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Vol. 34, No.

Journal of Semiconductors

September 2013

The effect of the film thickness and doping content of SnO2 :F thin films prepared by
the ultrasonic spray method
Achour Rahal1; 2 , Said Benramache1; 3; , and Boubaker Benhaoua1
1 VTRS

Laboratory, Institute of Technology, University of El-oued 39000, Algeria


Laboratory, Institute of Technology, University of El-oued 39000, Algeria
3 Material Sciences Laboratory, Faculty of Science, University of Biskra 07000, Algeria
2 Physics

Abstract: This paper reports on the effects of film thickness and doping content on the optical and electrical
properties of fluorine-doped tin oxide. Tin (II) chloride dehydrate, ammonium fluoride dehydrate, ethanol and
HCl were used as the starting materials, dopant source, solvent and stabilizer, respectively. The doped films were
deposited on a glass substrate at different concentrations varying between 0 and 5 wt% using an ultrasonic spray
technique. The SnO2 :F thin films were deposited at a 350 C pending time (5, 15, 60 and 90 s). The average
transmission was about 80%, and the films were thus transparent in the visible region. The optical energy gap of
the doped films with 2.5 wt% F was found to increase from 3.47 to 3.89 eV with increasing film thickness, and
increased after doping at 5 wt%. The decrease in the Urbach energy of the SnO2 :F thin films indicated a decrease
in the defects. The increase in the electrical conductivity of the films reached maximum values of 278.9 and 281.9
(cm) 1 for 2.5 and 5 wt% F, respectively, indicating that the films exhibited an n-type semiconducting nature.
A systematic study on the influence of film thickness and doping content on the properties of SnO2 :F thin films
deposited by ultrasonic spray was reported.
Key words: SnO2 ; fluoride; thin film; film thickness; TCO; ultrasonic spray technique
DOI: 10.1088/1674-4926/34/9/093003
EEACC: 2520

1. Introduction
SnO2 is an n-type semiconductor material. Because of its
good adsorptive properties and chemical stability, it can be
deposited onto glass, ceramics, oxides, and substrate materials of other types1; 2 . It has a high melting point and good
transmission, and does not easily react with oxygen and water vapor in the air, so it has a high specific volume and good
cycling performance. Gas sensors based on SnO2 thin films
are used to detect a variety of hazardous gases, combustible
gases, industrial emissions, and pollution gases1; 3 . In addition, SnO2 thin films are also used for film resistors, electric conversion films, heat reflective mirrors, semiconductor
insulatorsemiconductor (SIS) heterojunction structures, and
surface protection layers of glass. At present, its most common
application is as the anode material of solar cells1 5 .
Undoped SnO2 is a highly transparent, widely applicable
material with n-type conductivity and wide band gap energy
(Eg > 3.7 eV)6 . Thin films of SnO2 have been fabricated
using a variety of methods, including spray pyrolysis4 , ultrasonic spray pyrolysis5 , chemical vapour deposition7 , activated reactive evaporation8 , ion-beam assisted deposition,
sputtering9 , and solgel methods10 . Among these, we will
focus more particularly in this paper on the spray ultrasonic
technique that is a low-cost method suitable for large-scale production. It has several advantages in producing highly transparent thin films, such as a relatively homogeneous composition, simple deposition on glass substrates because of the low
substrate temperatures involved, easy control of film thickness,
and a fine and porous microstructure. It is possible to alter the

mechanical, electrical, optical and magnetic properties of SnO2


nanostructures.
In the experimental study, the transparent SnO2 thin films
were prepared using the ultrasonic spray technique on a glass
substrate. The films were deposited at a substrate temperature
of 350 C pending time of 5, 15, 60 and 90 s at various concentrations between 0 and 5 wt%. We studied the effects of the film
thickness and doping content on the electrical conductivity and
optical properties of transparent conductive SnO2 :F thin films.

2. Experimental procedure
The spray solution was prepared by dissolving 0.2 M of Tin
(II) chloride dehydrate (SnCl4 , 2H2 O) in a solvent containing
an equal volume of absolute ethanol solution (99.995% purity),
and then a drop of HCl solution was stirred at 50 C for 120
min. The weight percentages of [F/Sn] were 0, 2.5 and 5 wt%
of ammonium fluoride dehydrate (NH4 F, 2H2 O), which was
added to the solution. The mixture was stirred at 60 C for 180
min to yield a clear and transparent solution. The substrate was
R217102 glass of size 1  1  0.1 cm3 , and prior to pumping,
the substrate (R217102 glass) was cleaned with alcohol in an
ultrasonic bath and blow-dried with dry nitrogen gas.
The resulting solution was sprayed onto heated glass substrates using an ultrasonic nebulizer system (Sonics), which
transformed the liquid to a steam formed by uniform and fine
droplets of 35 m average diameter (given by the manufacturer). The deposition was performed at various times varying between 5 and 90 s, and the films were realized at a substrate temperature of 350 C11; 12 . The optical properties of

Corresponding author. Email: saidzno2006@gmail.com


Received 19 February 2013, revised manuscript received 21 March 2013

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J. Semicond. 2013, 34(9)

Achour Rahal et al.

