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Physical investigations on undoped and


Fluorine doped SnO 2 nanofilms on flexible
substrate along with wettability and...

Article in Materials Science in Semiconductor Processing · March 2017


DOI: 10.1016/j.mssp.2016.12.019

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Materials Science in Semiconductor Processing 61 (2017) 17–26

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Materials Science in Semiconductor Processing


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

Physical investigations on undoped and Fluorine doped SnO2 nanofilms on MARK


flexible substrate along with wettability and photocatalytic activity tests

S. Ben Ameura, , A. Barhoumia, H. Bel hadjltaiefb, R. Mimounic, B. Duponcheld, G. Leroye,
M. Amloukc, H. Guermazia
a
Research Unit: Physics of insulators and semi insulator materials, Faculty of Science of Sfax, University of Sfax, Road of Soukra Km 3.5, B.P: 1171, 3038
Sfax, Tunisia
b
Laboratory of « Eau, Energie et Environnement», National Engineering school of Sfax, University of Sfax, B.P1173.W.3038, Sfax, Tunisia
c
Research Unit: Physics of semi-conductor devices, Faculty of Science of Tunis, Tunis El Manar University, 2092 Tunis, Tunisia
d
UDSMM, University Lille North of France, ULCO, 59140 Dunkerque, France
e
UDSMM, University Lille North of France, ULCO, 62228 Calais, France

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.

3.1. Structural characterization


2. Experimental details

Fig. 1 depicts XRD patterns of undoped SnO2 (TO), F-doped SnO2


2.1. Films preparation
(FTO) thin films, deposited at 250 °C on PEI substrate as well as that of
the PEI substrate. All the diffraction peaks of TO and FTO thin films
Undoped and Fluorine doped tin oxide thin films were prepared on
matched well the tetragonal rutile structure of SnO2 according to
PEI substrate using a chemical spray pyrolysis technique. SnCl4 was
JCPDS file card no. 72-1147 with (110) preferred orientation. In
used as a precursor for tin. It was dissolved in methanol. The precursor
addition, XRD reflection peaks related to PEI substrates were detected.
concentration was (0.1 M), served as a starting solution in which
No other diffraction lines correspond to other tin oxide or tin fluorine
ammonium fluoride (NH4F) was dissolved with an appropriate
varieties were detected in XRD patterns, which is probably related to
amounts to achieve F concentration. F content in the starting solution
low F content ([F]/[Sn] =1%).
was 1%. Nitrogen was used as the gas carrier (pressure at 0.35 bar)
Hence, the texture coefficient TC (hkl) which indicates the max-
through a 0.5 mm-diameter nozzle. As reported previously, the nozzle-
imum preferred orientation of the films and the preferential direction
to-substrate plane distance was fixed at the optimal value of 27 cm
of the growth of most number of grains along that plane, is calculated
[24]. During the deposition process, the precursor mixture flow rate
from X-ray data, using the following formula [27]:
was taken constant at 4 mL/min throughout the films deposition. Film
thicknesses were found to be 200 nm. I(hkl ) / I0(hkl )
TC(hkl ) =
N−1ΣI(hkl ) / I0(hkl ) (2)
2.2. Characterization techniques
where I(hkl) is the measured intensity of X-ray reflection, I0(hkl) is the
2.2.1. Physical investigations corresponding intensity for randomly oriented sample taken from the
Crystallographic structure and surface morphologies of TO and FTO
thin films were investigated by using X-ray diffraction (Analytical X
Pert PROMPD) with Cu kα radiation (λ=1.5406 Å) and by means of an
atomic force microscope (AFM) in contact mode. The wettability
measurements have been made using a contact angle meter (Micro-
Drop analysis DSA 100 M) at room temperature. The optical properties
of these films were measured by UV–vis–NIR spectrophotometer
(Shimadzu UV 3100) in the wavelength ranging from 300 to
2000 nm. Finally, photoluminescence measurements were performed
at room temperature by means of Perkin Elmer LS-55 Luminescence/
Fluorescence spectrophotometer with 325 nm excitation.

