structural and morphological properties of the films

were investigated using X-ray diffraction, Raman spectroscopy, atomic force microscopy and
scanning electron microscopy. The X-ray diffraction analysis shows that the films of MoO3

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and WO3 were well crystallized in orthorhombic and monoclinic phase respectively with the
crystallites preferentially oriented towards (200) direction parallel a-axis for both() samples.

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In literature, we have shown in previous papers that structural and surface morphology of
metal thin films play an important role in the gas detection mechanism. In this article, we
have studied the response evolution of MoO3 and WO3 thin films sensors ethanol versus time,
( )working temperature and the concentration of the ethanol. It was found that these films had
high sensitivity to ethanol, which made them as a good candidate for the ethanol sensor.
Finally, the photocatalytic activity of the samples was evaluated with respect to the
degradation reaction of a wastewater containing methylene blue (MB) under UV-Visible light
irradiation. The Molybdenum trioxide exhibits a higher degradation rate than the tungsten
trioxide thin films under similar experimental conditions.
Keywords: MoO3, WO3 thin films; thermal evaporated method; gas sensor and
photocatalytic activity.

Page 1 of 27

1. Introduction
During the recent years, the continuous development of global industrialization has become a
major issue to be addressed for research to reduce the industrial pollutions. The concern over

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environmental protection and increasing demands for monitoring hazardous and inflammable
gases in industry and home have attracted extensive interests in developing gas sensors for

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these gases. As the demands for solar energy, pure air and water, and disposing of poisonous
and hazardous pollutant are increasing, the use of semiconductor photocatalysts for

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environmental purification has attracted considerable attention due to their applicability for
the removal of wide variety of pollutants due to the advantages of small size, low cost, simple
operation and good reversibility [1-3]. In addition, many semiconductor oxides have become

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the most promising devices among the solid-state chemical sensors such as WO3, MoO3,
SnO2, TiO2, ZnO, In2O3 and CuO, explored to detect the toxic and inflammable gases, like O3,

NOX, H2, NH3 and ethanol [4-7]

Among of theses oxides, molybdenum trioxide (MoO3) and tungsten trioxide (WO3) as an ntype semiconductor, with their semiconducting properties have been extensively studied

because of their particular physical properties [8] and good chemical stability [9, 10]. In fact,

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these oxide have been used in many area application such as in solar cells [11] and due to its
efficient absorption of most UV-light and part of visible light these material have been one of

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active photocatalyst.

Molybdenum trioxide (MoO3) is one of the most important transitional metal oxides (TMOs)
due to its rich chemistry associated with multiple valence states, high thermal and chemical
stability. Generally, it exists in three kinds of polymorphs, namely orthorhombic -MoO3,
monoclinic -MoO3 and hexagonal MoO3. Previously, -MoO3 has long been used as the
lithium storage host materials in view of the thermodynamically stable, intriguing layered
structure and recently, MoO3 thin films have been selected as a semiconductor showing a
strong sensitivity demonstrated in photocatalytic applications [12].
In the last decades chemical sensors based on semiconducting oxide materials, such as WO3
have been extensively investigated owing to their low cost, good stability and simplicity in
fabricating sensors. Indeed, we note that the crystalline phase of tungsten trioxide (WO3) thin
films is considered as one of the most interesting materials in the field of gas sensors based on
metals oxides semiconductors and the monoclinic phase is an attractive candidate for
photocatalytic applications under solar irradiation because it exhibits the proper bad-gap

Page 2 of 27

energy for the adsorption of visible light [13]. For these reasons, the synthesis of these oxides
has attracted the attention of researchers as a way to prepare it through various methods like
spray pyrolysis [14], sputtering [15], flash evaporation [16], chemical vapor deposition [17],
sol-gel coating [18] and thermal evaporated technique [19].

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The present work aims to reach the comparative characterization between MoO3 and WO3
thin films prepared by thermal evaporated technique. These films have been investigated by
using XRD, Raman technique, atomic force microscopy and scanning electron microscopy.

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Finally, sensing characteristics of MoO3 and WO3 thin films toward ethanol gas have been
reported and their photocatalytic activity was evaluated in the degradation of MB under UV-

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Visible irradiation.

2.1.

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2. Experimental
Films preparation

Molybdenum trioxide and tungsten trioxide thin film were obtained in two steps. First, the

commercially available high purity MoO3 and WO3 powder (Aldritch, 99.9%) were deposited
by evaporation in a high vacuum chamber under pressure of about 10-9 Pa using a tantalum

boat filament. Second, the thin films obtained were placed into Pyrex pre-sealed tube and the
samples was heat treated by annealing in flowing oxygen during 1 h at 500 C using a

Characterization techniques

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2.2.