Fig. 1. The transmission spectra of SnO2 :F thin films at different doping levels with 513 nm.

Fig. 2. The transmission spectra of SnO2 :F thin films as a function of


film thickness with 2.5 wt%.

Table 1. Transmission T , band gap energy Eg , Urbach energy Eu ,


electrical conductivity  and refractive indices n at 25 C for SnO2 :F
thin films measured at different film thicknesses.
Samples
Ta
Eg
Eu

n
(%)
(eV)
(meV) (cm) 1

longer wavelengths ( > 1000 nm), all the thin films become
transparent, and the transmission of the SnO2 :F thin films decreases with increasing film thickness. As can be seen, a region
of ( < 400 nm) is the absorption edge region in the layers due
to the transition between the valence band and the conduction
band. At this region, the transmittance decreases because of the
onset fundamental absorption. We note that the film thickness
effect is clearly observed in the layer quality.
It is preferred that the energy gap is evaluated from the optical absorption. A stoichiometric composition of the films is
indicated by a sharp absorption edge at a wavelength that corresponds to the forbidden energy gap. Almost at the absorption
edge, the absorption coefficient can be calculated using the expression14 :
1 1 R2
D ln
:
(1)
d
T
SnO2 is a semiconductor with a large direct band gap; and
the optical gap energy Eg (Table 1) was obtained from the
transmission spectra using the following relations15 :

Doping level at 513 nm (wt%)


0
70
3.99
2.5
79
3.89
5
80
4.05
Film thickness at 2.5 wt% (nm)
30
86
3.47
90
83
3 .68
342
82
3.86
513
79
3.89
a:

403.2
093.6
319.6

3.4
278.9
166.6

1.4751
1.4726
1.4741

119.3
109.1
101.5
093.6

53.9
64.6
281.9
278.9

1.4706
1.4722
1.4733
1.4726

T is the transmission of the films at 800 nm.

the deposited films was measured in the range 3002500 nm


using an ultravioletvisible spectrophotometer (UV, Lambda
35), and the electrical conductivity of the films was measured
in a coplanar structure obtained from the evaporation of four
golden strips on the film surface. All the spectra were measured
at room temperature (RT).

3. Results and discussion


The optical transmission spectra of the SnO2 :F films deposited at different concentrations are shown in Fig. 1. Both
SnO2 :F films exhibit a good transmission (80%) in the visible
range with a sharp absorption edge. The good transmittance of
the SnO2 :F film may be due to the reduction in the intrinsic defects, like oxygen interstitials, caused by the small percentage
of doped F that acts as a surfactant, as observed by Ref. [13].
The absorption edge shifts from the lower wavelength region
to the higher wavelength, changing with the increase in F content to 5 wt%, indicating fundamental transmission that corresponds to electron excitation from the valence and conduction
bands. It is found that the optical band gap changes after doping
(Table 1).
The transmittance spectra are strongly influenced by the
film thickness. Figure 2 shows that the investigated transparent
conducting SnO2 :F thin films have a good transmission (80%
90%) in the VIS and NIR domains (3001000 nm). For the

.h/2 D C.h

Eg /;

(2)

where R is the absorbance, d the film thickness, T the transmittance spectra of the thin films, the absorption coefficient values, C a constant, h the photon energy, and Eg the energy band
gap of the semiconductor, as shown in Table 1. This is determined from the graph of .h/2 as a function of photon energy
(h/ by extrapolation of the linear region to .h/2 D 016 .
Moreover, we used the Urbach energy, which is related to the
disorder in the film network, and expressed as17 :
A D A0 exp

h
;
Eu

(3)

where A0 is a constant and Eu is the Urbach energy, as shown


in Table 1.
Figure 3 shows the typical variation in .h/2 drawn as a
function of the photon energy h of the SnO2 :F thin films as a
function of film thickness. It is used to extrapolate the optical
band gap.
In Fig. 4 we reported on the variation in the optical band
gap energy Eg and the Urbach energy Eu as a function of the
doping level (Fig. 4(a)) and film thickness (Fig. 4(b)) of the

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Fig. 3. The typical variation in .h/2 drawn as a function of the photon energy h of SnO2 :F films with film thickness.

