48 Vol.31 No.1 Velázquez-Nevárez G A et al: Preparation, Characterization and Electronic...

DOI 10.1007/s11595-016-1328-5

Preparation, Characterization and Electronic Properties

of Fluorine-doped Tin Oxide Films

Velázquez-Nevárez G A1, Vargas-García J R1, Lartundo-Rojas L2, CHEN Fei3,

SHEN Qiang3, ZHANG Lianmeng3
(1.Deptartment of Materials and Metallurgical Engineering, National Polytechnic Institute, Mexico 07738 DF Mexico; 2. Nanosciences
and Micro and Nanotechnology Center, National Polytechnic Institute, Mexico 07738 DF Mexico; 3. State Key Laboratory of Advanced
Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China)

Abstract: Tin oxide (SnO2) and fluorine doped tin oxide (FTO) films were prepared on glass substrates
by sol-gel spin-coating using SnCl4 and NH4F precursors. Fluorine doping concentration was fixed at 4 at%
and 20 at% by controlling precursor sol composition. Films exhibited the tetragonal rutile-type crystal structure
regardless of fluorine concentration. Uniform and highly transparent FTO films, with more than 85% of optical
transmittance, were obtained by annealing at 600 ℃. Florine doping of films was verified by analyzing the
valence band region obtained by XPS. It was found that the fluorine doping affects the shape of valence band
of SnO2 films. In addition, it was observed that the band gap of SnO2 is reduced as well as the Fermi level is
upward shifted by the effect of fluorine doping.
Key words: tin oxide films; fluorine doping; energy band diagram

1 Introduction techniques including chemical vapor deposition (CVD)

In search of cost-effective transparent conducting
oxides (TCOs), tin oxide has attracted much attention
as one of the most important substitutes for indium
doped tin oxide (ITO) because of its relatively low
cost and good electrical and optical properties [1-3].
Tin is known to exhibit stable oxidation states of
2 and 4; however oxidation states that lie between
those values have also been identified[4-6]. Such sub-
oxides are of enormous interest due to increased
carrier concentration, as a result of oxygen vacancies,
which dominate their electrical conductivity. One way
to control the concentration of oxygen vacancies in
SnO2 is the addition of controlled amounts of specific
impurity elements from the IIB, IIIB, VB and VIIB
groups. Elements such as Zn, In, Ga, Al, Sb and F
have been employed as dopants in the preparation
of SnO2 films[7,8]. Among them, fluorine doped SnO2
(FTO) films have been reported to show the lowest
resistivity[2]. FTO films have been prepared by several
©Wuhan University of Technology and SpringerVerlag Berlin Heidelberg 2016
(Received: Oct. 20, 2015; Accepted: Nov. 19, 2015)
Velázquez-Nevárez G A: E-mail: gvelazquezn1300@alumno.
ipn.mx
[9]
, sputtering[10], spray pyrolysis[11] and sol-gel spin-
coating[12]. Sol-gel spin-coating, in particular, is one
of the simplest and low-cost techniques to prepare
thin films over large areas with uniform thickness and
control of morphology and stoichiometry[13]. Despite
the promising results in the preparation of FTO films,
the fluorine doping remains a challenge because of
the difficulties of demonstrating the effective doping
of SnO 2. Tunable band structure of semiconductor
heterojunctions and doped conducting oxides have
been confirmed by XPS studies[14]. In this study, we
report the preparation of transparent and uniform FTO
films by sol-gel spin-coating and investigate the effects
of fluorine doping on the valence band of SnO2 films.
2 Experimental
2.1 Sol-gel
Fluorine-doped tin oxide precursor solutions
were prepared from tin chloride penta-hydrate
(SnCl4•5H2O, Sigma-Aldrich, purity 99%) as metal
source, anhydrous ethanol (Merck, purity 99%) as
solvent and acetylacetone (C 5H 8O 2, Sigma-Aldrich,
purity 99%) as a chelating agent. Ammonium
fluorine (NH 4 F, Sigma-Aldrich, purity 98%) was
Journal of Wuhan University of Technology-Mater. Sci. Ed. www.jwutms.net Feb.2016 49