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programmed tubular oven order to obtain the most stable structure of these oxides.

The spectra of X-Ray Diffraction of molybdenum trioxide as well as tungsten trioxide were
analysed by a copper-source diffractometer (Analytical X Pert PROMP D), using Cu K1
radiation (=1.5418 A). Raman spectra were measured at room temperature using HORIBA
Jobin HR 800 system.

A 632.8 nm line of a He-Ne laser was used for off-resonance

excitation. Topography of obtained thin films was performed via atomic force microscopy at
taping mode (AFM, VEECO digital instrument 3A), and electron probe microanalysis (SEM).
The sensing properties of samples under ethanol were investigated according to the
experimental protocol described in fig 1 [20]. The operating temperature ranges from 175 to
250 C in order to determine the optimal working temperature of these films. To investigate
the ethanol gas sensing properties of MoO3 and WO3 samples, the sensors were introduced in
a test chamber in order to control the sensor temperature under variable gas concentrations.

Page 3 of 27

The ethanol concentration in dry air can be calculated by applying the following equation.

[C ]% = [

xd1
] 100
xd1 + d1 + d 2

(1)

Pethanol
Patm

(2)

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x=

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Where x is the molar fraction of the vapor at Tethanol =30 C, given by:

With Pethanol is the partial pressure of the vapor at a given temperature Tethanol , and Patm the

Rethanol Rair
(3)
Rethanol

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The response of sensor (S) is defined as: S =

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atmospheric pressure.

Where Rair and Rethanol are the resistance of the film before and after introduction of ethanol
respectively.

Finally, the photocatalytic activity of as MoO3 and WO3 thin films was estimated by
measuring the decomposition rate of methylene blue (MB) aqueous solution under UV

irradiation of Mercury lamp. The experiments were carried out using cylindrical batch reactor
opened at the air. The UV irradiation source was a high pressure mercury lamp (Philips HPK,

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125W) and the visible irradiation source was a halogen lamp (Duralamp, 250W). Methylene
blue MB (Aldrich) was chosen as a model molecule for the photocatalytic test. The

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temperature of MB solution was kept at room temperature, by a constant flow of water,

circulated through the reactor. Initial concentration of MB was 14 mg/L. The MB solution
was stirred at magnetic stirrer for 1 h in dark, in order to attain equilibrium adsorption. The
aqueous suspension containing the MoO3 and WO3 thin films as photocatalyst and MB was
irradiated with UV light under constant stirring. To see the effect of UV irradiation on MB
solution, the analytical samples were collected from the solution after every 30, 60, 90 and
120 minutes from the suspension, and then centrifuged. The concentration of MB in each
sample was analyzed using UVVis spectrophotometer.

3. Results and discussion

3. 1. Microstructural study
XRD pattern of the thermal evaporated molybdenum oxide and tungsten oxide thin
films annealed at 500 C in flowing oxygen is shown in fig 2. It is clearly seen from fig 2.a

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that the diffraction peaks of molybdenum oxide are indexed to orthorhombic -MoO3 with
cell parameters a=13.82 nm, b=3.694nm and c=3.954 nm, which is consistent with the
standard values of bulk MoO3 (JCPDS 65-2421). In this condition of annealing no peaks of
the substochiometric phases were observed from this XRD analysis, indicating that the

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molybdenum atoms was satisfied and the stoechimoetric is obtained. The sharp diffraction
peak located at 12.8 is much stronger than the rest, which confirms that the thin film is well
crystallized and it exhibits a strong (200) preferred orientation occurred in a direction at the

along (200) direction was reported also by Ling Liu et al [21].

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crystal formation process. The orthorhombic crystal structure with a preferred orientation

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X ray diffraction analysis of tungsten oxide showed in fig 2. b, a number of diffraction peaks
can be observed in the XRD patterns of the WO3 thin films positioned at 10.95, 24.35, 28.36,

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34.20, 41.75, 49.77 and 55.84 match well with the monoclinic structure of tungsten trioxide
WO3 (PDF: 24-0747) and a preferred orientation along the direction (200) is observed [22].
Diffraction spectra patterns plea here in favor of a monoclinic structure, with crystallites

standing perpendicularly to glass substrate plane and this behavior has been already recorded
by Caiteanu et al [23].

The strong and sharp peaks show that WO3 has good crystallinity, which has been proven to

be an important factor for the sensing performance.