Fig. 5. The variation in the refractive index of SnO2 :F thin films as a


function of band gap energy with doping level and film thickness.

Eg to EF Ev > Eg . As can be seen in Figs. 4(a) and 4(b), the


decrease in the Urbach energy to the minimum value indicates
that the decrease in the defects, which is related to the disorder
in the film network, is expressed as in Refs. [11, 12, 20].
The refractive index (n/ is an important parameter for optical materials and applications. The TM (/ and Tm (/ of the
film in the spectral region of weak and medium absorption can
be calculated by the expression21 :
q
n D N C .N 2 S 2 /1=2 ;
(4)
where N is obtained using the below relation21 from the transmission spectrum of the glass substrate, and S is the refractive
indices of the glass substrate. As a result, S D 1.47 in this study.
N D 2S

Fig. 4. The variation in the band gap energy Eg and Urbach energy
Eu of SnO2 :F thin films as a function of the (a) doping level, and (b)
film thickness.

SnO2 :F thin films. Figure 4(a) shows that the optical band
gap energy increases with increasing film thickness for all the
films. This may be attributed to the similar ionic radius between
F and Sn. The band gap is broadened due to the increases in the
transition tail width and shift effect, as reported in Refs. [11,
1820]. Figure 4(b) shows that the gap energy of the SnO2 :F
thin films decreases with increasing doping level from 0 to 2.5
wt% and then increases with 5 wt%. This effect is known as
the BurnsteinMoss effect. In the BurnsteinMoss effect, the
Fermi-level EF position moves above the conduction band Ec
minimum, and thus the absorption edge shifts from Ec Ev D

TM Tm
S2 C 1
C
:
TM Tm
2

(5)

The calculated refractive indices as a function of the optical band gap energy of the SnO2 :F thin films with the film
thickness and doping level are shown in Fig. 5. It is clear that
the refractive index n is in the range of 1.471.476 in the visible
region, and it increases with the increase in the film thickness
up 342 nm then decreases with 513 nm. This behavior is due to
the increase in the optical band gap energy of SnO2 :F with 2.5
wt%. It is also evident from Fig. 5 that F doping can improve
the refractive index, and with the increase in the F content, the
refractive index n decreases. In addition, the refractive index
of SnO2 /SnO2 :F/glass is according with a bulk SnO2 :F (1.47).
The hot probe method was used to determine the conductivity type. It was seen that all the films exhibited n-type conductivity22 . Figure 6 shows the variation in the electrical conductivity  of SnO2 :F films as a function of the doping level
(Figs. 6(a)) and film thickness (Figs. 6(b)). As can be seen,
with an increase in the film thickness from 30 to 342 nm,
the electrical conductivity of the SnO2 :F thin films increases
from 53.93 to 281.96 (cm) 1 , which means an increase in
the carrier concentration. We also obtained, for the effect of
the doping level, an increase in the electrical conductivity with
2.5 wt%. This corresponds to the high value measured with the
film thickness. The increase in the conductivity of the films has
been explained by the displacement of the electrons, with the
latter coming from the F ion donors in the substitutional sites of

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References

Fig. 6. The variation in the electrical conductivity of SnO2 :F thin films


as a function of the (a) doping level, and (b) film thickness.

Sn. The maximum conductivity value was obtained of the film


thickness of 342 nm and 2.5 wt%, which is 281.96 (cm) 1 ,
due to the minimum disorders retched at this point.

4. Conclusion
In summary, high-quality transparent SnO2 :F film was deposited on a glass substrate at a substrate temperature of 350 C
using the ultrasonic spray technique. The conductivity and optical properties were investigated, and all the films were found
to demonstrate an optical transparency of above 80% in the
visible region. The optical gap energy of the doped film with
2.5 wt% F was found to increase from 3.47 to 3.89 eV with
increasing film thickness. The gap energy of the SnO2 :F thin
films improved after doping at 5 wt%. The decrease in the Urbach energy to the minimum value indicated the decrease in the
defects. The increase in the electrical conductivity of the films
reached maximum values of 278.9 and 281.9 (cm) 1 of the
doped films with 2.5 and 5 wt%, respectively, indicating that
the films exhibit an n-type semiconducting nature. A systematic study of the influence of film thickness and doping content
on the properties of SnO2 :F thin films deposited by ultrasonic
spray was examined.

Acknowledgments
The authors would like to thank Dr. F. Chabane, Prof. M.S.
Aida, Dr. O. Belahssen, Dr. D. Bensahal and Mr. B. Gasmi for
helpful counseling.

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