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A R T I C L E I N F O A BS T RAC T
Keywords: A successful deposition of undoped and Fluorine doped tin oxide (TO and FTO) nano films at relatively low
Thin films temperature 250 °C on flexible substrate (Polyethyerimide) was obtained using the spray pyrolysis technique.
Flexible substrate The Fluorine doping effects on the structural, morphological and optical properties were investigated. XRD
Wettability measurements permit textural characterization, and show that the films have a tetragonal polycrystalline
Optical properties
structure. The increase of crystalline size and reduction of defects and strain with Fluorine doping improve the
Photocatalysis
crystalline quality. This is may be due to the substitution of O−2 by F-. Furthermore, the structural changes of
the films affected the surface roughness which became rough with the Fluorine. This was confirmed by
wettability measurements. Moreover, the gap energy exhibits a slight red-shift with F-doping. The photo-
luminescence spectra showed that Fluorine doping increased the radiative centers, which is confirmed by
structural results. The photocatalytic performance of TO and FTO nanofilms were investigated by degradation of
crystal violet dye under UV radiations. Results showed that TO and FTO exhibit high photocatalytic activities,
which can be enhanced by H2O2 addition.
1. Introduction activities of SnO2 films are not widely studied, while many researchers
reported to the use of SnO2 powder for the photocatalytic activity [8,9].
With increasing diversity in industrial products, environmental Nevertheless, several practical problems arising from the use of powder
problems related to industrial effluents are becoming more and more are obvious during the photocatalytic process such as the difficulty
complex. The residual dyes from different sources like textile, bleaching separating the insoluble catalyst from the suspension, as well as
and pharmaceutical industries, dyeing, paper and pulp industry recycling of the catalyst powders. To overcome these problems, more
introduce a variety of organic pollutants into natural resources of attention has been focused to use thin films. Hence, Jana et al. [10]
water. Among various methods, the photocatalytic degradation has reported that SnO2 thin films presented a high photocatalytic activity
been demonstrated as one of the most important, innovative and green for the photodegradation of methyl orange (MO) dye.
technologies for water treatment. In this process the organic pollutants This activity is indeed sensitive to structural, morphological and
are effectively and directly degraded in the presence of photocatalyst, optical properties of such films. Also, the physical properties of SnO2
through photocatalytic oxidation–reduction reactions [1]. thin films can be modified by doping with donor elements that
Recently, metal oxide semiconductors in photocatalysis have substitute tin (IV) sites such as antimony (Sb) [11], indium (In) [12],
attracted a lot of attention such as TiO2 [2], ZnO [3], MgO [4], and or donor elements that replace the oxygen sites such as fluorine (F)
SnO2 [5]. Hence, these oxides have been used to degrade harmful [13]. On the other hand, it has been reported that physical properties of
organic pollutants. Among them, SnO2 has been shown to be an active thin films were highly dependent on several experimental conditions
photocatalyst material for the degradation of many organic compounds [14–16], such as deposition method [17–19], temperature [20,21], as
[6], thanks to its chemical stability [7]. However, the Photocatalytic well as the substrate nature. The glass substrate is widely used for
⁎
Correspondence to: Faculty of Science of Sfax, University of Sfax, B.P: 1171, 3038 Sfax, Tunisia.
E-mail address: sameh.benameur@yahoo.fr (S.B. Ameur).
http://dx.doi.org/10.1016/j.mssp.2016.12.019
Received 30 May 2016; Received in revised form 7 December 2016; Accepted 18 December 2016
1369-8001/ © 2016 Published by Elsevier Ltd.
S.B. Ameur et al. Materials Science in Semiconductor Processing 61 (2017) 17–26
display applications, but it is too heavy and brittle to be used in Photodegradation duration is chosen equal to 210 min without and
different geometries. To overcome these problems, flexible substrates in the presence of H2O2. The absorbance measurements (Shimadzu
are suitable as alternative ones. In recent years, transparent conductive 160 A UV–visible spectrophotometer) were recorded in the range of
oxide (TCO) thin oxides such as ZnO and SnO2 thin films deposited on 200–800 nm for each 30 min irradiation to evaluate the photodegrada-
flexible substrates are a subject of research for their special merits tion efficiency η (%) using the following formula [26]:
which can be applied to large scale area [22]. These flexible substrates
⎛ C⎞
exhibit advantages such as lightweight, mechanically robust and can η (%) = ⎜1 − ⎟ × 100
potentially be manufactured using cost-effective synthesis techniques. ⎝ C0 ⎠ (1)
The successful growth of ZnO thin films on Polyethyerimide (PEI) where C0 and C (mg L−1) are the liquid-phase concentration of the CV
substrate at relatively low temperature (250 °C) by spray pyrolysis [23] at the initial and any time t, respectively, at the maximal adsorption
encouraged us to deposit SnO2 on PEI substrate at the same experi- wavelength. The concentration of CV is linear proportion to absorption
mental conditions using this humid process. The aims of this paper are (A), thus C/C0= A/A0. According to Beer–Lambert's law, A=εlC, where
to grow undoped and F-doped SnO2 films having thickness of about ε is the molar absorption coefficient and l is the thickness of the
200 nm by spray pyrolysis technique on PEI flexible substrates at low absorption.
temperature (250 °C). A specific emphasis is put on the effect of Since, molar absorption coefficient (ε) and thickness of the cell (l)
Fluorine on the physical properties of SnO2 thin films grown on PEI are constant, so, the changes in the concentration of CV with time can
substrate. Results obtained by all investigation tools were correlated be detected using UV–visible spectrophotometer.
and discussed. Furthermore, the photocatalytic performance of un-
doped and Fluorine doped SnO2 thin films are studied by means of the
3. Results and discussions
photodegradation of crystal violet (CV) dye.