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Raman spectra of MoO3 and WO3 thin films are shown in fig 3. For the molybdenum oxide
thin films, Fig 3.a, the Raman spectrum display three well-defined peaks located at 336, 816

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and 994 cm-1. The Raman band at 336 assignated to Mo-O-Mo bend, the known Mo -O-Mo
stretching modes correspond to the bridging oxygens (OMo2) are observed at 816 cm-1.the
Raman-active band at about 993 cm-1 is corresponding to the stretching mode of the Mo-O
and this peak associated with the unique molybdenyl band, which is responsible for the
layered structure of orthorhombic -MoO3.We also observe a spectra at 661 cm-1 assigned to
Mo-O stretching mode of triply coordinated oxygen and the low intensity Raman peaks
positioned on lower wavenumber side at 286 and 454 can be attributed to O=Mo=O wagging
and O-Mo-O scissoring modes respectively [24]. The position and relative intensity of Raman
peaks are in good agreement with previously reported MoO3 [25, 26]. Fig 3.b shows the
Raman spectra of thermal evaporated tungsten oxide thin films. The very intense Raman band
at 803 cm-1 and the intense band at 712 cm-1 are assigned to symmetric stretching and
asymmetric stretching vibrations of O-W-O [27]. The Raman band at 272 cm-1 appears with a
weak signal at 326 cm-1 are attributed to the bending vibration (O-W-O) and fig 3 present a
schematic drawing of the atomic motions for the Raman vibration of molybdenum trioxide

Page 5 of 27

and tungsten trioxide. XRD and Raman measurements confirmed the crystal structure of
monoclinic WO3 and similar results have been reported by Pyper et al in WO3 thin films
prepared using sol-gel spin coating process [28].

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3. 2. Morphological study
Tapping mode atomic force microscopy (AFM) and scanning electron microscopy (SEM)

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have been performed in order to study the surface morphology of MoO3 and WO3 thin films.
A 2D AFM and SEM micrographs for MoO3 thin films is presented in Fig 4. The AFM image

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showed in Fig 4. a reveals that this material has a disturbed surface and shows a rough surface
morphology. In fact, the root mean square roughness (Rms) is around of 108 nm and this high
value may be of interest for possible sensitivity applications. This result is confirmed by the

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scanning electron microscopy showed in Fig 4.b, and as seen from the micrographs of
thermal evaporated molybdenum trioxide thin films, we observe homogeneous morphologies,
quasi spherical grains, no crack has been observed and the films adhere perfectly to the

substrate [29]. For the tungsten trioxide thin films, Fig 5.a and b showed the 2D AFM
morphology and SEM micrographs. Fig 5. a. present a columnar surface morphology with

distinct visible grain boundaries having a preferred a-axis orientation witch confirm our XRD

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measurements of tungsten oxide thin films. These oxide film is found to have a root mean
square (Rms) roughness of 2 nm, same results was reported by Valyukh et al in WO3 thin

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films prepared reactive de magnetron sputtering [30]. The surface morphology of WO3 is also
characterized by scanning electron microscopy and as seen from the micrograph, the films are
formed from well defined crystallites with dimensions less than 50 nm. This morphology of
these films renders them for applications as gas sensors and as effective catalysts [31, 32].
3. 3. Gas sensing properties

Semiconductor metal oxides such as MoO3 and WO3 have been widely used for sensing gases
and vapors, this sensing mechanism based on the change in conductance (or resistance) of the
semiconductor in the presence of toxic gases. The oxygen adsorbed on the oxide crystals
surface as ions are formed by abstracting free electrons from the metal oxide semiconductors
and reducing the electrical conductivity, this adsorbed oxygen on the sensor surface depends
on operating temperature, concentration of additives, particle size, and specific surface area of
the sensor.

Page 6 of 27

In order to determine the optimal operating temperature, the gas sensing characteristics of
molybdenum trioxide and tungsten trioxide thin films toward 1000 ppm and 5000 ppm of
ethanol vapor were measured at different operating temperature ranging from 175 to 250 C.
Fig 6 and 7 show the dynamic responses of MoO3 and WO3 thin films tested three times for

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duration of 1 min at every operating temperature. The conductance increased upon exposure
to ethanol vapor and recovered completely to the initial value upon the removal of ethanol.
The sensor responses were quite stable and reproducible for repeated test cycles for both

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MoO3 and WO3 thin films [33, 34]. Besides, it is also worth noting from this figure that the
molybdenum oxide detects the vapor of ethanol only for a concentration of 0.5% which not

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the case for the tungsten trioxide which detects at 1 and 5 %. This behavior can be explained
by the fact that the free oxygen molecules are absorbed on WO3 surface and capture electrons