2.2.2. Photocatalysis experiments


The photo-catalytic experiments were carried out in a 100 mL Pyrex
open vessel, placed on a magnetic stirrer and under UV-A lamp
(λmax=365 nm, Black-Ray B 100 W UV-lamp, V 100 AP series). The
distance between the solution and the UV source was kept constant at
30 cm, in all experiments. The FTO or TO catalyst (surface area
2×1 cm2) was introduced into the vessel containing 50 mL of the
aqueous solution of Crystal violet (CV) with initial concentration of
C0=12.5 mg/L and pH (6.5). The Crystal violet is a cationic dye with
molecular formula C25N3H30Cl.
Before illumination, the dispersion was magnetically stirred for
60 min (in the dark), in order to ensure adsorption equilibrium
between the sample surface and the organic dye [25]. Fig. 1. XRD patterns of TO/PEI, FTO/PEI films and PEI substrate.

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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).

3.2. Surface morphology

Nanoscale surface morphological study of TO and FTO thin films


was carried out using atomic force microscopy. It gives some informa-
tion about the morphological properties of films and the root mean
square (RMS) roughness. Fig. 3 shows the 2D and 3D topographic
views of AFM images obtained for all films in 2 × 2μm scale. It is
observed from the 3D images that the grain size is improved with
Fluorine doping, which is confirmed by the XRD results.
The root mean square (RMS) roughness was found to be (5.416 nm
± 0.162 nm) and (10.786 nm ± 0.324 nm) for TO and FTO, respec-
tively. As shown, the introduction of Fluorine causes an increase of
Fig. 2. Variation of the texture coefficient of TO and FTO thin films. RMS roughness. This evolution can be explained by the increase of the
crystallite size already demonstrated by XRD investigation [33,34].
JCPDS 72–1147 card, and N is the number of observed diffraction
peaks. The variation of the texture coefficient of the prepared TO and 3.3. Wettability study
FTO thin films is shown in Fig. 2. The higher values of TC was obtained
for (110) reflection in both films, which confirm the (110) preferential Controlling the surface wettability is important which involves the
orientation in these films. Moreover, we notice that F-doping further interaction between a liquid and solid in contact. The wettability of
favors growth in (110) direction. Indeed, the TC of the other planes solid surfaces is governed not only by chemical property but also by the
decreases and reach values close to unity, indicating randomly orien- surface roughness. The apparent contact angle can be determined by
tated planes. using Young's equation [35]:
The lattice parameters values a and c for the tetragonal phase of γSV − γSL
FTO and TO thin films are gathered in Table 1. cos θ =
γLV (7)
The lattice parameters (a and c) are found to exhibit slight
variations. These variations are attributed to the incorporation of F- where γSV ,γSL and γLV refer to the interfacial tensions with solid–vapor,
ions into the SnO2 lattice. Being comparable ionic radii of F- (r F − = solid–liquid and liquid–vapor, respectively. Young's angle θ is a result
0.133 nm) and O2- (r O2− = 0.132 nm) [28] substitution is the dominant of the thermodynamic equilibrium of the free energy at the solid–
mechanism in the incorporation of F- ions into the SnO2 lattice [19]. liquid–vapor interphase. The photograph of water droplet on TO and
For further structural characterization, we calculated the micro- FTO thin films is given in Fig. 4. The static contact angles of TO and
structural parameters. Indeed, the stacking fault probability α, the FTO films are found to be 80.44° ( ± 0.01°) and 85.42° ( ± 0.01°)
crystallite size D, the dislocation density δ and the microstrain ε are respectively. The contact angle increases with Fluorine doping. As it is
calculated from the preferential orientation peak (110) using the known the surface roughness is assumed to be among principal factors
following system of equations [29–31]: which impinges surface wettability [36,37], which is in agreement with
AFM observations.
α = (2π 2 /45 3 ) Δ (2θ )/ tan θ (3)
The variation of the hydrophobicity is due to the difference in
0.9λ adhesion forces (Van Der Wall's forces) between water and the solid
D=
β cos θ (4) surfaces [38]. Indeed, it is noted that FTO film has the lowest adhesion
work (77.8×10−3 N/m) compared to TO one (81.8×10−3 N/m), which
1 can be related to the difference in the anion charge between F- and O2-.
δ=
D2 (5) So, it is revealed that doping by Fluorine enhances the film hydro-
⎛ 1 ⎞⎡⎛ λ ⎞ ⎤ phobicity.
ε=⎜ ⎟ ⎢ ⎜ ⎟ − (β cos θ ) ⎥
⎝ sin θ ⎠ ⎣ ⎝ D ⎠ ⎦ (6)
3.4. Optical study
where Δ (2θ) =(2θ)exp - (2θ)0, (2θ)0 is the diffraction angle of bulk SnO2
(JCPDS 72–1147) and β is the full width at half maximum (FWHM) of 3.4.1. Optical band gap energy
diffraction peaks. The optical transmittance and absorbance of TO and FTO thin films
Calculated values are listed in Table 1. It is obvious that micro- were plotted in Fig. 5. These films have a high transmittance coefficient
strain, dislocation density and stacking fault probability α values around 80% in the visible and near infrared regions. Doping with
decrease whereas grain size increases, in FTO thin films, which Fluorine leads to decrease in the optical transmittance in the UV–vis
indicates that F-doping improves the crystalline quality of SnO2 thin range (200–660 nm) and to an increase in the Vis-NIR region beyond
films. Many reasons can explain this; ions are supposed to occupy the 660 nm. The high optical transmittance of films suggests that these
position of oxygen because of their similar ionic radius, the comparable films can be used as a window layer in solar cells and in different
energy of bond (Sn–F bond: 26.75 kJ mol–1, Sn–O bond: optoelectronic devices like in flat plate collectors. Moreover, we can
31.05 kJ mol−1); also, the F- charge is only half of O2- charge, which easily notice that doping SnO2 by Fluorine leads to an enhancement in