employed as the fluorine source. First, the chelating (101), (200), (211), (220), (310) and (301) planes of the
agent and solvent were mixed by magnetic stirring at tetragonal rutile-type crystal structure of SnO2 (JCPDS:
50 ℃ for 15 min. Then, SnCl 4•5H2O was dissolved 41-1445)[15]. All films are polycrystalline in nature.
in the previous mixture at 50 ℃ for 15 min to obtain No other crystalline phases such as SnF2 are observed
0.2 mol·L-1 SnCl4•5H2O solution. The acetylacetone/ despite the relatively high doping concentration.
tin chloride molar ratio was kept constant at 6 (Racac = Fig.1 (b) shows a slight shift of the (110) reflection
6). Ammonium fluorine was added to the tin chloride position for FTO films with 20 at% F, suggesting the
solution and stirred for 2 h at 65 ℃. The FTO precursor incorporation of fluorine into the crystal structure of
solutions were formulated to obtain 4 and 20 at% F SnO2. The shift of the (110) reflection to a lower angle
doping concentration. The final solutions were aged for is associated with the substitution of O-2 ions by F-
48 h at room temperature, before the film preparation. ions. The ionic radius of F- (1.33 Å) is too close to that
2.2 Film preparation by spin-coating of O-2 (1.32 Å) [16].
Undoped and fluorine-doped SnO2 films were
prepared on amorphous glass (Fluka) substrates 25 mm
× 25 mm × 1 mm in size. Previous to film preparation,
the glass substrates were sequentially cleaned with
acetone, ethanol and deionized water in ultrasonic bath.
Then, the substrates were blown dried using extra dry
air. Spin-coating parameters were as follows: 300 rpm
for 5 s and then 3 000 rpm for 30 s. The wet films thus
prepared were dried at 200 ℃ for 10 min by using a
hot-plate. Multi-layer films were prepared by repeating
the spin-coating and drying sequence for 5 times.
Annealing treatment was applied for densification of
multi-layer films at 600 ℃ for 2 h in air. The heating
rate was 10 ℃/min. Previous to observations, the
films were coated with Au-Pd layer to increase the
conductivity. The crystalline phase of SnO2 and FTO
films was investigated by X-ray diffraction (XRD;
BRUKER D8 Advanced) with grazing geometry using
an incident X-ray beam from 0.5º to 3.0º. The film
surface morphology was examined by using a field
emission scanning electron microscope (FESEM) JEOL
JSM-6071F. The valence band of films was investigated
by X-ray photolectron spectroscopy (XPS) using a
thermo scientific model K-alpha apparatus with an Al
Kα X-ray source (1 487 eV). The optical transmittance
of films was measured by UV-vis spectroscopy (Perkin
Elmer Lambda 35) in the wavelength range of 200
– 700 nm at room temperature. The uncoated glass
substrate was used as a blank reference for base line
determination.