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from the conduction band of WO3 to form chemisorbed oxygen ions, becomes O2-, and
creates a space charge region at the interface or grain boundaries [35, 36]. Fig 8 and 9
compare the sensing characteristic of MoO3 and WO3 toward 0.1 and 0.5 % of ethanol at

working temperature of 175-250 C. The highest response of MoO3 and WO3 found at 200 and
175 respectively and this experiment results can be concluded that the tungsten trioxide
exhibited a higher response of the ethanol vapor at low temperature and concentration,

however, when operated at T 175 C the stability and reproducibility of the WO3 sensors

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disintegrated showed in fig 10, this excellent sensing performance of WO3 thin films toward
ethanol are promising for industrial application. For the molybdenum trioxide thin films, the

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response decreases sharply when the operating temperature is higher than the optimal
temperature of 200 C.

3. 4. photocatalysts properties

The photocatalytic activity of WO3 and MoO3 thin films was tested for the degradation of a
wastewater pollutant, this degradation of methylene blue (MB) under UV-Visible light
irradiation was monitored by recording the decrease in the absorption of MB (=664nm).
Temporal evolution of the spectral changes during the degradation of the MB aqueous
solution mediated by MoO3 and WO3 thin films under visible light after reaction for 120 min
is displayed in Fig 11.a and b. The surface area and degree of crystallinity of the
photocatalyst can play a determinant role in the photocatalytic activity [37, 38].
The maximum characteristic absorption peak of MB at 664 decreases rapidly with the
irradiation time extended. Fig 12 describes the evolution of the MB degradation in the

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presence of MoO3 and WO3 thin films as a photocatalyst, where C0 and Ct are the initial
concentration after the equilibrium adsorption and the residual concentration of MB
respectively. In this test, the MB concentration decreases slowly in the presence of WO3 thin
films. So we can conclude that the molybdenum trioxide exhibited the best photocatalytic

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activity toward the degradation of MB under irradiation by mercury lamp, and by calculation,
after 120 min irradiation, 81% and 72 % of MB molecules were photodegraded over thin
films of MoO3 and WO3 respectively. This enhancement in photocatalytic performance may

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be attributed to the influence of the surface area and the higher root mean square roughness

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[39].

Conclusion

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Thin films of MoO3 and WO3 were deposited by the thermal vacuum evaporation technique
on glass substrates at 500 C in flowing oxygen for 1 h with the aim to get the most stable
structure of these oxides. The XRD patterns clearly show the preferred growth along (200) for

both MoO3 and WO3 with orthorhombic and monoclinic structure respectively. Moreover,
sensing properties and the photocatalytic activity of MoO3 and WO3 thin films towards

ethanol gas have been investigated. The results revealed that WO3 with Rms of about 2nm
exhibited markedly higher response value, lower optimal operating temperature and much

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better response recovery characteristics to lower concentration of ethanol vapor due to high
specific surface. In addition, the prepared oxides exhibited good photocatalytic properties,

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stability and reproducibility of gas sensors. Our results implied that the thermal evaporated
molybdenum trioxide and tungsten trioxide are good candidates for high performance ethanol
sensors, and a good photocatalytic activity.

Page 8 of 27

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[38] T. Liu, B. Li, Y. Hao and Z. Yao MoO3-nanowire membrane and Bi2Mo3O12/MoO3
nano-heterostructural photocatalyst for wastewater treatment, Chemical Engineering
Journal 244 (2014) 382-390.
[39] A. Fujii, Z. Meng, C. Yogi, T. Hashishin, T. Sanada and K. Kojima Preparation of
Pt-loaded WO3 with different types of morphology and photocatalytic degradation of
methylene blue, Surface and Coatings Technology (2014).

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List of Figures

Figure 1: Experimental set-up for ethanol vapor detection

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Figure 2: X-ray diffractogram of (a) MoO3 and (b) WO3 thin films annealed at 500C for 1 h
in flowing oxygen.

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Figure 3: The Raman spectra of (a) MoO3 and (b) WO3 thin films annealed at 500C for 1 h
in flowing oxygen with the schematic drawing of the atomic motions for the Raman vibration
of molybdenum trioxide and tungsten trioxide.

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Figure 4: 2D AFM micrographs (a) and SEM micrographs (b) of MoO3 thin films annealed
at 500C for 1 h in flowing oxygen

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Figure 5: 2D AFM micrographs (a) and SEM micrographs (b) of WO3 thin films annealed at
500C for 1 h in flowing oxygen

Figure 6: Dynamic response of MoO3 thin films at a various operating temperature of 175,
200, 225 and 250 C exposed to 0.5 % of ethanol vapor for a period of 1 min.
Figure 7: Comparison of dynamic response of MoO3 thin films exposed to 0.5 % for a period
of 1 min at a various operating temperature from 175 to 250 C.