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S.B. Ameur et al. Materials Science in Semiconductor Processing 61 (2017) 17–26
may reduce the strain in the lattice [32]. Thus, geometrically the
introduction of F- reduces the defects (Table 1).
Table 1
Microstructural parameters of TO and FTO thin films on PEI substrate.
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S.B. Ameur et al. Materials Science in Semiconductor Processing 61 (2017) 17–26
Fig. 3. The AFM 2-D and 3-D surface images of (a) TO and (b) FTO thin films.
⎛1 + R ⎞ 4R
n=⎜ ⎟+ − k2
⎝1 − R ⎠ (1 − R )2 (9)
αλ
k=
4π (10)
Fig. 7 shows the refractive index of TO and FTO thin films. We note
that n decreases with doping by Fluorine which is consistent with the
Fig. 4. Photographs of water droplet on (a)TO and (b)FTO thin films. enhancement of the optical transmittance.
Also, Fig. 7 show that the refractive index of FTO in the infrared
UV radiation absorption for λ < 260 nm. Also, both TO and FTO regions obeys the Cauchy relation [40]. In fact, for the refractive index
nanofilms have high edge absorption in the ultraviolet range. we can use Wemple and Di-Domenico model to determine the
From the absorption data, we can determine the optical band gap dispersion parameters for these thin films [41]:
energy value. To determine the energy band gap values, we have
plotted (αhν )2 versus (hν ) (Fig. 6) according to Tauc model for direct E0 Ed
n2 − 1 =
band gap [21]: E02 − E2 (11)
(αhν ) = A (hν − Eg)1/2 (8)
where E is the photon energy, E0 represents the single-oscillator
where A is a constant, α is the absorption coefficient. energy and Ed represents the dispersion energy, which is a measure
Eg values are found to be 3.72 and 3.52 eV for TO and FTO thin of the intensity of inter-band optical transitions. The values of E0 and
films, respectively. We note a red shift of band gap observed by doping Ed were obtained by the fit of the linear part of the curve (n2−1)−1
with Fluorine. This red shift will be confirmed by PL measurements. versus (hυ)2 as seen in Fig. 8. The values of E0 and Ed are listed in
Table 2.
3.4.2. Refractive index and extinction coefficient In addition, we can also determine from the refractive index at high
Refractive index is one of the fundamental properties for optical frequencies (n∞), the average oscillator wavelength λ0 and the oscil-
materials, because it is related to the electronic polarizability of ions lator length strength S0 from the following relations [42]:
and the local field inside materials. The evolution of the refractive index
S0 λ 02
of optical materials is considerably important for the applications in n2 − 1 =
λ 2
integrated optic devices, such as switches, filters and modulators, 1 − ( λ0 ) (12)
where refraction index is the key element for device design. The
refractive index n (λ) can be determined from the following equation where λ is the wavelength of the incident light. Eq. (13) can be also
[39]: expressed as [43]:
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S.B. Ameur et al. Materials Science in Semiconductor Processing 61 (2017) 17–26
Fig. 7. The refractive index dispersion curve of TO and FTO thin films.
n∞2 − 1 ⎛ λ ⎞2
= 1 − ⎜ 0⎟
2
n −1 ⎝λ⎠ (13)
n∞2 = 1 + S0 λ 02 (14)
The values of n∞, λ0 and S0 of all samples are added in Table 2.
Fig. 9 shows the evolution of the extinction coefficient. As known,
the extinction coefficient k indicates the energy losses and it was related
to the crystalline quality, for that the FTO has the little optical loss (λ >
660 nm), in agreement with the increase of transmittance. Doping by
Fluorine reduces the energy losses.
Fig. 8. A plot of (n2-1)−1 versus (hν) 2
of all films.
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S.B. Ameur et al. Materials Science in Semiconductor Processing 61 (2017) 17–26
Table 2
Calculated values of oscillator parameters: Ed, E0, λ0, S0 and n∞.
Fig. 9. The evolution of the extinction coefficient of TO and FTO thin films.
ε∞ ωp2
ε1 ≈ ε∞ − λ2
4π 2c 2 (17)
ε∞ ωp2
ε2 ≈ λ3
8π 3c 3τ (18)
The calculated values are added in Table 3. It is found that all 3.5. Photoluminescence study
optical parameters ε, ω p and τ were influenced by Fluorine doping. The
optical conductivity σop and the free carrier concentration to effective PL of tin oxide thin films is believed to be greatly affected by free
mass ratio N / me* increased with doping by Fluorine. It is known that and bound exciton, interstitial vacancies or defects and impurities.
the optical conductivity is linked to the extinction coefficient. It However, oxygen vacancies are well known to be most frequently
increases for FTO leading to an increase of light absorption (k value observed defects in oxides and are usually act as radiative centers in
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S.B. Ameur et al. Materials Science in Semiconductor Processing 61 (2017) 17–26
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S.B. Ameur et al. Materials Science in Semiconductor Processing 61 (2017) 17–26
Fig. 14. The photodegradation efficiency of all catalysts versus UV irradiation time: (a)
TO, (b) TO with H2O2, (c) FTO and (d) FTO with H2O2 catalyst.
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