3 Results and discussion

Fig.1 (a) shows the representative XRD patterns
of SnO2 and FTO films prepared with 4 at% and 20 at%
F. Irrespective of doping, films exhibit well-defined
reflections at 2θ = 26.60º, 33.90º, 37.96º, 51.81º,
54.70º, 61.82º and 65.86º corresponding to the (110),
SEM images of the surface morphology for
undoped SnO2 and FTO (20 at% F) films are shown
in Fig.2. SEM images reveal uniform granular
morphology and no significant variation in grain size
50 Vol.31 No.1 Velázquez-Nevárez G A et al: Preparation, Characterization and Electronic...
with the doping of fluorine, indicating that sol-gel spin-
coating preparation conditions are appropriate to obtain
uniform films with smooth surface morphology.
Fig.3 shows the XPS spectrum from Sn3d core
levels of FTO with 20 at% F. The main Sn peaks
from 3d3/2 and 3d5/2 levels were observed at 495 and
486.6 eV, respectively, in good agreement with those
reported in the literature[17]. Deconvoluted spectra for
Sn3d core level suggests the presence of Sn4+, Sn-F
and Sn0. The XPS analysis indicates a comparatively
higher proportion of Sn4+. No F1s core level signal
was observed from FTO films, however, the peaks
at binding energies of 495.6 and 487.2 eV have been
assigned to the bond between fluorine and tin (Sn-F)[18],
which might be indicative of fluorine doping. The small
peaks at 493.3 and 484.8 eV are probably due to the
reduction of Sn4+ to Sn0 during Ar+ sputtering in XPS
measurements[19]. To verify the fluorine doping, XPS
spectra from FTO films were recorded at low energies
(i e, valence band region), which has been suggested
in the literature for heterojunctions and doping [20,21].
Figs.4 (a) and 4 (b) depict the valence band spectra
for SnO2 and FTO films. These spectra clearly reveal
that fluorine doping affects the shape of valence band
(VB). The maximum of the valence band (VBM) from
extrapolation of the leading edges were estimated to be
2.97 eV for SnO2 and 3.24 eV for FTO (4 at% F). Table
1 summarizes the VBM values as a function of fluorine
doping concentration in SnO2 films.
Fig.5 shows the UV-vis transmittance spectra for
SnO2 and FTO films doping with 4 at% and 20 at%
F. FTO films exhibit lower transmittance compared
to SnO2 films. These results suggest that the optical
quality of SnO2 films might decrease because of the
light scattering caused by increased carriers from
doping. In the visible region, the average transmittance
for SnO 2 is 92% and that for FTO films is 87%
and 88% for 4 at% and 20 at% F, respectively. The
optical band gap (Eg) was determined by using Tauc’s
equation [22] based on the relationship between the
 Journal of Wuhan University of Technology-Mater. Sci. Ed. www.jwutms.net Feb.2016
absorption coefficients (α) and the incident photon
energy (hν). Fig.6 displays the relationship between
(αhν)2 and hν for SnO2 and FTO films. The values of Eg
were determined by extrapolating the lineal portion of
the curves. Table 1 indicates the Eg values for SnO2 and
FTO films.
The energy difference between conduction
band and Fermi level, that is, the conduction band
minimum (CBM) was calculated from Eg and VBM
values as it has been suggested for ZnS/Cu (In,Ga)Se2
heterojunction[23]. The CBM values for SnO2 and FTO
films were found to be 0.6, 0.3 (4 at% F) and 0.24 (20
at% F) eV. Based on this analysis, an estimated energy
band diagram for every film is shown in Fig.7. The
band gap of SnO2 is reduced as well as the Fermi level
is upward shifted by the effect of F doping.
4 Conclusions
Highly transparent, uniform and smooth FTO
films have been prepared by sol-gel spin-coating. FTO
films exhibited lower transmittance than SnO2 films.
The average transmittance for SnO2 and FTO films was
found to be 92%, 87% (4 at% F) and 88% (20 at% F).
It was demonstrated that the fluorine doping affects the
shape of valence band of SnO2 films. In addition, it was
observed that the band gap of SnO2 is reduced as well
as the Fermi level is upward shifted by the effect of
fluorine doping.
References
[1] Dolbec R, El Khakani MA, Serventi AM, et al. Microstructure and