Table 1
Microstructural parameters of TO and FTO thin films on PEI substrate.

a (Å) c (Å) 2θ (deg) β (deg) α D (nm) δ (1014) (lines/m2) ε (10−3)

TO 4.736 3.286 26.596 0.050 0.327 61.1 2.67 7.25


FTO 4.740 3.279 26.615 0.067 0.263 87.6 1.30 2.70

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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)

where R is the reflectance and k is the extinction coefficient given by


[39]:

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. 6. Plots of (αhν )2 versus the photon energy (hν ).

Fig. 7. The refractive index dispersion curve of TO and FTO thin films.

Fig. 5. Transmittance, absorbance and reflectance spectra of TO and FTO.

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.

3.4.3. Dielectric permittivity


ε2 (λ ) = 2n (λ ). k (λ ) (16)
Using the above values of the refractive index n and the extinction
coefficient k, the real and imaginary parts of the dielectric permittivity In Fig. 10, it is found that in infrared range the dispersion of ε1 is
are calculated using the following expressions [39]: linear as a function of the square of the wavelength (λ2), while the
ε1 (λ ) = n2 (λ ) − k 2 (λ ) (15) absorption ε2 is linear with λ3. Such behaviors are in good agreement

21
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∞.

Ed (eV) E0 (eV) λ0 (nm) S0 (nm−2×10−6) n∞

TO 2.52 6.30 208 9 1.18


FTO 28.42 7.58 164 139 2.18

Fig. 9. The evolution of the extinction coefficient of TO and FTO thin films.

with the classical theory of the dielectric permittivity which was


expressed by the following equations (ωτ > > 1) [44]:

ε∞ ωp2
ε1 ≈ ε∞ − λ2
4π 2c 2 (17)

ε∞ ωp2
ε2 ≈ λ3
8π 3c 3τ (18)

where ε∞ is the dielectric constant at high frequencies, ωp is the plasma


pulsation and τ is the relaxation time. The plots of ε1 are similar to the
refractive index because of the small values of k. The values of ε2
depend mainly on the k values. ε2 has low values which proves that the
energy loss of light through thin films is low. In addition, it is clearly
Fig. 10. Real part ε1 of the dielectric permittivity versus λ2 and the imaginary part ε2 of
noticed that doping by Fluorine leads to a decrease in permittivity of the dielectric permittivity versus λ3.
SnO2 films.
The theoretical extrapolation of ε1 (λ2) at low wavelengths provides
Table 3
the dielectric constant ε∞ which shows a decrease with doping, as seen Values of optical parameters: ε∞ , ωp, τ and N/me* of all samples.
in Table 3. From the slope of this curve, we have deduced the values of
ωp for TO and FTO thin films, (Table 3) which increases with doping. ε∞ ωp (1014 τ (10– N/me* σop
In the same line, from the slope of the linear dependence of the ε2 (λ3) rads−1) 13
s) (1047 g−1cm−3) (Scm−1)

and the knowledge of ωp we have determined the relaxation time τ TO 5.79 4 0. 49 3 33


