The African Review of Physics (2012) 7:0018 177

Characterization of SnO2:F Films Deposited by Atmospheric Pressure Chemical

Vapour Deposition for Optimum Performance Solar Cells

M. A. Olopade1,*, O. E. Awe2, A. M. Awobode2 and N. Alu3

1
Department of Physics, University of Lagos, Nigeria
2
Department of Physics, University of Ibadan, Nigeria
3
Physics Advance Laboratory, Sheda Science and Technology Complex, Abuja, Nigeria

An atmospheric pressure chemical vapour deposition (APCVD) system was designed and fabricated for the deposition of
F-doped SnO2 (FTO) thin films on soda lime glass (SLG) with the aim of growing FTO thin films for local fabrication of
solar cells. Tin (IV) chloride [SnCl4] and Hydrogen Fluoride (HF) were used as the precursor and dopant, respectively. The
deposition time and the substrate temperature were varied to optimize the growth of the FTO thin films. The prepared films
were characterized by means of UV-visible spectroscopy, Profilometer and Four point probe methods. We observed that the
deposition time and substrate temperatures influenced the optical and electrical properties of the deposited thin films. The
SnO2:F films grown at optimum APCVD conditions have thicknesses of 460nm, average sheet electrical resistance of
15.8/sq and transmittance of 80%. The solar cells grown with these FTO thin films gave efficiencies of 0.13% and 0.28%,
respectively.

1. Introduction Sequel to the irregular supply of electricity in

Nigeria [21], the drive to find alternatives to the
Thin films of transparent conductive oxides (TCO),
present sources of electric power generation has
such as ITO (SnO2:In), FTO (SnO2:F) and ATO
increased. One of these alternatives is the use of
(SnO2:Sb), AZO (ZnO:Al), GZO ( ZnO:Ga) are
renewable energy especially thin film photovoltaic
particularly attractive because of their high optical
[22,23]. One major problem hindering thin film
transparency in the visible region, good electrical
photovoltaic researches in the country is the non-
conductivity and high infrared reflectivity [1].
availability of Transparent Conducting Oxides
These transparent conducting oxides find
(TCOs). Also, they are quite expensive and they
numerous applications, some of which include
are imported for usage. To this end, this research
liquid crystal displays, wave guide electron
work is aimed at the local production of TCOs
devices, light emitting diodes, dye-sensitized solar
especially SnO2:F, which is required as the
cells, thick film sensors, transparent electrodes in
transparent conducting layer of dye sensitized solar
solar cells, flat panel displays, organic light
cells [22] and superstrate structure of solar cells
emitting diodes, and heat mirrors [2-12].
[24].
Dopants such as antimony (Sb), Indium (In),
The properties of deposited SnO2 thin films
and Fluorine (F) are frequently used to dope SnO2
were found to be dependent on the processing
thin films. However, recently Lithium (Li) has been
conditions, solvents and the nature of precursors
used as dopant with SnO2 [13]. Fluorine, due to its
used as stated in [25-29], which made us to
similar ionic radii (1.17 for F- and 1.22 for O2),
consider these parameters in this research. In order
may substitute for the anion (O2-) in SnO2 and as
to locally fabricate FTO thin films of low thickness
donor in SnOx: F [14].
with high transmittance and low resistance, we
In the recent times, various techniques have
designed and constructed an Atmospheric Pressure
been developed for transparent conducting oxides
Chemical Vapour deposition (APCVD) set up for
thin film deposition. The screen printing technique
this purpose. The APCVD method was chosen due
[15], chemical vapour deposition [15], reactive
to its low cost of deposition [30] and the optical
evaporation [16], dc and rf sputtering [17, 18], sol-
and electrical characterizations of the deposited
gel [19], and pulsed laser ablation [20] are some of
film were examined. The experimental details,
the deposition methods being used for the
results obtained and the conclusion of our research
preparation of ITO and FTO thin films.
are highlighted in sections that follow.
______________________
*
molopade@unilag.edu.ng
The African Review of Physics (2012) 7:0018 178