Physical Properties of Nanostructured Tin Oxide Thin Films Grown
by Means of Pulsed Laser Deposition[J]. Thin Solid Films, 2002, 419:
230-236
[2] Elangovan E, Ramamurthi K. A Study on Low Cost-high Conducting
Fluorine and Antimony-doped Tin OxideThin Films[J]. Applied
51
Surface Science, 2005, 249: 183-196
[3] Treharne RE, Durose K. Fluorine Doped ZnO Thin Films by RF
Magnetron Sputtering[J]. Thin Solid Films, 2011, 519: 7 579-7 582
[4] Lee SC, Lee JH, Oh TS, et al. Fabrication of Tin Oxide Film by Sol-gel
Method for Photovoltaic Solar Cell System[J]. Solar Energy Materials
& Solar Cells, 2003, 75: 481-487
[5] Ardizzone S, Cappelleti G, Ionita M, et al. Low-temperature Sol-gel
Nanocrystalline Tin Oxide Integrated Characterization of Electrodes
and Particles Obtained by Common Path[J]. Electrochimica Acta,
2005, 50: 4 419- 4 425
[6] Ibrahim NB, Abdi MH, Abdullah MH, et al. Structural and Optical
Characterization of Undoped and Chromium Doped Tin Oxide
Prepared by Sol-gel Method[J]. Applied Surface Science, 2013, 271:
260-264
[7] Kumara GRA, Ranasinghe CSK, Jayaweera EN, et al. Preparation of
Fluoride-doped Tin Oxide Films on Soda-lime Glass Substrates by
Atomized Spray Pyrolysis Technique and their Subsequent Use in Dye-
sensitized Solar Cells[J]. Journal of Physical Chemistry, 2014, C118:
16 479-16 485
[8] Zhang L, Ge S, Zuo Y, et al. Ferromagnetic Properties in Undoped and
Cr-doped SnO2 Nanowires[J]. Scripta Materialia, 2010, 63: 953-956
[9] Brown JR, Haycock PW, Smith LM, et al. Response Behavior on Tin
Oxide Thin Films Gas Sensors Grown by MOCVD[J]. Sensors and
Actuators B: Chemical, 2000, 63: 109-114
[10] Kelly PJ, Bradley JW. Pulsed Magnetron Sputtering-process Overview
and Applications[J]. Journal of Optoelectronics and Advanced
Materials, 2009, 11: 1 101- 1 107
[11] Zhang B, Tian Y, Zhang JX, et al. The Role of Oxygen in Fluorine-
doped SnO2 films[J]. Physica B, 2011, 406: 1 822-1 826
[12] Wu S, Yuan S, Shi L, et al. Preparation, Characterization and Electrical
Properties of Fluorine-doped Tin Dioxide Nanocrystals[J]. Journal of
Colloid and Interface Science, 2010, 346: 12-16
[13] Banerjee A, Kundoo S, Saha P, et al. Synthesis and Characterization
of Nano-Crystalline Fluorine-doped Tin Oxide Thin Films by Sol-gel
Method[J]. Journal of Sol-Gel Science and Technology, 2003, 28 (1):
105-110
[14] Bhardwaj A, Rajput A, Shukla AK, et al. Mg 3 Sb 2 -based Zintl
Compound: a Non-toxic, Inexpensive and Abundant Thermoelectric
Material for Power Generation[J]. RSC Advances, 2013, 3: 8 504-8 516
[15] Tran QP, Fang JS, Chin TS. Properties of Fluorine-doped SnO 2
Thin Films by a Green Sol-gel Method[J]. Materials Science in
Semiconductor Processing, 2015, 40: 664- 669
[16] Kim H, Park HH. A Study on the Electrical Properties of Fluorine
Doped Direct-patternable SnO2 Thin Films[J]. Ceramics International,
2012, 38S: S609-S612
[17] NIST X-Ray Photoelectron Spectroscopy Database[DB]. http://www.
nist.gov/srd/nist20.htm
[18] Park JH, Jang S, Byun D, et al. Fluorine Doped Gallium Tin Oxide
Composite Films as Transparent Conductive Oxides on Polyethylene
Terephthalate Film Prepared by Electron Cyclotron Resonance Metal
Organic Chemical VaporDeposition[J]. Thin Solid Films, 2011, 519:
6 863-6 867
[19] Mirzaee M, Dolati A. Effects of Tin Valence on Microstructure, Optical
and Electrical Properties of ITO Thin films Prepared by Sol-gel
Method[J]. Journal of Sol-Gel Science and Technology, 2015, 75: 582-
592
[20] Martínez AI, Huerta L, O-Rueda de León JM, et al. Physicochemical
Characteristics of Fluorine Doped Tin Oxide Films[J]. Journal of
Physics D: Applied Physics, 2006, 39: 5 091-5 096
[21] Vequizo JJM, Ichimura M. Fabrication of Electrodeposited SnS/SnO2
Heterojunction Solar Cells[J]. Japanese Journal of Applied Physics,
2012, 51: 10NC38-1 – 10NC38- 4
[22] Tauc J, Grigorovici R, Vancu A. Optical Properties and Electronic
Structure of Amorphous Germanium[J]. Physica Status Solidi B, 1966,
15: 627-637
[23] Larina L, Shin D, Kim JH, et al. Alignment of Energy Levels at the
ZnS/Cu(In,Ga) Se2 Interface[J]. Energy & Enviromental Science, 2011,
4: 3 487-3 493