whose values are given in Table 3. FTO 5.05 8 3.30 10 895
Furthermore, the values of the free carrier concentration to effective
mass ratio N / me* are calculated from the following relation [45]:
increases too). Moreover, this evolution is in good agreement with the
4πNe 2 above results and confirmed the substitution of O−2 with F- in the SnO2
ωp2 = .
ε∞ me* (19) lattice. The substituted oxygen ion seems providing freer electrons,
which may cause an increase of carrier concentration in FTO films.
In addition, the optical conductivity σop is deduced from this
Furthermore, we remark that the relaxation time is higher in FTO films
equation [45]:
due to interactions induced by F doping.
σop = Ne 2τ / me*. (20)

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

TO and FTO films, respectively. Six peaks were observed at 385 nm


(3.22 eV), 401 nm (3.09 eV), 430 nm (2.88 eV), 450 nm (2.75 eV),
487 nm (2.54 eV) and 517 nm (2.4 eV), and five peaks at 387 nm
(3.21 eV), 402 nm (3.08 eV), 432 nm (2.87 eV), 483 nm (2.56 eV) and
529 nm (2.34 eV) for the TO and FTO thin films, respectively. In this
case, Shewale et al. [47] found five peaks at 366 nm, 396 nm, 427 nm
491 nm and 708 nm for FTO. All peaks location is in good agreement
with the results reported in literature [48]. Also, It can be seen that
undoped and F-doped SnO2 thin films exhibit approximately similar
type of PL signals, demonstrating that F doping do not give rise to new
PL phenomena.
Indeed, the energy corresponding to all the observed emission
peaks is less than the thin film optical band gap of all the films; they
cannot be assigned to the direct transition the direct transition between
the Sn 4p a hole and in O 2p valence band [49,50]. Therefore, the
emission peak might correspond to the electron transition from the
donor level formed by oxygen vacancy to the valence band in the film.
The electron in the donor level jumps to the valence band and the
transition generates violet light emission [20,49,51]. The Visible
emission peaks were then observed, violet, blue and green emissions
for all samples. The violet emission at 404–424 nm can be ascribed to
the luminescence centers formed by tin interstitials (Sni) [52]. Set of
peaks in the blue range 450–490 nm can be assigned to oxygen
vacancies (VO) or luminescent centers in the films [53]. The green
emission observed at 517–528 nm can be attributed to electron
transitions mediated by defect levels formed by singly charged oxygen
vacancies [54]. Thus, the decreased PL intensity indicates high
quantum efficiency and possibly a high photocatalytic activity.

3.6. Photocatalytic activities

The photocatalytic activity of TO and FTO nanofilms is studied by


the degradation of crystal violet (CV) dye solution at room temperature
during 210 min under both dark and UV irradiation. The change in CV
concentration can be monitored by means of the variation in the
absorption intensity. Firstly, under dark reaction conditions (figure not
shown), the results show that the photodegradation efficiencies are
around (3% ± 0.5%) and (2% ± 0.5%) for TO and FTO, respectively.
This is explained by the wide band-gap of SnO2 (3.52–3.72 eV), that
makes it activated especially by UV light. Hence, the absorption spectra
of CV during UV irradiation with different catalytic films (TO and FTO)
are presented in Fig. 12. It is found that the strong absorption band of
CV centered at 578 nm, decreases gradually upon increasing irradia-
tion time. Generally, the basis process of photocatalysis consists of
ejection an electron from the valence band (VB) to the conduction one
(CB) of the semiconductor which creates a hole (h+) in the valence band
Fig. 11. (a) Experimental PL spectra of TO and FTO nanofilms, the best Gaussian fit to and a free electron in the conduction band. Many researchers reported
the measured PL peaks in (b) TO and (c) FTO nanofilms.
the most probable mechanism for the photocatalytic degradation of
crystal violet. In addition, Bhattacharjee et al. [6] reported the
luminescence processes [46]. Furthermore, in a transparent conduct- photocatalytic process of the degradation MV6B by nanoparticles of
ing oxide such as TO and FTO, PL properties depend strongly on the SnO2. Diallo et al. [55] reported for X (any pollutants) the photo-
oxygen deficiency as well as on the nature and quantity of impurities catalytic process described using the following equations, showing in
trapped into the host lattice. Fig. 11(a) shows PL spectra of TO and Fig. 13:
FTO thin films using a 325 nm excitation. As shown in this figure, PL
spectra are composed of several over lapped peaks, one principal SnO2 + hν → e− + h+
emission in the Ultra violet region and the others in the visible range. H2 O + h+ → OH− + H+
Generally, the main UV emission originate from the near band edge OH− + h+ → •OH
Transition (NBE). Doping with Fluorine leads, indeed, to an enhance- e− + O2 → •O2−
ment of PL emission peaks. This enhancement can be due to the CV + hν → CV *
increase of donor's levels density caused by the substitution of O2- by CV * + •O2− or •OH → Degradation products (aromatic intermediates
F-. This is consistent with the increase in the free carrier concentration
+ CO2 + H2 O)
to effective mass ratio N / me*, calculated from absorption data. In fact
the increase in the free carrier concentration can favor radiative The generation of these active oxygen species (•O2- and •OH) are
recombination and thus results in PL enhancement. significantly initiated by the degradation of CV dye into less harmful
For the sake of clarity, the decomposition of the photoluminescence organic or aromatic intermediates such as carboxylic acids prior to
broad peak is resolved by Gaussian fita as shown in Fig. 11(b)-(c) for conversion into carbon dioxide [56,57].