2. Experimental Details
The soda lime glass (SLG) was used as substrate
for the deposition of FTO thin films in this
research. The soda lime glasses were soaked in
aqua regia for 24 hours (mixture of HCl and HNO3
in the ratio 3:1, respectively) to remove the sodium
content of the glass because it increases the
resistance of the FTO thin film when deposited on
it [30]. The SLG were carefully removed from the
aqua regia and cleaned with acetone, then ethanol
and blown dried. A simple pictorial arrangement of
our precursors and deposition set up is as shown in
Figs. (a) and (b), respectively. The FTO thin films
on the SLG were prepared by atmospheric pressure
chemical vapour deposition (APCVD) with Tin
(IV) chloride (SnCl4) and Hydrogen Fluoride (HF)
as the precursor and dopant. High purity N2 was Fig.(a): The precursor section of the APCVD set up at
used as the carrier gas and H2O was used as the the Sheda Science and Technology Complex.
activator.
The experimental conditions were as follows:
SnCl4 (99% pure) and HF (99% pure) were gasified
in volumetric flasks by bubbling with N2. Also, the
HF was heated at 520C. The flow rates were
0.54  0.1L/min for SnCl4 and 0.090 
0.1 L/min for HF. The activator gas (H2O vapour)
was carried with air and gasified at 300C using a
pump, which was regulated by using a regulator. Its
flow rate was 0.767  0.1 L/min. The carrier gas
(N2) flow rate was 0.5  0.1 L/min. The susceptor
of the APCVD machine is movable and thus it
allows for multiple, or graded deposition across the
same substrate. The temperature of the glass
surface (substrate) during deposition was varied
from 320oC-360oC, while the deposition time was
varied from 60s to 140s. Several runs of the
experiment were carried out and the best of the Fig.(b): The entire APCVD set-up showing the
films were characterized for their optical and arrangement of the precursor, dopant and depositing
electrical properties. The optical transmission section.
spectra were obtained using UV-Visible
spectroscopy (AvaSpec-2048 Fiber Optic 3. Results and Discussion
Spectrometer), while the sheet resistances of the
films were obtained using the four point probe 3.1. Effects of time of deposition on the light
system (Jandel universal four point probe) and the transmission and sheet resistance of films
film thickness was measured using a Dektak 3ST The sheet resistances of the films prepared at the
surface profiler on an etched step edge. same substrate temperature (3000C) decreases with
Some of the best characterized films were increase in deposition time as shown in Fig. 1,
selected and used as window layers for the growth whereas the transmittance of the films decreases
of superstrate structure of Cu2ZnSnS4 thin film with increase in deposition time as shown in Fig. 2.
solar cells. The fabricated solar cells were These results obtained are in agreement with [31].
characterized by current-voltage measurement in It shows that there is an optimization of the FTO
the dark and under a calibrated A.M 1.5 light film thickness to achieve the sufficient electrical
source with a solar simulator (New Port). conductivity and at the same time keep the optical
absorption losses low (high transmittance). It was
observed that films with large time of depositions
The African Review of Physics (2012) 7:0018 179

were thicker and had milky appearances when conductivity (low sheet resistance values) but poor
observed in air. These reveal an improved transmittance to light in the UV region.

Sheet resistance(/sq) and 100

80
Transmittance(%)

60

40 sheet resistance
Transmittance
20

0
60 80 100 120 140
Time of deposition(secs)

Fig.1: Dependence of sheet resistance and transmittance of FTO film on deposition time.

100
Transmittance(%)

80
60
sample A(60s)
40 sample B(80s)
sample C(100s)
20 sample D(120s)
sample E(140s)
0
300
340
380
420
460
500
540
580
620
660
700
740
780
820
860
900

Wavelength(nm)

Fig.2: UV-Visible light transmission of FTO films prepared at different deposition time.

3.2. Effects of deposition (substrate) passage of light in the visible region through the
temperature on the light transmission and sheet films. These results are in agreement with those in
resistance of films [31,32]. These observations are due to the efficient
incorporation of donors at higher temperature and
As shown in Fig. 3, both sheet resistance and
defect concentrations as suggested by [32]. Also,
transmittance of the films were increasing as the
these results reveal that both the optical and
substrate deposition temperature was increasing.
electrical properties of SnO2:F thin films are
The increase in both the sheet resistance and the
sensitive to substrate temperature. The
transmittance of the films indicates that the
transmittance of the films in Fig. 4 confirms that
conductivity of the films reduces with an increase
the transmittance trend in Fig. 3 is quite in order.
in substrate temperature while the transmittance
increases, which shows an improvement of the
The African Review of Physics (2012) 7:0018 180

100

Sheet resistance(/sq) and

80

Transmittance(%)
60

40 sheet resistance
Transmittance
20

0
320 330 340 350 360
Deposition temperature(0C)

Fig.3: Dependence of sheet resistance and transmittance of FTO film on deposition temperature.

100

80
Transmittance(%)

sample F(320)
60
sample G(330)
40
sample H(340)
20 sample I(350)
sample J(360)
0
300
350
400
450
500
550
600
650
700
750
800
850
900

Wavelength (nm)

Fig.4: UV-Visible light transmission of FTO films prepared at different substrate temperature.

3.3. Solar Cells temperature were studied viz-a-viz the optical and
electrical properties of these films. As expected, the
The SnO2:F thin films used in the fabrication of
transmittance and sheet resistances of the films
solar cells were deposited at optimum conditions of
decrease with an increase in time of deposition, but
substrate temperature (3400C) and time of
increase with an increase in substrate temperature.
deposition (100 secs). These films had sheet
The substrate temperature influences both the
resistances of 15.8 /sq, transmittance of 80% and
incorporation of ratio of dopant into the SnO2 film
thickness of 460nm. Cu2ZnSnS4 thin film solar
during the growth as well as the defect
cells in the superstrate structure were fabricated
concentration. The optimized SnO2 films have
with these FTO films. These solar cells had a
sheet resistance of 15.8 /sq and transmittance of
structure of (SLG)/FTO/Ag/CdS/CZTS/Al with
80%. It is hoped that this research will assist the
buffer layer thicknesses of 40nm and 60nm,
local fabrication of SnO2: F thin films that will
respectively. The efficiencies of these solar cells
enhance the fabrication of solar cells in the country
are 0.28 % (40nm) and 0.13 % (60nm),
at reduced cost. A key aspect of this work is that
respectively [33].
the process technology used in this research can be
4. Conclusion scaled up to high volume production of FTO thin
films wherein other deposition parameters
In this research work, we have employed a simple
necessary for good FTO thin films can be
technique (APCVD method) to grow SnO2: F thin
considered.
films. The effect of deposition time and substrate
The African Review of Physics (2012) 7:0018
Acknowledgments
This research was supported by the Physics
Advance Laboratory of the Sheda Science and
Technology Complex, Abuja under the STEP-B
Programme. M. A. Olopade thanks the Agency for
hosting him during his Research Leave to the
Centre.
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Received: 26 July,2011
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