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Figure 8: Dynamic response of WO3 thin films exposed to (a) 0.1% and (b) 0.5 % for a period
of 1 min at a various operating temperature from 175 to 250 C.

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Figure 9: Comparison of dynamic response of WO3 thin films exposed to (a) 0.1% and (b) 0.5
% for a period of 1 min at a various operating temperature from 175 to 250 C.
Figure 10: Response factor of MoO3 and WO3 thin films in flowing oxygen exposed to 0.1 and
0.5% for a period of 1 min at a various operating temperature from 175 to 250 C.
Figure 11: Methylene blue absorbance spectra at different irradiation times using (a) MoO3
and (b) WO3 thin films as a photocatalyst.
Figure 12: Photocatalysis of methylene blue: normalized concentration of MB as a function
of the irradiation time at different sintering temperatures for thin films of (a) MoO3 and (b)
WO3.

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Figure 1: Experimental set-up for ethanol vapor detection

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20

30

2 ()

40

50

60

10

20

30

40

50

142

400

-222

220
-112

100

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10

600
501

210

101
400 201

Intensity(a.u)

200

Intensity (a.u)
0

200

(b) tungsten oxide annealed in flowing oxygen at 500 C

(a) Molybdenum oxide annealed in flowing oxygen at 500 C

60

2 ()

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Figure 2: X-ray diffractogram of (a) MoO3 and (b) WO3 thin films annealed at 500C for 1 h
in flowing oxygen.

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200

400

800

1000 1200 1400 1600 1800 2000

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326

200

400

600

800

1000 1200 1400 1600 1800 2000

Raman schifts (cm-1)

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Raman shift (cm-1)

272

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135

Raman intensity (a.u)

1010.6

951.7

661.9
600

(b) tungsten oxide annealed in flowing oxygen at 500 C

457.4

286.2
336.8

993.9

Raman Intensity (a.u)

816.4

(a) molybdenum oxide annealed in flowing oxygen at 500 C

Figure 3: The Raman spectra of (a) MoO3 and (b) WO3 thin films annealed at 500C for 1 h
in flowing oxygen with the schematic drawing of the atomic motions for the Raman vibration
of molybdenum trioxide and tungsten trioxide.

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Figure 4: 2D AFM micrographs (a) and SEM micrographs (b) of MoO3 thin films annealed
at 500C for 1 h in flowing oxygen.

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Figure 5: 2D AFM micrographs (a) and SEM micrographs (b) of WO3 thin films annealed at
500 C for 1 h in flowing oxygen

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Figure 6: Dynamic response of MoO3 thin films at a various operating temperature of 175,
200, 225 and 250 C exposed to 0.5 % of ethanol vapor for a period of 1 min.

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Figure 7: Dynamic response of WO3 thin films exposed to (a) 0.1% and (b) 0.5 % for a period
of 1 min at a various operating temperature from 175 to 250 C.

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Figure 8: Comparison of dynamic response of MoO3 thin films exposed to 0.5 % for a period
of 1 min at a various operating temperature from 175 to 250 C.

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Figure 9: Comparison of dynamic response of WO3 thin films exposed to (a) 0.1% and (b) 0.5
% for a period of 1 min at a various operating temperature from 175 to 250 C.

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MoO3 exposed to 0.5 % of ethanol vapor

WO3 exposed to 0.1 % of ethanol vapor

0.3

0.2

0.0

0.1

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Response factor

WO3 exposed to 0.5 % of ethanol vapor

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175

200

225

250

T(C)

Figure 10: Response factor of MoO3 and WO3 thin films in flowing oxygen exposed to 0.1 and
0.5% for a period of 1 min at a various operating temperature from 175 to 250 C.

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Figure 11: Methylene blue absorbance spectra at different irradiation times using (a) MoO3
and (b) WO3 thin films as a photocatalyst

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Figure 12: Photocatalysis of methylene blue: normalized concentration of MB as a function

of the time for thin films of (a) MoO3 and (b) WO3.

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Page 26 of 27

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Research highlights
The main points (highlights) in this work are

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Outlining adequacy an original combination of several characterization means.

Structural, morphological and gas sensing properties for both MoO3 and WO3 thin
films have been studied.

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These films had high sensitivity to ethanol, which made them as a good candidate for
the ethanol sensor.

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The photocatalytic activity of MoO3 and WO3 thin films has been studied.

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