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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.

powerful oxidation ability to degrade organic dye. Indeed, XRD data


show that TO nanofilms exhibit smaller grain sizes and consequently
have a smother surface. The effect of the crystallite size can be seen,
confirming the conclusion of the high photocatalytic activity for TO
samples [7]; (ii) PL intensity increased with doping by Fluorine. Thus,
the decrease of TO PL intensity indicates high quantum efficiency and
possibly a high photocatalytic activity [54]. This may be another reason
for high photocatalytic performance of TO nanofilms with respect to
FTO ones.
The photodegradation efficiency reaches about 80% after 210 min
UV time irradiation. So to enhance the photocatalytic activities of TO
and FTO films, we added the H2O2 in the CV solution. The effect of
H2O2 was not widely studied for this dye. Fig. 14 show that the
photodegradation of CV exhibits an enhancement by both FTO and TO
samples, upon H2O2 addition. The photodegradation efficiency in-
creases to (96% ± 5%) and (92% ± 5%) for TO and FTO respectively
after 210 min under UV irradiation exposure. This fact can be
explained in terms of the favorable production of (•OH) provided by
H2O2 [25]. These results regarding the enhancement of the degradation
of organic molecules when adding small amounts H2O2, are consistent
Fig. 12. The absorbance spectra of Crystal violet solution: (a) TO and (b) FTO catalyst at with previous works [26].
different irradiation times.

3.6.1. Stability of the photocatalyst materials


The stability of the photocatalyst is a key factor that determines
long-term efficiency. Therefore, the stability of the TO and FTO
photocatalyst was investigated by several recycle tests experiment.
The photostability of the proposed photocatalysts was evaluated in
four consecutive experiments by using fresh CV solutions at concen-
tration of 12.5 mg/L (Fig. 15). The photodegradation removal effi-
ciency of CV dye during photocatalytic activity by TO and FTO
nanofilms decreased as recycling number of runs increases. After the
photocatalysts were recycled four times, the degradation rate decreased
Fig. 13. Photodegradation process of CV solution dye by SnO2 thin films. to 61% and 55% for TO and FTO, respectively.
We noted a slight decrease in activity is attributed to the loss of
From Fig. 14, it is obvious that TO degraded CV faster than FTO photocatalyst during washing. Hence, this result further proves that
under similar experimental conditions. Two possible reasons for the cyclic usage of these photocatalysts is feasible with satisfactory stability
higher degradation rate of TO compared to FTO are: (i) the reason may in treating organic compounds.
be due to the lower hydrophobicity and the higher adhesion work of TO
film compared to FTO one, which increases the effective contact surface 4. Conclusion
with the pollutant species. In fact, Sangchay [58] reported that the film
which has a lower contact angle measurement has a most hydroxyl In this work, SnO2 and SnO2:F nanofilms were deposited onto
group in the surface. These hydroxyl radicals (•OH) have therefore a flexible PEI substrate by the spray pyrolysis technique at relatively low
temperature of 250 °C. X-ray diffraction shows that the films are

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S.B. Ameur et al. Materials Science in Semiconductor Processing 61 (2017) 17–26

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The authors would like to express their gratitude for the financial
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